JP4888105B2 - Curable composition, cured film and laminate - Google Patents

Description

  The present invention relates to a curable composition having hard coat properties, a cured film using the same, and a laminate thereof.

  Conventionally, from the aspect of ensuring the performance of information communication equipment and safety measures, using a photocurable composition on the surface of the equipment, a hard coat film having scratch resistance, adhesion, high refractive index, etc. An antistatic coating film is formed.

  In recent years, there has been remarkable progress in the development and generalization of information and communication equipment, and there has been a demand for further improvements in performance and productivity such as hard coat coatings and antistatic coatings. Various proposals used have been made.

  For example, the following technical proposals can be cited (see Patent Documents 1 to 3). Patent Document 1 discloses a method of preparing a conductive paint by mixing conductive powder such as tin oxide and a plurality of monomer components in an organic solvent using a ball mill or the like. Patent Document 2 discloses a method of preparing a dispersion for conductive paint by mixing antimony-doped tin oxide and an ultraviolet curable silane coupling agent in an organic solvent using a ball mill. Further, Patent Document 3 discloses a method of preparing a conductive coating material by dispersing conductive oxide fine powder in a mixed solvent of an easily dispersible low boiling point solvent and a hardly dispersible high boiling point solvent.

However, even if it becomes possible to create a curable composition having good physical properties such as high refractive index, hard coat properties, antistatic properties, and light resistance by the above method, it is highly hydrophobic such as an organic solvent. Since the metal oxide having an average primary particle size of 100 nm or less cannot be stably dispersed and stabilized at the primary particle level with respect to the medium, the transparency of the coating film, the temporal stability of the photocurable coating, etc. Prone to problems from a viewpoint.
Japanese Patent Laid-Open No. 04-172634 Japanese Patent Laid-Open No. 06-264209 JP 2001-131485 A

  Accordingly, the present invention provides a coating film having excellent physical properties in all of high refractive index properties, antistatic properties, hard coat properties, transparency and light resistance while containing a metal oxide having an average primary particle size of 100 nm or less. It is an object of the present invention to provide a curable composition that is stable over time, a cured film using the same, and a laminate thereof.

A metal oxide having an average primary particle size of 5 to 100 nm,
An acid anhydride group in the compound (A) having an acid anhydride group represented by the following general formula (1);
In the compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond, and in the compound (C) having two or more functional groups capable of reacting with an acid anhydride group A carboxyl group in the compound (D) having a carboxyl group obtained by reacting a functional group capable of reacting with the acid anhydride group of
The weight average molecular weight obtained by reacting a functional group capable of reacting with a carboxyl group and a functional group capable of reacting with a carboxyl group in the compound (E) having an unsaturated double bond is 3,000 to 20,000. A certain acrylate compound or methacrylate compound (X)
A curable composition comprising an amino group-containing photocurable compound obtained by reacting a primary amine or a secondary amine ,
Metal oxides
Titanium, zinc, zirconium, antimony, indium, tin,及 Beauty, contains at least one element selected from the group consisting of aluminum, furthermore,
And the solid content 100 parts by weight of the total amount of the metal oxide and the amino group-containing photocurable compound, 1 to 80 parts by weight
Contained, and
The amino group-containing photocurable compound is
Against ethylenically unsaturated double bonds 100 moles in the acrylate compound or methacrylate compound (X), primary amine or secondary amine is 0.5 to 50 mol
It is related with the curable composition made to react by the ratio which becomes .

  General formula (1)

(Here, R1 represents a tetravalent aliphatic group or an aromatic group.)

  Further, the compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond has one functional group capable of reacting with an acid anhydride group and three or more unsaturated groups. The curable composition is a compound (B1) having a double bond.

  In addition, the compound (C) having two or more functional groups capable of reacting with an acid anhydride group has a compound (C1) having two or more functional groups capable of reacting with an acid anhydride group and an unsaturated double bond. It is related with the said curable composition characterized by these.

  The present invention also relates to the above curable composition, wherein the primary amine or secondary amine is an aliphatic monoamine.

  Moreover, this invention relates to the said curable composition characterized by further including a solvent and a solvent contains 10 to 100 weight% of hydroxyl-containing solvents with respect to all the solvents.

  Moreover, this invention relates to the cured film characterized by hardening the said curable composition.

  Moreover, this invention relates to the manufacturing method of the cured film formed by apply | coating the said curable composition to a base material, irradiating an active energy ray, and making it harden | cure.

  Moreover, this invention relates to the laminated body manufactured by the said manufacturing method.

  Moreover, the present invention relates to the antireflection film wherein the laminate is.

  The curable composition of the present invention contains a metal oxide having an average primary particle size of 100 nm or less, and has excellent physical properties in all of high refractive index properties, antistatic properties, hard coat properties, transparency and coating properties. It is particularly suitable for hard coating agents such as plastic optical parts, optical disks, antireflection films, touch panels, film-type liquid crystal elements, and plastic laminates. Furthermore, when it is applied to a substrate having a high refractive index and a similar refractive index, no reflection interference fringes are generated, and it is suitably used for optical applications. Moreover, since the refractive index of the hardened | cured material containing a metal oxide composition is controllable highly, it is suitable also as an optical semiconductor element sealing material.

  First, the curable composition of this invention is demonstrated.

This curable composition comprises at least a metal oxide having an average primary particle size of 5 to 100 nm,
An acid anhydride group in the compound (A) having an acid anhydride group represented by the following general formula (1);
In the compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond, and in the compound (C) having two or more functional groups capable of reacting with an acid anhydride group A carboxyl group in the compound (D) having a carboxyl group obtained by reacting a functional group capable of reacting with the acid anhydride group of
The weight average molecular weight obtained by reacting a functional group capable of reacting with a carboxyl group and a functional group capable of reacting with a carboxyl group in the compound (E) having an unsaturated double bond is 3,000 to 20,000. It contains an amino group-containing photocurable compound obtained by reacting a certain acrylate compound or methacrylate compound (X) with a primary amine or a secondary amine, and includes two or more kinds of metal oxides and two kinds Each of the above amino group-containing photocurable compounds may be included.

  General formula (1)

(Here, R ¹ represents a tetravalent aliphatic group or an aromatic group.)
The metal oxide is a metal oxide having an average primary particle size of 5 to 100 nm. The average primary particle diameter of the metal oxide can be measured by directly observing the particles themselves using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

  In the case of a metal oxide having an average primary particle diameter of less than 5 nm, the cohesive force between the fine particles is very large, so that it is very difficult to disperse at a primary particle level with high transparency. On the other hand, in the case of a metal oxide having an average primary particle size of more than 100 nm, it is easy to disperse at the primary particle level, but since the particle size is large, scattering is likely to occur with respect to light such as visible light. There arises a problem that deteriorates the transparency.

As the metal oxide, titanium, zinc, zirconium, antimony, indium, tin,及 beauty, those containing at least one element selected from the group consisting of aluminum preferred. In particular, those containing any one element of antimony, indium, tin and zinc are more preferable because of their good conductivity.

  Specifically, antimony pentoxide, titanium oxide, zinc oxide, zirconium oxide, silicon oxide, antimony-doped tin oxide (ATO), tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO) Zinc antimonate (AZO), indium-doped zinc oxide (IZO), tin oxide, ATO-coated titanium oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, and the like. These metal oxides may be used in combination of two or more.

Commercially available products of metal oxides include: Nissan Chemical Industries, Ltd .: San Epoch EFR-6N, Sun Epoch EFR-6NP (antimony pentoxide), Ishihara Sangyo Co., Ltd .: SN-100P (ATO), FS- 10P (ATO), SN-102P (ATO), FS-12P (ATO), ET-300W (ATO-coated titanium oxide), TTO-55 (A) (titanium oxide), TTO-55 (B) (titanium oxide) , TTO-55 (C) (titanium oxide), TTO-55 (D) (titanium oxide), TTO-55 (S) (titanium oxide), TTO-55 (N) (titanium oxide), TTO-51 (A ) (Titanium oxide), TTO-51 (C) (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (titanium oxide), TTO-S-3 (titanium oxide), TTO-S -4 (Oxidized oxide Tan), TTO-F-1 (iron-containing titanium oxide), TTO-F-2 (iron-containing titanium oxide), TTO-F-3 (iron-containing titanium oxide), TTO-F-11 (iron-containing titanium oxide) , ST-01 (titanium oxide), ST-21 (titanium oxide), ST-30L (titanium oxide), ST-31 (titanium oxide), manufactured by Mitsubishi Materials Corporation: T-1 (ITO), S-1200 (Tin oxide), T-1 (ATO), EP SP-2 (PTO), manufactured by Mitsui Kinzoku Kogyo Co., Ltd .: Pastoran (ITO, ATO), manufactured by CI Kasei Co., Ltd .: Nanotech ITO, Nanotech SnO2, Nanotech TiO2 , Na Notekku Al2O3, NANOTEC ZnO, Shokubai Kasei Kogyo KK: TL-20 (ATO), TL-30 (ATO), TL-30S (PTO), TL-120 (ITO), TL-13 (ITO), Hakusuitec Co., Ltd .: PazetCK (aluminum-doped zinc oxide), PazetGK (gallium-doped zinc oxide), Sakai Chemical Industry Co., Ltd .: SC-18 (aluminum-doped zinc oxide), FINEX-25 (zinc oxide) ), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP (zinc oxide), FINEX-75 (zinc oxide), STR-60C (titanium oxide), STR-60C-LP (titanium oxide) ), STR-100C (titanium oxide), manufactured by Sumitomo Osaka Cement Co., Ltd .: OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide), Nippon Electric Works Co., Ltd. Ltd.: PCS (zirconium oxide), T-01 (zirconium oxide), PCS-60 (zirconium oxide), manufactured by Nippon Aerosil Co., Ltd.: Aluminum Oxide C (aluminum oxide), A EROSILMOX80 (silicon oxide / aluminum oxide), AEROSILMOX170 (Silicon oxide / aluminum oxide), AEROSILCOX84 (silicon oxide / aluminum oxide), and the like.

  The amino group-containing photocurable compound used in the present invention is obtained by reacting an acrylate compound or a methacrylate compound (X) with a primary amine or a secondary amine. It is used for imparting dispersion stability, improving compatibility with an organic component such as an acrylate compound or a methacrylate compound (X), which is a photocurable compound in the cured film, and improving the hard coat property of the cured film.

<< Acrylate compound or methacrylate compound (X) >>
The acrylate compound or methacrylate compound (X) as a raw material for the amino group-containing photocurable compound will be described below.

The acrylate compound or the methacrylate compound (X) is an acid anhydride group in the compound (A) having an acid anhydride group represented by the general formula (1);
In the compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond, and in the compound (C) having two or more functional groups capable of reacting with an acid anhydride group A carboxyl group in the compound (D) having a carboxyl group obtained by reacting a functional group capable of reacting with the acid anhydride group of
The weight average molecular weight formed by reacting a functional group capable of reacting with a carboxyl group in the compound (E) having a functional group capable of reacting with a carboxyl group and an unsaturated double bond is 3,000 to 20,000. A compound.
<Compound (A) having acid anhydride group represented by formula (1)>
General formula (1)

(Here, R ¹ represents a tetravalent aliphatic group or an aromatic group.)

The compound (A) is an aliphatic tetracarboxylic dianhydride or an aromatic tetracarboxylic dianhydride.

Examples of the aliphatic tetracarboxylic dianhydride in which R ¹ is a tetravalent aliphatic group include acid dianhydrides having a tetravalent aliphatic group skeleton that is an alkyl skeleton having 4 to 10 carbon chains, Specific examples include aliphatic tetracarboxylic dianhydrides such as a butane skeleton, a cyclobutane skeleton, a hexane skeleton, a cyclohexane skeleton, and a decalin skeleton.

  Examples of the aliphatic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride.

Furthermore, the aromatic tetracarboxylic dianhydride which is a tetravalent aromatic group of R ¹ specifically includes a phenyl skeleton, a benzophenone skeleton, a biphenyl skeleton, a phenyl ether skeleton, a diphenyl sulfone skeleton, a diphenyl sulfide skeleton, a perylene. Examples thereof include aromatic tetracarboxylic dianhydrides, which are acid dianhydrides of skeletons such as a skeleton, a fluorene skeleton, a tetrahydronaphthalene skeleton, and a naphthalene skeleton.

  Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride having a biphenyl skeleton, oxydiphthalic dianhydride, and diphenyl sulfone tetracarboxylic dianhydride. 9,9-bis (3,4-dicarboxyphenyl) having a fluorene skeleton, such as an anhydride, diphenyl sulfide tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride having a naphthalene skeleton ) Fluorene dianhydride, or 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, tetrahydronaphthalene carboxylic dianhydride having a tetrohydronaphthalene skeleton, ethylene glycol bis ( Anhydrotrime Tate), glycerin bis (anhydrotrimellitate) monoacetate, and the like. Commercially available products include “Ricacid TMTA-C”, “Ricacid MTA-10”, “Ricacid MTA-15”, “Ricacid TMEG Series”, “Ricacid TDA”, “Ricacid DSDA”, etc. It is done.

Among these aromatic tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride has a biphenyl skeleton, and can efficiently introduce the biphenyl skeleton into the amino group-containing photocurable compound of the present invention. This is particularly preferable because it can have both hard coat properties of the cured film and good dispersibility of the metal oxide.
<Compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond>
The functional group capable of reacting an acid anhydride group, a hydroxyl group, although such amino group, the easy control of the reaction, the hydroxyl group is particularly preferred.

  Examples of the compound having an unsaturated double bond include acrylate and methacrylate.

  Examples of such hydroxyl group-containing acrylate compounds or methacrylate compounds include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate. 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-hydroxy-3-phenoxypropyl methacrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, glycerol Mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dihydroxy acrylate, glycero (Meth) acrylate, isocyanuric acid EO-modified diacrylate, pentaerythritol mono (meth) acrylate, dipentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, pentaerythritol tri ( Examples thereof include (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

  For the purpose of increasing the hardness, pentaerythritol tri (meth) acrylate and dipentaerythritol are used as the compound (B1) having one functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds. Tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

Specific commercial products include Biscoat # 300 (manufactured by Osaka Organic Chemical Co., Ltd.), KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.), PETIA (manufactured by Daicel UCB), Aronix M305 (manufactured by Toagosei Co., Ltd.), NK Ester A-TMM-3LMN (manufactured by Shin-Nakamura Chemical Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-444 (manufactured by Sartomer Co., Ltd.), light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) , KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), Aronix M402 (manufactured by Toagosei Co., Ltd.) and the like. In particular, KAYARAD PET30 (manufactured by Nippon Kayaku Co., Ltd.) containing pentaerythritol tri (meth) acrylate as a main component is more preferable because the dispersibility of the metal oxide is good.
<Compound (C) having two or more functional groups capable of reacting with an acid anhydride group>
The functional group capable of reacting an acid anhydride group, a hydroxyl group, although such amino group, the easy control of the reaction, the hydroxyl group is particularly preferred.

Examples of the compound (C) having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butane. Aliphatic acids such as diol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, spiroglycol Diols;
Aromatic diols such as hydroquinone, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, bisphenol, bisphenoxyethanol fluorene, bisphenol fluorene, biscresol fluorene;
N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2-hydroxyethyl) aniline, N, N-bis (2-hydroxyethyl) methylamine, N, N-bis (2-hydroxyethyl) ) Propylamine, N, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N, N-bis (2-hydroxyethyl) octylamine, N, N-bis Tertiary amino group-containing diol compounds such as (2-hydroxyethyl) benzylamine and N, N-bis (2-hydroxyethyl) cyclohexylamine;
Other examples include sulfur atom-containing diols and bromine atom-containing diols.

Furthermore, polymer-type polymer polyols can also be used as the compound (C) of the present invention. For example, polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer or random copolymer of tetramethylene glycol and neopentyl glycol, etc. Ether polyols;
Polyester polyols which are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Polycarbonate polyols obtained by reaction of glycol or bisphenol with a carbonic acid ester or reaction of phosgene with glycol or bisphenol in the presence of alkali;
Examples thereof include caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin polyol, polybutadiene polyol such as hydrogenated polybutadiene polyol, and polyol such as silicone polyol.

  Moreover, the compound which has two hydroxyl groups and one or more carboxyl groups in a molecule | numerator can be used as a compound (C). For example, dimethylolbutanoic acid, dimethylolpropionic acid, and derivatives thereof (caprolactone adduct, ethylene oxide adduct, propylene oxide adduct, etc.), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2- Examples include carboxy-1,4-cyclohexanedimethanol.

  Examples of the compound (C) having 3 or more hydroxyl groups in the molecule include polyhydric alcohols such as trimethylol ethane, polytrimethylol ethane, trimethylol propane, polytrimethylol propane, pentaerythritol, polypenta. Examples include erythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin and the like.

  In order to improve the photocurability of the curable composition and the hard coat property of the cured film in the present invention, the compound (C) has two or more functional groups capable of reacting with an acid anhydride group and an unsaturated double bond. Particularly preferred is a compound (C1) having Examples of the compound (C1) include EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL, ECH-modified propylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, EO-modified 1,6-hexanediol diacrylate, ECH-modified hexahydrophthal Acid diacrylate, ECH modified phthalic acid diacrylate, bisphenol A diglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, bisphenol A diepoxy acrylic acid adduct, PO modified bisphenol A diglycidyl ether diacrylate, etc. Is mentioned.

  Specific commercial products include: Nagase ChemteX Corporation: Denacol Acrylate DA-212, Denacol Acrylate DA-250, Denacol Acrylate DA-722, Denacol Acrylate DA-721, Denacol Acrylate DA-911 , Denacol acrylate DA-920, Denacol acrylate DA-931, Denacol acrylate DA-911M, manufactured by Nippon Kayaku Co., Ltd .: KAYARAD R-167, MAX-2104, manufactured by San Nopco Co., Ltd .: RCC13-361, Osaka Organic Co., Ltd .: V # 540, Kyoeisha Chemical Co., Ltd .: Epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 3000A, Epoxy ester 3002A, Epoxy ester 3000M, and the like. In particular, Denacol Acrylate DA-911M (manufactured by Nagase ChemteX Corp.), whose main component is EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL, has good dispersibility of metal oxides and at the same time has a hard coat property of the cured film It is more preferable because it is high.

In addition, a polyfunctional amine compound etc. can be used as a compound (C). The polyfunctional amine compound is not particularly limited as long as it is a compound having two or more primary or secondary amino groups in one molecule. For example, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, Aliphatic polyamines such as pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, isophoronediamine, dicyclohexylmethane-4, Examples include alicyclic polyamines such as 4′-diamine, and aromatic polyamines such as phenylenediamine and xylylenediamine.

In the present invention, these compounds (C) may be used alone or in combination.
<Compound having carboxyl group (D)>
The compound (D) having a carboxyl group includes a compound (A) having an acid anhydride group represented by the general formula (1), one functional group capable of reacting with the acid anhydride group, an unsaturated double bond, And a compound (C) having two or more functional groups capable of reacting with an acid anhydride group.

  The molar ratio of the three components is not particularly limited but is preferably compound (A) / compound (B) / compound (C) = 1 / 0.01 to 1.99 / 0.01 to 1.99, more preferably Is 1 / 0.1 to 1.5 / 0.1 to 1.5. When the ratio of the compound (B) and / or the compound (C) exceeds 1.99, a large excess of the compound (A) occurs, so that a large amount of the unreacted compound (B) and / or compound (C) is large. In other words, the dispersibility of the metal oxide and the hard coat property of the coating film may be deteriorated.

  The molar ratio is greatly related to the molecular weight of the amino group-containing photocurable compound, which is one of the factors affecting the dispersibility of the metal oxide, and the ratio of the compound (B) in the molar ratio. The molecular weight tends to increase as the ratio of the compound (C) increases. As a weight average molecular weight of an amino group containing photocurable compound, 3000-20,000 are preferable, More preferably, it is 4000-10,000. If the molecular weight is less than 3000, the dispersibility of the metal oxide and / or the stability over time of the coating agent may be lowered. If the molecular weight exceeds 20,000, the viscosity of the system becomes very high and the metal oxide Dispersibility may be reduced.

The reaction between the compound (A) having an acid anhydride group represented by the general formula (1) and the hydroxyl group-containing acrylate compound or methacrylate compound which is the compound (B) and / or the compound (C) is represented by the general formula (1). ) Is a reaction of two carboxylic acid anhydride groups possessed by the compound (A) having an acid anhydride group represented by formula (A)) with a hydroxyl group each possessed by a hydroxyl group-containing acrylate compound or methacrylate compound, and as such is well known in the art. It has been. For example, an aromatic tetracarboxylic dianhydride and a hydroxyl group-containing acrylate compound or methacrylate compound may be combined with a catalyst such as 1,8-diazabicyclo [5.4.0] -7-undecene in an organic solvent such as cyclohexanone. In the presence, the reaction can be carried out at a temperature of 50 to 120 ° C. In this case, a polymerization inhibitor such as methoquinone can be added to the reaction system.
<Compound (E) having a functional group capable of reacting with a carboxyl group and an unsaturated double bond>
Examples of the functional group capable of reacting with a carboxyl group include an epoxy group, an oxazoline group, an amino group, a carbodiimide group, an isocyanate group, or an isothiocyanate group .

  Examples of the compound having an unsaturated double bond include acrylate and methacrylate.

  Examples of the epoxy group-containing (meth) acrylate compound (E) include epoxy group-containing (meth) acrylates such as glycidyl methacrylate and glycidyl acrylate.

  The reaction between the compound (D) having a carboxyl group and the epoxy group-containing (meth) acrylate compound (E) is carried out by reacting the carboxyl group that the compound (D) has and the epoxy group that the epoxy group-containing (meth) acrylate compound (E) has This reaction is well known per se in the art. For example, this reaction can be performed at a temperature of 50 to 120 ° C. in the presence of an amine catalyst such as dimethylbenzylamine.

  These reactions may be performed without a solvent or may be performed in a solvent inert to the reaction. Examples of such solvents include hydrocarbon solvents such as n-hexane, benzene and toluene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, diethyl ether, Ether solvents such as tetrahydrofuran or dioxane, halogen solvents such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, or parkrene, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N- Examples include polar solvents such as dimethylimidazolidinone. Two or more of these solvents may be used in combination.

  The amino group-containing photocurable compound can be obtained by reacting the acrylate compound or methacrylate compound (X) with a primary amine or a secondary amine. At this time, a known acrylate compound or methacrylate compound other than the acrylate compound or methacrylate compound (X) may be included as necessary.

  Further, the primary amine or secondary amine is 0.5 to 50 mol, preferably 1.0 to 30 with respect to 100 mol of the ethylenically unsaturated double bond of the entire acrylate compound or methacrylate compound (X). The reaction at a molar ratio is preferable in terms of achieving both the dispersibility of the metal oxide and the photocurability.

  When the reaction ratio of primary amine or secondary amine is less than 0.5 mol, it is difficult to obtain good pigment dispersibility because the ratio of amino groups in the resulting amino group-containing photocurable compound is small, The transparency of the cured film tends to deteriorate. In addition, when it exceeds 50 mol, the ratio of the amino group in the resulting amino group-containing photocurable compound becomes very large, so that good pigment dispersibility is obtained, but on the other hand, the ratio of ethylenically unsaturated double bonds Therefore, the photocurability at the time of preparing the coating film becomes poor, and the hard coat property of the cured film tends to be lowered.

  The primary amine or secondary amine constituting the amino group-containing photocurable compound is an amine compound having at least one primary amino group or secondary amino group in one molecule, and has low rigidity. Aliphatic amines are more preferred. Furthermore, when an amine compound having two or more primary amino groups or secondary amino groups in the molecule is used, a plurality of acrylate compounds or methacrylate compounds react in a complex manner with respect to one amine compound molecule. The product has a problem of high molecular weight and easy gelation. Therefore, it is possible to obtain a versatile amino group-containing photocurable compound by reducing the amount of amine compound added to the acrylate compound or methacrylate compound, or by controlling the reaction conditions.

  Moreover, the amine compound may have other polar functional groups other than the amino group that does not react with the acrylate compound or the methacrylate compound. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

  Among the primary amines constituting the amino group-containing photocurable compound, monoamines include aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2 -Aminopentane, 3-aminopentane, isoamylamine, 1-aminohexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane, aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2 -Methylpropane, 3- Mino-1-propene, 3-aminomethylheptane, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauri Loxypropylamine, 3-myristoxypropylamine, 2-aminomethyltetrahydrofuran, aniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene 1-aminoanthraquinone, 2-aminoanthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, 2-aminobenzophenone, 4-aminoben Phenone, o-aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, α-phenylethylamine, phenesylamine, p-methoxyphenesylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol And allylamine.

  Among the secondary amines constituting the amino group-containing photocurable compound, monoamines include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, din -Propylamine, di-n-butylamine, disec-butylamine, N-ethylisoamylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecholine, 3-pipecholine, 4-pipecoline, 2,4- Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-methylaminoethanol, 3- Methylamino-1,2-propanediol, 1-pi Razine ethanol, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-pyrrolidinol, indoline, N-butylaniline, N-methylbenzylamine, 3-benzylaminopro Examples include pionic acid ethyl ether, 4-benzylpiperidine, and diphenylamine.

  Further, among the primary amine and secondary amine constituting the amino group-containing photocurable compound, examples of the amine compound having a plurality of amino groups in the molecule include 3-aminopyrrolidine, dimethylaminoethylamine, ethylamino Ethylamine, diethylaminoethylamine, N, N-diisopropylaminoethylamine, 1,2-diaminopropane, 1,3-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 2-hydroxyethyl Aminopropylamine, bis- (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis- (3-aminopropoxy) ethane, 1,3-bis- (3-aminopropoxy) -2,2 -Jimee Rupropane, 1,2-diaminobutane, 1,4-diaminobutane, laurylaminopropylamine, diethanolaminopropylamine, N-aminoethylpiperidine, N-aminoethyl4-pipecoline, N-aminopropylpiperidine, N-aminopropyl 2-Pipecoline, N-aminopropyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylmorpholine, iminobispropylamine, methyliminobispropylamine, 4-piperidinecarboxamide, 4-aminomethyl- 1-butylpiperidine, 4-aminomethylpiperidine, 1,3-di- (4-piperidyl) -propane, 4-piperidinopiperidine, N-aminopropylaniline, 3-aminopyrrolidine, N-methylpiperazine, N- Ethyl piperazine N-allylpiperazine, N-isobutylpiperazine, N-aminopropylpiperazine, 1-cyclopentylpiperazine, N-phenylpiperazine, 1- (2-pyridyl) piperazine, 1- (4-pyridyl) piperazine, homopiperazine, N-methyl Examples include homopiperazine.

  The amine compounds shown above may be used alone or in combination of two or more.

  Among these, an aliphatic monoamine having only a secondary amino group is preferable because it has good dispersibility, and the Michael addition reaction is completed in one stage and coloring due to the reaction is small. Aliphatic monoamines having only secondary amino groups include dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, Disec-butylamine, N-ethyl-1,2-dimethylpropylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 2 -Methylaminoethanol, 3-methylamino-1,2-propanediol, 1-piperazineethanol, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3- Pyrrolidinol, etc. . In particular, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, and di-n-butylamine have better dispersibility and dispersion stability. Therefore, it is preferable.

  The amino group-containing photocurable compound is obtained by reacting the acrylate compound or methacrylate compound (X) with the primary amine or secondary amine in a solvent in which two components can be dissolved. An amino group-containing photocurable compound in which an amino group is introduced at the end of the molecule by Michael addition of an amino group in a primary amine or a secondary amine to an ethylenically unsaturated double bond in an acrylate compound or a methacrylate compound It is. Regarding the reaction temperature, the reaction proceeds rapidly even at room temperature, preferably 10 to 110 ° C, more preferably 20 to 80 ° C. When the reaction temperature is less than 10 ° C., the solubility of the acrylate compound or methacrylate compound as a raw material or the amino group-containing photocurable compound as a reaction product is likely to precipitate, the reaction rate decreases, and the reaction time decreases. Prolonged time tends to cause problems such as decreased productivity. In addition, when the reaction temperature exceeds 110 ° C., the reaction product is colored, which affects the color of the curable composition using the colored amino group-containing photocurable compound and the cured film. .

  Regarding the solvent used when the acrylate compound or methacrylate compound (X) is reacted with the primary amine or secondary amine, the raw material acrylate compound or methacrylate compound, and primary amine or secondary amine There is no particular limitation as long as it does not react with the solvent. Examples of the solvent include cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, toluene, xylene, butanol, isopropanol, propylene glycol monomethyl ether, dimethyl adipate, dimethyl succinate, and dimethyl glutarate.

The addition amount of the metal oxide in the curable composition, the solid content total amount of 100 parts by weight of the metallic oxide and the amino group-containing photocurable compound, preferably 1 to 80 parts by weight, more preferably 10 to 70 weight Part. When the addition amount of the metal oxide is less than 1 part by weight, the antistatic property derived from the metal oxide may be inferior, and when it exceeds 80 parts by weight, the film forming property may be inferior due to the small amount of the organic component.

  For example, as described above, the curable composition comprises a (meth) acrylate compound (X) and a primary or secondary amine as an ethylenically unsaturated double in the (meth) acrylate compound (X). Reacting at a ratio of 0.5 to 50 moles of primary or secondary amine with respect to 100 moles of bond to produce an amino group-containing photocurable compound; and said amino group-containing photocuring The active compound and a metal oxide having an average primary particle size of 5 to 100 nm can be mixed.

  Even if the curable composition of the present invention is prepared by simply mixing a metal oxide powder and an amino group-containing photocurable compound, the intended effect can be obtained sufficiently. However, mechanically mixed with a kneader, roll, attritor, super mill, dry pulverizer, etc., or a solution containing an amino group-containing photocurable compound is added to a suspension system using a metal oxide powder and an organic solvent. If a close mixing system such as deposition of an amino group-containing photocurable compound on the surface of the metal oxide is performed, even better results can be obtained.

  For dispersion or dissolution of a metal oxide, amino group-containing photocurable compound or curable composition in a non-aqueous vehicle such as an organic solvent, and mixing thereof, a paint conditioner (manufactured by Red Devil), a ball mill, Sand mill (Shinmaru Enterprises "Dynomill", etc.), Attritor, Pearl Mill (Eirich "DCP Mill", etc.), Coball Mill, Homomixer, Homogenizer (M Technique Co., Ltd. "Clearmix", etc.), wet jet A disperser such as a mill (“Genus PY” manufactured by Genus Co., Ltd., “Nanomizer” manufactured by Nanomizer Co., Ltd.), a micro bead mill (“Super Apec Mill”, “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.), or the like can be used. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and used in stages.

  The curable composition of the present invention contains at least a metal oxide and an amino group-containing photocurable compound, and further contains a solvent and various additives as long as the objects and effects of the present invention are not impaired. Can do. Specifically, solvents, photopolymerization initiators, photocurable compounds, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared rays Examples include absorbents, antioxidants, silane coupling agents, conductive polymers, conductive surfactants, inorganic fillers, pigments, and dyes.

  Although it does not restrict | limit especially as a manufacturing method of the curable composition containing components other than a metal oxide and an amino group containing photocurable compound, Several methods are mentioned. Specifically, first, a metal oxide and an amino group-containing photocurable compound are mixed and dispersed in an organic solvent to obtain a stable metal oxide dispersion, and then various other additives are added and adjusted. From the beginning, a method of dispersing and manufacturing a metal oxide, an amino group-containing photocurable compound, an organic solvent and other additives are mixed.

  When adding a solvent, it is preferable to perform a curing treatment after volatilizing the solvent. The amount of the solvent added is not particularly limited, but is preferably 1 to 95 parts by weight, more preferably 60 to 80 parts by weight in 100 parts by weight of the total composition. If the amount of the solvent added is less than 1 part by weight, the viscosity of the curable composition may be increased, which may cause a problem in coating properties. If the amount exceeds 95 parts by weight, the amount of solvent to be volatilized becomes very large, which is a work environment. Problems may arise.

  The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol , 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene Glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate , Isoamyl acetate, dimethyl adipate, dimethyl succinate, dimethyl glutarate, tetrahydrofuran, and methyl pyrrolidone. These organic solvents may be used in combination of two or more.

  Among them, the hydroxyl group-containing solvent has good wettability with respect to a metal oxide having a highly hydrophilic particle surface property. Therefore, when it is contained in the solvent composition, the dispersibility of the metal oxide and its paint ( This is preferable because it is very effective in improving the temporal stability of the curable composition) and also improves the leveling property of the coating process. The hydroxyl group-containing solvent content in the total solvent composition is preferably 10 to 100% by weight. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol Examples thereof include monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, diacetone alcohol, ethyl lactate, butyl lactate, and propylene glycol monomethyl ether. In particular, 3-methoxy-1-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and ethylene glycol mono n-butyl ether are preferable because the dispersibility and dispersion stability of the metal oxide become better.

  The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, monocarbonyl compounds, dicarbonyl compounds, acetophenone compounds, benzoin ether compounds, acylphosphine oxide compounds, aminocarbonyl compounds. Etc. can be used.

  Specifically, as the monocarbonyl compound, benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl -Ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4) , 7,10,13-pentaoxotridecyl) benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) ) Metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3- (3 4-dimethyl-9-oxo-9H thioxanthone-2-yloxy-N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline, and the like.

  Examples of dicarbonyl compounds include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-Isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one Polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla Mino-1- (4-morpholinophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino -Propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

  Examples of aminocarbonyl compounds include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino) benzoate. 2- (dimethylamino) ethylbenzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

  Commercially available photopolymerization initiators include Irgacure 184, 651, 500, 907, 127, 369, 784, 2959, manufactured by Ciba Specialty Chemicals Co., Ltd., Lucirin TPO manufactured by BASF, Esacure One manufactured by Nippon Sibel Hegner Co. can give.

  The photopolymerization initiator is not limited to the above compound, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization by ultraviolet rays. These photopolymerization initiators may be used alone or in combination of two or more.

  Although there is no restriction | limiting in particular regarding the usage-amount of a photoinitiator, It is preferable to use within the range of 1-20 weight part with respect to 100 weight part of whole quantity of a photocurable compound.

  A known organic amine or the like can be added as a sensitizer.

  Furthermore, in addition to the radical polymerization initiator, a cationic polymerization initiator may be used in combination.

  The curable composition may contain other binder resins and photocurable compounds in addition to the amino group-containing photocurable compound.

  Examples of the binder resin include polyurethane resin, polyurea resin, polyurethane urea resin, polyester resin, polyether resin, polycarbonate resin, epoxy resin, amino resin, styrene resin, acrylic resin, melamine resin, polyamide resin, phenol resin, vinyl resin. Etc. These resins may be used alone or in combination of two or more. The binder resin is preferably used within a range of 20 parts by weight or less based on the total amount of solids (components other than the solvent, hereinafter the same) of the curable composition (100 parts by weight).

  As a photocurable compound, for example, a compound having a polymerizable unsaturated double bond group such as a (meth) acrylic compound, a fatty acid vinyl compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, and an ethynyl compound is used. Can do. These compounds having a polymerizable unsaturated double bond group may further have a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, or a silanol group. The photocurable compound other than the amino group-containing photocurable compound is in the range of less than 50 parts by weight, particularly in the range of 5 to 40 parts by weight, based on the total amount of solid content of the curable composition (100 parts by weight). Is preferably used.

  Examples of the (meth) acrylic compound include benzyl (meth) acrylate, alkyl (meth) acrylate, alkylene glycol (meth) acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, and a hydroxyl group (meta ) Acrylic compounds, nitrogen-containing (meth) acrylic compounds, and the like. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.

  Specific examples of monofunctional (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (medium) ) Acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, alkylene (meth) acrylate having 1 to 22 carbon atoms such as docosyl (meth) acrylate. In the case of adjusting the polarity, it is preferable to use an alkyl group-containing (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms. For the purpose of adjusting the leveling property, it is preferable to use an alkyl (meth) acrylate having an alkyl group having 6 or more carbon atoms.

  Examples of alkylene glycol (meth) acrylates include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and polyethylene glycol mono (meth). A polyoxyalkylene chain having a hydroxyl group at the terminal, such as acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, etc. (Meth) acrylate having methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate , Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n- Pentaxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth) acrylate, ethoxytetrapropylene glycol (meth) ) Acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxy Tetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol Mono (meth) acrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain, such as (meth) acrylate; phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylic Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy or aryloxy group at the terminal, such as rate, phenoxypolyethylene glycol (meth) acrylate, and phenoxytetrapropylene ethylene glycol (meth) acrylate.

  Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalic acid β- (meth) acryloxyethyl monoester , Isophthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like.

  Examples of hydroxyl group-containing (meth) acrylic compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and 4-hydroxyvinylbenzene. , 2-hydroxy-3-phenoxypropyl (meth) acrylate and the like.

Nitrogen-containing (meth) acrylic compounds include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, N-propoxymethyl- ( Monoalkylol (meth) acrylamide such as (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N- Methoxymethyl (meth) acrylamide, N, N-di (methylol) acrylamide, N-ethoxymethyl-N-methoxymethyl methacrylamide, N, N-di (ethoxymethyl) acrylaminide, N-ethoxymethyl-N-propoxy Methyl methacrylate N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) meta Acrylamide-type unsaturated compounds such as acrylamide, N, N-di (pentoxymethyl) acrylamide, dialalkylol (meth) acrylamide such as N-methoxymethyl-N- (pentoxymethyl) methacrylamide; dimethylaminoethyl (meth) acrylate , diethylaminoethyl (meth) acrylate, methyl ethyl amino ethyl (meth) acrylate, dimethylamino styrene, the unsaturated compound having a dialkylamino group such as a diethylamino styrene; and, Cl as counterions ^-, Br @ -, I ^-, etc. Rogen'ion or QSO3 ^-: There are quaternary ammonium salts of dialkylamino group-containing unsaturated compound having a (Q alkyl group having 1 to 12 carbon atoms).

  Other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) Perfluoroalkanes having 1 to 20 carbon atoms such as acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate Can be mentioned perfluoroalkyl alkyl (meth) acrylates having an Le group.

  Furthermore, perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyl, alkylene, etc. such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, and perfluorodecylethylene; vinyltrichlorosilane, vinyltris (β-methoxyethoxy) Examples include alkoxysilyl group-containing vinyl compounds such as silane, vinyltriethoxysilane, and γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof; glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate.

  Examples of the fatty acid vinyl compound include vinyl acetate, vinyl butyrate, vinyl crotonic acid, vinyl caprylate, vinyl laurate, vinyl chloroacetate, vinyl oleate, and vinyl stearate.

  Examples of the alkyl vinyl ether compound include butyl vinyl ether and ethyl vinyl ether.

  Examples of the α-olefin compound include 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like.

  Examples of the vinyl compound include allyl compounds such as allyl acetic acid, allyl alcohol, allyl benzene, and allyl cyanide, vinyl cyanide, vinyl cyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, chlorostyrene, and the like. It is done.

The ethynyl compound, et Chinirubenzen, ethynyl toluene, 1-ethynyl-1-cyclohexanol, and the like.

  These may be used alone or in combination of two or more.

  Examples of photocurable compounds other than amino group-containing photocurable compounds include polyurethane poly (meth) acrylates having at least three functional groups, polyepoxy poly (meth) acrylates, etc., from the viewpoint of coating film strength and scratch resistance. Poly (meth) acrylates and polyfunctional acrylates having 3 or more acryloyl groups in the molecule can be preferably used.

  Polyepoxy poly (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to a (meth) acryloyl group, and (meth) acrylic to a bisphenol A type epoxy resin. There are acid addition products, (meth) acrylic acid addition products to novolac type epoxy resins, and the like.

  Polyurethane poly (meth) acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylate having a hydroxyl group, or isocyanate group-containing urethane obtained by reacting polyol and polyisocyanate under the condition of excess isocyanate group. Some are obtained by reacting a prepolymer with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

  Examples of polyols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, hexanetriol, trimellilol propane, polytetra Examples include methylene glycol and a condensation polymer of adipic acid and ethylene glycol.

  Examples of the polyisocyanate include tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.

  Examples of (meth) acrylates having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and the like.

  Examples of the (meth) acrylates having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and (meth) acryloyl isocyanate.

  The following can be illustrated as a commercial item of a photocurable compound.

Toa Gosei Co., Ltd .: Aronix M-400, Aronix M-402, Aronix M-408, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060,
Osaka Organic Chemical Industry Co., Ltd .: Biscote # 400
Kayaku Sartomer Co., Ltd .: SR-295,
Daicel UCB Co., Ltd .: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602,
Shin Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6 , NK oligo U-4HA, NK oligo U-6HA, NK oligo U-324A,
Manufactured by BASF: LaromerEA81,
Sannopco: Photomer 3016,
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP -3, Art resin H61,
Nippon Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B,
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I,
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330.

  Next, the cured film and laminated body of the present invention will be described.

  The cured film of the present invention is a film formed by curing the curable composition of the present invention. The manufacturing method includes, for example, applying the curable composition to an arbitrary substrate, and irradiating an active energy ray to cure the curable composition on the substrate.

  More specifically, this curable composition is coated on an arbitrary substrate so that the film thickness after drying is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and then cured. It can be formed by processing.

  At the time of formation, the cured film may be applied directly to the substrate, or one or more lower layers may exist between the cured film and the substrate.

  Examples of the base material include metals, ceramics, glass, plastics, wood, slate and the like, and are not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

  As a coating method, a known method can be used. For example, a method using a lot or a wire bar, or various coating methods such as microgravure, gravure, die, curtain, lip, slot or spin can be used. it can.

  The curing treatment can be performed by irradiating active energy rays such as ultraviolet rays, electron beams, visible rays having a wavelength of 400 to 500 nm, using a known technique. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm. As the electron beam source, a thermionic emission gun, an electrolytic emission gun, or the like can be used.

The active energy dose to be irradiated is preferably in the range of 5 to 2000 mJ / cm ² , and more preferably in the range of 50 to 1000 mJ / cm ² from the viewpoint of easy management in the process.

  These active energy rays can be used in combination with heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  The cured film may be formed by applying a curable composition to a substrate and naturally or forcibly drying it, followed by a curing treatment, or after coating and curing for natural or forced drying. However, it is more preferable to perform the curing treatment after natural or forced drying.

  In particular, in the case of curing with an electron beam, it is more preferable to carry out the curing treatment after natural or forced drying in order to prevent the inhibition of curing by water or the decrease in strength of the coating film due to the remaining organic solvent.

  The timing of the curing treatment may be simultaneous with coating or after coating.

  The resulting cured film is excellent in hard coat properties, transparency, light resistance, high refractive index properties, and antistatic properties, and therefore can be suitably used as an optical material. Therefore, the cured film of the present invention can be used as a laminated body as a front plate of various display devices such as a cathode ray tube and a flat display panel (liquid crystal display, plasma display, electrochromic display, light emitting diode display, etc.) or an input device thereof. Available.

  In addition, the cured film can be widely used for optical lenses, glasses lenses, optical recording disks (compact disks, DVD disks, Blu-ray disks, etc.), light cases, and the like.

The surface resistance value of the cured film is preferably 1 × 10 ¹² Ω / □ or less.

  The thickness of the cured film is preferably 0.1 to 30 μm.

  Furthermore, the refractive index of the cured film is preferably in the range of 1.4 to 1.8.

  The laminate of the present invention includes the cured film of the present invention and a substrate. As the substrate, those exemplified above can be arbitrarily used, and a plastic substrate is particularly preferable. The shape of the substrate is preferably a film shape, a lens shape, or a disk shape.

  In addition to these, the laminate preferably contains one or more layers having different refractive indexes, adhesive layers, information recording layers, and the like.

  The laminate including the film (M), the pressure-sensitive adhesive layer (M) or the information recording layer (M) having different refractive indexes can have a layer configuration such as the following (I) to (IX).

(I) Base material / (M) / cured film (II) Base material / cured film / (M)
(III) substrate / (M) / cured film / (M)
(IV) (M) / base material / cured film (V) (M) / base material / (M) / cured film (VI) (M) / base material / cured film / (M)
(VII) (M) / base material / (M) / cured film / (M)
(VIII) (M) / cured film / base material / cured film (IX) cured film / (M) / base material / cured film Other than the function of the cured product of the present invention, the film or information recording layer having a different refractive index It has the function of. The formation method is not particularly limited, and it is formed by a known method. For example, dry coating methods such as vapor deposition and sputtering, methods using lots and wire bars, and wet coating methods such as microgravure, gravure, die, curtain, lip, slot, and spin can be used. There is no limitation on the material used, and if necessary, one or more functions such as information recording function, anti-glare function, Newton ring prevention function, adhesive function, blocking of specific wavelength, adhesion improvement, color correction, etc. are given to the laminate. Any material that can be used can be used.

  The information recording layer may be any material as long as it causes some chemical change by laser light or the like and records information by the change, and the material is not particularly limited. Examples of organic materials include polymethine dyes, naphthalocyanine-based, phthalocyanine-based, squarylium-based, anthraquinone-based, xanthene-based, and triphenylmethane-based metal complex compounds, and one or a combination of two or more of the above dyes. Can be used. As the inorganic recording layer, metals such as Te, Ge, Se, In, Sb, Sn, Zn, Au, Al, Cu, and Pt, and semimetals can be used singly or in combination of two or more. The information recording layer may be a laminate or the like, and the mode of photochemical change may be any of phase change, bubble, and punching type. Further, it may be a magneto-optical recording layer mainly composed of Fe, Tb, or Co, or may be a spiropyran or a fluorinated photochromic material.

  From the viewpoint of antireflection, the high refractive index cured film is also preferably used as a laminate provided with a low refractive index coating cured film on the surface layer to provide an antireflection function. That is, it is preferable to use a laminate obtained by forming a cured film on a substrate such as a film and more preferably forming a coated cured film as the antireflection film.

  In a laminate in which reflection interference fringes are a problem, the blending amount of the metal oxide in the curable composition of the present invention is adjusted, and the difference in refractive index between the cured film and the substrate or the cured film and When an arbitrary layer exists between the substrate and the base material, it is preferable that the difference in refractive index between the cured film and the lower layer in contact with the cured film is within ± 0.02.

  The curable composition of the present invention can produce a cured product having a high refractive index by controlling the type and amount of metal oxide. Therefore, in order to improve the light extraction efficiency of the optical semiconductor element, it can be preferably used as an optical semiconductor element sealing material that requires that the refractive index of the resin layer be sequentially reduced from the optical semiconductor element side toward the outermost layer. .

  Examples of the optical semiconductor element include gallium nitride (GaN: refractive index 2.5), gallium phosphide (GaP: refractive index 2.9), gallium arsenide (GaAs: refractive index 3.5), and the like. Is a high material. Therefore, the refractive index of the cured product that becomes the optical semiconductor element sealing material is preferably 1.5 or more, more preferably 1.5 to 2.1, and still more preferably 1 from the viewpoint of increasing the light extraction efficiency. .7 to 2.1.

  As a method of achieving the optimum refractive index of the cured product, titanium oxide (refractive index 2.5 to 2.7), zirconium oxide (refractive index 2.4), zinc oxide (refractive index 1) is used as a metal oxide to be used. .95) and the like are preferable, and since the dispersant is required to have high refractive index, an amino group-containing photocurable compound having an aromatic skeleton is preferable.

Hereinafter, the present invention will be described in more detail based on production examples and examples. However, the following production examples and examples do not limit the scope of rights of the present invention. In Production Examples and Examples, parts and% represent parts by weight and% by weight, respectively. Moreover, a weight average molecular weight represents the standard polystyrene conversion molecular weight measured by GPC.
(Production Example 1)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 43.17 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), dipentaerythritol pentaacrylate (Nippon Kayaku) Co., Ltd .: KAYARAD DPHA) 80.52 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 32.67 parts, cyclohexanone 156.36 parts were charged to 85 ° C. . Next, 0.78 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 41.69 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 39.58 parts of cyclohexanone are added, and then 1.25 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (1). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 2,200, and a weight average molecular weight (MW) of 8,400.

To a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (1) with 5.53 parts of cyclohexanone, 0.36 parts of dibutylamine (moles of ethylenically unsaturated double bonds) Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (1A) (solid content 40%) )
(Production Example 2)
A 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 35.00 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), dipentaerythritol pentaacrylate (Nippon Kayaku) Co., Ltd .: KAYARAD DPHA) 65.28 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 52.98 parts, cyclohexanone 153.26 parts were charged to 85 ° C. . Next, 0.77 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 33.80 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 31.73 parts of cyclohexanone are added, and then 1.23 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (2). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,380, and a weight average molecular weight (MW) of 5,360.

In a solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (2) with 5.30 parts of cyclohexanone, 0.20 part of diethylamine (mole number of ethylenically unsaturated double bonds) / Mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (2A) (solid content 40%) Got.
(Production Example 3)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 40.00 parts biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), dipentaerythritol pentaacrylate (Nippon Kayaku) Co., Ltd .: KAYARAD DPHA) 22.27 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 81.33 parts, cyclohexanone 143.60 parts were charged and heated to 85 ° C. . Next, 0.72 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 38.63 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 36.69 parts of cyclohexanone were added, then 1.15 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (3). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,520, and a weight average molecular weight (MW) of 5,680.

To a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing the (meth) acrylate compound (3) with 6.04 parts of cyclohexanone, 0.70 part of 2-piperidineethanol (ethylenically unsaturated double The number of bonded moles / the number of moles of amine compound = 100/10) was added, and the mixture was stirred at 40 ° C. for 5 hours, then cooled to room temperature, and a cyclohexanone solution of amino group-containing photocurable compound (3A) (solid content 40% )
(Production Example 4)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 52.20 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) Company: KAYARAD PET-30) 54.55 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 39.51 parts, cyclohexanone 146.26 parts, charged to 85 ° C did. Next, 0.73 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.41 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 48.43 parts of cyclohexanone were added, and then 1.17 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (4). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,980, and a weight average molecular weight (MW) of 7,840.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing the (meth) acrylate compound (4) with 5.43 parts of cyclohexanone, 0.29 parts of N-methylhexylamine (ethylenically unsaturated dioxygen) was added. The number of moles of heavy bonds / the number of moles of amine compound = 100 / 4.24) was added, and the mixture was stirred at 40 ° C. for 5 hours, then cooled to room temperature, and a cyclohexanone solution of amino group-containing photocurable compound (4A) (solid 40%).
(Production Example 5)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 35.00 parts biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) Company: KAYARAD PET-30) 36.58 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 52.98 parts, cyclohexanone 124.55 parts, charged to 85 ° C did. Next, 0.62 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 33.80 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 32.12 parts of cyclohexanone are added, and then 1.00 part of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours.
After cooling to room temperature, a cyclohexanone solution of (meth) acrylate compound (5) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,280 and a weight average molecular weight (MW) of 4,380.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (5) with 5.49 parts of cyclohexanone, 0.33 parts of dibutylamine (moles of ethylenically unsaturated double bonds) Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (5A) (solid content 40%) )
(Production Example 6)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 35.00 parts biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd.) Company: KAYARAD PET-30) 36.58 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 52.98 parts, cyclohexanone 124.55 parts, charged to 85 ° C did. Next, 0.62 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 33.80 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 32.12 parts of cyclohexanone are added, and then 1.00 part of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours.
After cooling to room temperature, a cyclohexanone solution of (meth) acrylate compound (6) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,350, and a weight average molecular weight (MW) of 5,310.

In a solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (6) with 5.63 parts of cyclohexanone, 0.42 parts of diethylamine (mole number of ethylenically unsaturated double bonds) / Mole number of amine compound = 100/10) and stirred at 40 ° C. for 5 hours and then cooled to room temperature to obtain a cyclohexanone solution of amino group-containing photocurable compound (6A) (solid content 40%). It was.
(Production Example 7)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylic (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 39.34 parts, cyclohexanone 171.28 parts are charged 85 The temperature was raised to ° C. Next, 0.86 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.88 parts of cyclohexanone are added, then 1.37 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (7). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 2,000, and a weight average molecular weight (MW) of 8,050.

In a solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (7) with 5.32 parts of cyclohexanone, 0.22 part of diethylamine (mole number of ethylenically unsaturated double bonds) / Mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (7A) (solid content 40%) Got.
(Production Example 8)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylic (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 78.67 parts, cyclohexanone 210.61 parts are charged 85 The temperature was raised to ° C. Next, 1.05 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.35 parts of cyclohexanone are added, and then 1.68 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (8). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,250, and a weight average molecular weight (MW) of 4,980.

To a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing the (meth) acrylate compound (8) with 5.56 parts of cyclohexanone, 0.37 parts of dibutylamine (moles of ethylenically unsaturated double bonds) Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (8A) (solid content 40%) )
(Production Example 9)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 40.00 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid BT-100), dipentaerythritol penta Acrylic (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 33.07 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M), 120.78 parts, cyclohexanone 193.85 parts are charged 85 The temperature was raised to ° C. Next, 0.97 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 57.36 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 54.74 parts of cyclohexanone are added, then 1.55 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (9). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,400, and a weight average molecular weight (MW) of 5,460.

To a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (9) with 6.12 parts of cyclohexanone, 0.75 parts of 2-piperidineethanol (ethylenically unsaturated double The number of moles of bond / the number of moles of amine compound = 100/10) was added, and the mixture was stirred at 40 ° C. for 5 hours, then cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (9A) (solid content 40% )
(Production Example 10)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, 38.43 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid BT-100), pentaerythritol triacrylate (Nippon Kayaku Co., Ltd .: KAYARAD PET-30) 59.64 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 43.19 parts, cyclohexanone 141.26 parts The temperature was raised to 85 ° C. Next, 0.71 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 6 hours. Next, 55.11 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 53.20 parts of cyclohexanone were added, then 1.13 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (10). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,780, and a weight average molecular weight (MW) of 7,440.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (10) with 5.30 parts of cyclohexanone, 0.20 part of diethylamine (mole number of ethylenically unsaturated double bonds) / Mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (10A) (solid content 40%) Got.
(Production Example 11)
A 4-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid BT-100), 35.00 parts, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd .: KAYARAD PET-30) 54.31 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 78.67 parts, cyclohexanone 167.9 parts The temperature was raised to 85 ° C. Next, 0.84 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.92 parts of cyclohexanone are added, and then 1.34 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (11). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,090, and a weight average molecular weight (MW) of 4,280.

To a solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (11) with 5.41 parts of cyclohexanone, 0.28 parts of 1-aminohexane (ethylenically unsaturated double The number of moles of bond / the number of moles of amine compound = 100 / 4.24) was added, and the mixture was stirred at 40 ° C. for 5 hours, and then cooled to room temperature to prepare a cyclohexanone solution (solid content) of the amino group-containing photocurable compound (11A). 40%).
(Production Example 12)
A 4-neck flask equipped with a stirrer, reflux condenser, dry air inlet tube, thermometer, butanetetracarboxylic dianhydride (manufactured by Nippon Kayaku Co., Ltd .: Ricacid BT-100), 30.00 parts, pentaerythritol triacrylate (Nippon Kayaku Co., Ltd .: KAYARAD PET-30) 13.90 parts, EPOXY ACRYLATE FROM (POLY) PROPYLENE GLYCOL (manufactured by Nagase ChemteX Corporation: DA-911M) 90.58 parts, cyclohexanone 134.48 parts The temperature was raised to 85 ° C. Next, 0.67 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 47.32 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 45.51 parts of cyclohexanone are added, and then 1.08 part of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (12). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,190 and a weight average molecular weight (MW) of 4,450.

To a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (12) with 6.09 parts of cyclohexanone, 0.73 parts of dibutylamine (moles of ethylenically unsaturated double bonds) Number / mole number of amine compound = 100/10), and stirred at 40 ° C. for 5 hours, and then cooled to room temperature to obtain a cyclohexanone solution of amino group-containing photocurable compound (12A) (solid content 40%). Obtained.
(Production Example 13)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, ECH-modified 1,6-hexanediol diacrylate (Nippon Kayaku Co., Ltd .: KAYARAD R-167) 44.32 parts, cyclohexanone 176.26 parts The temperature was raised to 85 ° C. Next, 0.88 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.81 parts of cyclohexanone are added, and then 1.41 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (13). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 2,100, and a weight average molecular weight (MW) of 8,100.

To a solution obtained by diluting 20.0 parts of cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (13) with 5.56 parts of cyclohexanone, 0.37 parts of dibutylamine (ethylenically unsaturated double bond mole) Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (13A) (solid content 40%) )
(Production Example 14)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylic (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, bisphenol A diglycidyl ether acrylic acid adduct (Kyoeisha Chemical Co., Ltd .: Epoxy ester 3000A) 57.35 parts, cyclohexanone 189.29 parts are charged 85. The temperature was raised to ° C. Next, 0.95 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.63 parts of cyclohexanone are added, then 1.51 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (14). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,900, and a weight average molecular weight (MW) of 8,200.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing the (meth) acrylate compound (14) with 5.30 parts of cyclohexanone, 0.20 part of diethylamine (mole number of ethylenically unsaturated double bonds) / Mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (14A) (solid content 40%) Got.
(Production Example 15)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylic (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, bisphenol A diglycidyl ether methacrylic acid adduct (Kyoeisha Chemical Co., Ltd .: Epoxy ester 3000M) 60.67 parts, cyclohexanone 192.61 parts are charged 85 The temperature was raised to ° C. Next, 0.96 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst and reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.59 parts of cyclohexanone are added, then 1.54 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (15). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 2,050, and a weight average molecular weight (MW) of 8,060.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (15) with 6.23 parts of cyclohexanone, 0.82 part of dibutylamine (ethylenically unsaturated double bond mole) was added. Number / number of moles of amine compound = 100/10), stirred at 40 ° C. for 5 hours, and then cooled to room temperature to obtain a cyclohexanone solution (solid content 40%) of the amino group-containing photocurable compound (15A). Obtained.
(Production Example 16)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 96.94 parts, Neopentyl Glycol Digicydyl Ether (Nagase Chemtex Co., Ltd .: Denacol EX-211) 25.60 parts, cyclohexanone 157.54 parts are charged to 85 ° C. Warm up. Next, 0.79 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 48.06 parts of cyclohexanone are added, and then 1.26 parts of dimethylbenzylamine is added as a catalyst, followed by stirring at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (16). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,940, and a weight average molecular weight (MW) of 7,860.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (16) with 5.52 parts of cyclohexanone, 0.35 parts of dibutylamine (moles of ethylenically unsaturated double bonds) Number / number of moles of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (16A) (solid content 40%) )
(Production Example 17)
A 4-neck flask equipped with a stirrer, a reflux condenser, a dry air inlet tube, and a thermometer, butane tetracarboxylic dianhydride (manufactured by Shin Nippon Chemical Co., Ltd .: Ricacid BT-100), 35.00 parts, dipentaerythritol penta Acrylate (Nippon Kayaku Co., Ltd .: KAYARAD DPHA) 144.69 parts, 1,6-hexanediol (Wako Pure Chemical Industries, Ltd.) 10.44 parts, and cyclohexanone 190.12 parts were charged, and the temperature was raised to 85 ° C. Next, 0.95 part of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and the mixture was reacted at 85 ° C. with stirring for 8 hours. Next, 50.19 parts of glycidyl methacrylate (manufactured by Dow Chemical Japan Co., Ltd.) and 47.62 parts of cyclohexanone are added, then 1.52 parts of dimethylbenzylamine is added as a catalyst, and the mixture is stirred at 85 ° C. for 6 hours. To obtain a cyclohexanone solution of the (meth) acrylate compound (17). This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) of 1,500, and a weight average molecular weight (MW) of 5,800.

In a solution obtained by diluting 20.0 parts of a cyclohexanone solution (solid content 50%) containing (meth) acrylate compound (17) with 5.61 parts of cyclohexanone, 0.41 part of dibutylamine (moles of ethylenically unsaturated double bonds). Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (17A) (solid content 40%) )
(Production Example 18)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 80.0 parts of biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation), pentaerythritol triacrylate (Osaka Organic Chemistry) Industrial Co., Ltd. product: biscoat # 300) 250.0 parts, hydroquinone 0.16 parts, cyclohexanone 141.2 parts were charged, and the temperature was raised to 85 ° C. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) is added as a catalyst, and the mixture is stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (Dow Chemical Japan) is added. 77.3 parts and 33.9 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and (meth) acrylate. A cyclohexanone solution of compound (18) was obtained. This reaction solution was light yellow and transparent and had a solid content of 70%, a number average molecular weight (MN) 870, and a weight average molecular weight (MW) 2,830.

In a solution obtained by diluting 28.6 parts of a cyclohexanone solution (solid content 70%) containing (meth) acrylate compound (18) with 23.07 parts of cyclohexanone, 0.31 part of dibutylamine (moles of ethylenically unsaturated double bonds) Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (18A) (solid content 40%) )
(Production Example 19)
In a four-necked flask equipped with a stirrer, reflux condenser, dry air inlet tube, and thermometer, 100.0 parts of butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid BT-100), pentaerythritol tri Acrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD PET-30), 463.2 parts, 0.28 part of hydroquinone, and 563.2 parts of cyclohexanone were charged and heated to 85 ° C. Next, 2.82 parts of 1,8-diazabicyclo [5.4.0] -7-undecene (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, stirred at 85 ° C. for 8 hours, and glycidyl methacrylate (Dow Chemical Japan). (Made by Co., Ltd.) 143.4 parts and 146.5 parts of cyclohexanone were added, and then 4.53 parts of dimethylbenzylamine was added as a catalyst, stirred at 85 ° C. for 6 hours, cooled to room temperature, and a (meth) acrylate compound A cyclohexanone solution of (19) was obtained. This reaction solution was light yellow and transparent and had a solid content of 50%, a number average molecular weight (MN) 920, and a weight average molecular weight (MW) 2,200.

In a solution obtained by diluting 30.0 parts of a cyclohexanone solution (solid content: 50%) containing (meth) acrylate compound (19) with 9.1 parts of cyclohexanone, 0.3 part of dibutylamine (moles of ethylenically unsaturated double bonds) was added. Number / mole number of amine compound = 100 / 4.24), stirred at 40 ° C. for 5 hours, cooled to room temperature, and cyclohexanone solution of amino group-containing photocurable compound (19A) (solid content 40% )
(Production of metal oxide dispersion paste: Examples 1 to 17, Comparative Examples 1 and 2)
Using each amino group-containing photocurable compound prepared in the above production example, metal oxide dispersion was performed according to the formulation shown in Table 1 to prepare a metal oxide dispersion paste. Dispersion methods are temporary dispersion (using zirconia beads (1.25 mm) as a medium and dispersion for 1 hour with a paint shaker) and main dispersion (using zirconia beads (0.1 mm) as a medium). (Dispersion with machine UAM-015).

In Table 1,
Sb ₂ O ₅ : “San-Epoch EFR-6N” manufactured by Nissan Chemical Industries, Ltd. (average primary particle size: 20 nm)
ATO: “T-1” manufactured by Mitsubishi Materials Corporation (average primary particle size: 20 nm)
ITO: “Nanotech ITO” manufactured by CI Kasei Co., Ltd. (average primary particle size: 30 nm)
PTO: “EP SP-2” manufactured by Mitsubishi Materials Corporation (average primary particle size: 10 nm)
Al-doped ZnO: “PazetCK” (average primary particle size: 30 nm) manufactured by Hakusuitec Co., Ltd.
SnO ₂ : “S-2000” manufactured by Mitsubishi Materials Corporation (average primary particle size: 20 nm)
ZrO ₂ : “PCS-60” manufactured by Nippon Electric Works Co., Ltd. (average primary particle size: 20 nm)
ATO-coated TiO ₂ : “ET-300W” manufactured by Ishihara Sangyo Co., Ltd. (average primary particle size: 45 nm)
SiO ₂ : “AEROSIL50” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 30 nm)
Al ₂ O ₅ : “Aluminium Oxide C” manufactured by Nippon Aerosil Co., Ltd. (average primary particle size: 13 nm)
Commercially available multifunctional monomer: “Beamset 750” (bisphenol A ethylene oxide modified acrylate, molecular weight (MW) 512, manufactured by Arakawa Chemical Industries, Ltd.
MIBK: methyl isobutyl ketone methobuta: 3-methoxy-1-butanol (coating and evaluation of cured film: Examples 1 to 13, Comparative Examples 1 and 2)
A curable composition having the composition shown in Table 2 was prepared using the metal oxide dispersion paste prepared above. The obtained curable composition was coated on a 100 μm-thick PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd.) with a bar coater so that the film thickness after drying was 5 μm. Thereafter, ultraviolet rays of 400 mJ / cm ² were irradiated with a high-pressure mercury lamp to form an antistatic hard coat layer (cured film). The resulting antistatic hard coat layer was evaluated for surface resistance, scratch resistance, pencil hardness, transparency (haze), and light resistance by the following methods. The results are shown in Table 2.

In Table 2,
Photo-curable compound (1): “Shikko UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd.
Photo-curable compound (2): “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Solvent: PGME (propylene glycol monomethyl ether)
* 1: Unmeasured because the metal oxide paste was poorly dispersed (production and evaluation of antireflection film (laminate): Examples 14 to 19)
(Preparation of low refractive index coating liquid)
1,2,9,10-Tetraacryloyloxy-4,4,5,5,6,6,7,7-octafluorodecane 50% by weight, silica sol 30% dispersion (MEK- manufactured by Nissan Chemical Industries, Ltd.) ST) 120 parts by weight, 2 ', 2'-bis ((meth) acryloyloxymethyl) propionic acid (2-hydroxy) -4,4,5,5,6,6,7,7,8,8,9 9,10,10,11,11,11-nonadecafluoroundecyl 10 parts by weight, butyl alcohol 900 parts by weight, photopolymerization initiator (Nippon Kayaku Co., Ltd. KAYACURE BMS) 5 parts by weight, A low refractive index coating solution was prepared.

Using the metal oxide dispersion paste of Example 4, each curable composition having a composition according to the formulation shown in Table 3 was prepared. This curable composition was applied to an easy-adhesion-treated surface of a 100-μm-thick easy-adhesion-treated PET film (refractive index of the easy-adhesion-treated layer = 1.60) using a bar coater so that the dry film thickness was 6 μm. . The obtained coating layer was dried at 100 ° C. for 1 minute and then irradiated with 400 mJ / cm ² of ultraviolet rays with a high-pressure mercury lamp. Further, the low refractive coating liquid was applied on the obtained cured film with a spin coater while adjusting the layer thickness so that the wavelength of light having a dry film thickness of λ / 4 was about 550 nm. The obtained coating layer was dried at 100 ° C. for 1 minute, and then irradiated with 400 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp to obtain a laminate.

  About the obtained laminated body, while measuring the refractive index of the cured film by the following method, the scratch resistance, pencil hardness, transparency (haze), refractive index, and reflection interference fringe of the cured film were evaluated. Furthermore, regarding the temporal stability of the curable composition, the viscosity change after 2 weeks at 40 ° C. was evaluated. The results are shown in Table 3.

In Table 3, photocurable compound (1): “purple light UV-1700B” manufactured by Nippon Synthetic Chemical Co., Ltd.
Photopolymerization initiator: “Irgacure 184” manufactured by Ciba Specialty Chemicals
Base material: 100 μm thick easy-adhesion-treated PET film (“Cosmo Shine A-4100” manufactured by Toyobo Co., Ltd., coated on easy-adhesion-treated surface (refractive index 1.60))
Solvent: PGME (propylene glycol monomethyl ether)
(Evaluation methods)
(1) Surface resistance The surface resistance (Ω / □) of the cured film was evaluated according to the following criteria.

When the surface resistance is 1 × 10 ¹² or less: A
When the surface resistance is higher than 1 × 10 ¹² and 1 × 10 ¹⁴ or less: B
When the surface resistance exceeds 1 × 10 ¹⁴ : D
(2) Scratch resistance The coated material was set on a Gakushin tester, and was shaken 10 times with a load of 250 g using steel wool No. 0000. About the taken-out coating material, the degree of a crack was judged according to the following five-step visual evaluation. It shows that the abrasion resistance of a cured film is so favorable that a numerical value is large.

5: No scratches 4: Slight scratches 3: Scratches are observed, but the substrate is not visible 2: Scratches are present, and part of the cured film is peeled 1: The cured film is peeled off The substrate is exposed (3) Pencil hardness In accordance with JIS-K5600, using a pencil hardness tester (Scratching Tester HEIDON-14 manufactured by HEIDON), the hardness of the pencil core is variously changed and the load is changed. The test was conducted 5 times at 500 g. The hardness of the core when the scratch was not scratched or scratched only once in 5 times was defined as the pencil hardness of the cured film. Considering the practical properties required, the pencil hardness of the cured film is
2H or more: A
H: B
Lower than H: D
It was determined.
(4) Transparency (Haze value)
Turbidity (Haze value) in the obtained coated product was measured using a Haze meter.
(5) Light resistance Yellowing with the passage of time during continuous light irradiation is extremely undesirable for application development. Therefore, yellowing during continuous light irradiation was confirmed.

First, the coated material was exposed for 24 hours with a light resistance tester (light source: xenon lamp, illuminance: 100 W / cm ² , black panel temperature: 60 ° C., 60% RH). Thereafter, the coated material was placed on white paper, and coloring was measured using a colorimeter (Minolta CR-300). The colorimetric value was displayed as L ^* a ^* b ^* , and the guideline for yellowing of the cured film was judged from the b ^* value. The smaller the value of b ^* value, the smaller the degree of yellowing and the better the light resistance. In consideration of practical required physical properties, the b ^* value of the cured film is
Less than 3.5: A
3.5 or more: D
It was determined.
(6) Refractive index The refractive index of the obtained cured film was measured using an Abbe refractometer manufactured by Atago Co., Ltd.
(7) Reflective interference fringes The obtained interference interference fringes of the cured film were visually evaluated according to the following criteria.

A: Reflective interference fringes cannot be observed D: Reflective interference fringes can be observed (8) Stability over time The obtained curable composition is packed in a brown bottle and left in a light-shielded state at 40 ° C. for 2 weeks to change its viscosity. Evaluation was made according to the following criteria.

A: Viscosity increase rate of less than 10% D: Viscosity increase rate of 10% or more

Claims (9)

A metal oxide having an average primary particle size of 5 to 100 nm,
An acid anhydride group in the compound (A) having an acid anhydride group represented by the following general formula (1);
In the compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond, and in the compound (C) having two or more functional groups capable of reacting with an acid anhydride group A carboxyl group in the compound (D) having a carboxyl group obtained by reacting a functional group capable of reacting with the acid anhydride group of
The weight average molecular weight obtained by reacting a functional group capable of reacting with a carboxyl group and a functional group capable of reacting with a carboxyl group in the compound (E) having an unsaturated double bond is 3,000 to 20,000. A certain acrylate compound or methacrylate compound (X)
A curable composition comprising an amino group-containing photocurable compound obtained by reacting a primary amine or a secondary amine ,
Metal oxides
Titanium, zinc, zirconium, antimony, indium, tin,及 Beauty, contains at least one element selected from the group consisting of aluminum, furthermore,
And the solid content 100 parts by weight of the total amount of the metal oxide and the amino group-containing photocurable compound, 1 to 80 parts by weight
Contained, and
The amino group-containing photocurable compound is
Against ethylenically unsaturated double bonds 100 moles in the acrylate compound or methacrylate compound (X), primary amine or secondary amine is 0.5 to 50 mol
The curable composition made to react by the ratio used as follows .
General formula (1)

(Here, R1 represents a tetravalent aliphatic group or an aromatic group.) Compound (B) having one functional group capable of reacting with an acid anhydride group and an unsaturated double bond comprises one functional group capable of reacting with an acid anhydride group and three or more unsaturated double bonds compound (B1) the curable composition according to claim 1 Symbol mounting, characterized in that a has and. The compound (C1) having two or more functional groups capable of reacting with an acid anhydride group is a compound (C1) having two or more functional groups capable of reacting with an acid anhydride group and an unsaturated double bond. claim 1 or 2 the curable composition according to wherein there. The curable composition according to any one of claims 1 to 3 , wherein the primary amine or the secondary amine is an aliphatic monoamine. Further comprising a solvent, and the solvent is, curable composition according to any one of claims 1-4, characterized in that it comprises 10 to 100 wt% of hydroxyl group-containing solvent to the total solvent. Cured film, which is formed by curing the curable composition according to any one of claims 1-5. The manufacturing method of the cured film formed by apply | coating the curable composition in any one of Claims 1-5 to a base material, irradiating an active energy ray, and making it harden | cure. A laminate produced by the production method according to claim 7 . The laminate according to claim 8, which is an antireflection film.