JP5996918B2 - Two-part photocurable composition - Google Patents

Description

  The present invention relates to a two-part photocurable composition comprising a curable composition (I) and a curing accelerator (II), and an electric / electronic device equipped with an FPD obtained by coating and curing the curable composition.

  Conventionally, by providing an air gap between the liquid crystal module or organic EL module, which is an image display part of a mobile phone, a touch panel, etc., and the uppermost transparent protective cover (PET film, tempered glass, acrylic plate, etc.) Even if the protective cover breaks due to the impact from the structure, the liquid crystal module is not affected (air gap structure). In recent years, for example, in order to improve visibility and impact resistance of liquid crystal displays and organic EL displays, light containing urethane acrylate or epoxy acrylate having a photopolymerizable functional group, especially ultraviolet light ( UV) curable optical elastic resin curable compositions are beginning to be used. However, due to the complexity of the design of the outermost protective cover for the purpose of imparting design to mobile phones and touch panels, the area where UV light, which is a trigger for curing, does not transmit increases, and unreacted parts There is a problem that it exists. As a specific example of the failure location, the periphery of the protective cover is decorated when the FPD (flat panel display) such as a liquid crystal panel or an organic EL panel is bonded to the protective cover or the touch panel, or when the protective cover and the touch panel are bonded. This corresponds to the bottom (dark area) where light is not transmitted, such as black frame (black print) applied for the purpose, touch panel electrode, flexible printed circuit board (FPC) connected to FPD, and FPD by photocurable liquid composition In pasting, there was a problem that an unreacted liquid composition remained in the dark part and leaked, causing contamination of the FPD.

  As a countermeasure, for example, a method of completely curing in a heated atmosphere after UV irradiation by adding a thermal polymerization initiator in addition to an initiator for UV curing has been proposed. However, this improvement method can ensure curability in the dark part, but if the front protective cover is a plastic material such as PET film or acrylic plate, it may be deformed or discolored by heating, and the applicable range is limited. Along with this, heating for a long time is indispensable for curing, and improvement in productivity is also required.

  As another countermeasure, there is a technique using a UV curing initiator and a redox type curing initiator in combination (Patent Documents 1 to 4). For example, an organic peroxide is used as the redox type curing initiator, and a reducing polymerization accelerator such as a transition metal compound or amine is added to the system as a curing reaction accelerator, so that the reaction can be carried out quickly even at room temperature. There is a method to start and redox cure the dark part, but the cured product obtained by redox curing often exhibits strong coloring and whitening, and if high quality is required for appearance such as FPD bonding, only in the dark part It is necessary to take a technique in which a redox curable resin is present in advance. That is, supplying a photocurable resin composition containing a photopolymerization initiator and an organic peroxide in the state where a redox curable resin composition containing a reducing agent is previously present in the dark part, and performing light irradiation. In the dark portion, the redox polymerization reaction is caused by radically active species generated when the reducing agent of the redox curable resin and the organic peroxide of the photocurable resin composition come into contact with each other. Cured with. Various reducing agents are used for redox curing. For example, as described in Patent Document 2, amines such as N, N-dimethylaniline, amine derivatives such as methylthiourea, oxime compounds, cobalt naphthenate, and copper naphthenate. Examples include transition metal compounds of the fourth period such as, reduced organic compounds such as ascorbic acid, and mercaptans, and these are used alone or in combination. In using these reducing agents, when the redox curing rate is slow, there is a problem that the liquid resin composition leaks from the end portion and causes contamination of the FPD. So far, the reducing agent contributes significantly to an increase in the curing rate. And the combination is not specifically reported. Moreover, in order to use the redox curable resin composition for FPD bonding in addition to the curing speed, it is necessary to appropriately select a reducing agent that does not cause a defect in the FPD. Mercaptans operate by corroding the ITO glass of the FPD. It may cause defects.

Japanese Patent Laid-Open No. 5-320284 JP 2009-108274 A Japanese Patent Application Laid-Open No. 2009-079204 WO2006 / 112420 Publication JP 2010-248347 A

  An object of the present invention is to provide a two-part photocurable composition that can quickly cure a dark part at room temperature. Furthermore, by using the two-component photocurable composition of the present invention for FPD bonding, dark areas can be quickly cured at room temperature, high appearance quality can be obtained, and there is no risk of affecting FPD operability. An object is to provide an FPD and an electric / electronic device equipped with the FPD.

  As a result of intensive studies by the present inventors in view of the above circumstances, the compound (A) having at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), a peroxide system In the two-component photocurable composition comprising the curable composition (I) containing the polymerization initiator (C) and the curing accelerator (II) containing the reducing agent (D), the fourth period is used as the reducing agent. It has been found that the above-mentioned problems can be solved by using both the transition metal compound (E) and the amine compound (F), and the present invention has been completed.

  That is, a curable composition containing a compound (A) having at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a peroxide polymerization initiator (C). A two-component photocurable composition comprising (I) and a curing accelerator (II) containing a reducing agent (D), wherein the transition metal compound (E) in the fourth period is used as the reducing agent (D). And an amine compound (F).

  It is preferable that the transition metal compound (E) in the fourth period is at least one selected from cobalt, copper, a naphthenic acid or octylic acid metal soap of vanadium, and an acetylacetone complex of vanadium.

  The amine compound (F) is at least one selected from tributylamine, N, N-dimethyltoluidine, N, N, N′N′-tetramethyl-1,6-hexanediamine, and N-methyldiethanolamine. Is preferred.

The polymerizable carbon-carbon double bond of the component (A) has the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
It is preferable that it is group represented by these.

  It is preferable that the peroxide polymerization initiator (C) is cumene hydroxy peroxide.

  The amount of the photopolymerization initiator (B) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the component (A), and the amount of the peroxide polymerization initiator (C) is 100 parts by weight of the component (A). It is preferably 0.01 to 20 parts by weight with respect to parts by weight, and the reducing agent (D) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of component (A).

  The weight ratio of the transition metal compound (E) in the fourth period to the amine compound (F) (transition metal compound in the fourth period / amine compound) is preferably 1/5 to 1/30.

  It is preferable that the two-component photocurable composition described above is for FPD bonding.

  The present invention relates to an electric / electronic device equipped with an FPD obtained by applying and curing the two-pack photocurable composition for FPD bonding described above.

  According to the present invention, it is possible to obtain a two-component photocurable composition that can be rapidly cured by light and that can be rapidly cured even in a dark part at room temperature.

It is a figure of the preparation methods of the sample for resistance value measurement of ITO glass. It is a figure of the resistance value measuring method of ITO glass. It is a figure which shows the example of application | coating of the curable composition component (I) and hardening accelerator component (II) of one Embodiment of this invention. It is a figure which shows the example of the method of FPD bonding which concerns on FIG. 3 of one Embodiment of this invention. It is a figure which shows the example of the method of FPD bonding concerning FIG. 3, 4 of one Embodiment of this invention. It is a figure which shows the example of the method of FPD bonding which concerns on FIGS. 3-5 of one Embodiment of this invention.

  The two-component photocurable liquid composition of the present invention is described in detail below.

Two-component photocurable composition The two-component photocurable composition of the present invention comprises a compound (A) having at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B). , A curable composition (I) containing a peroxide-based polymerization initiator (C) and a curing accelerator (II) containing a reducing agent (D), and the fourth period as the reducing agent (D). The transition metal compound (E) and the amine compound (F) are used.

<< Curable composition (I) >>
First, the curable composition (I) in the two-component photocurable composition will be described in detail.

<Compound (A)>
Although the polymerizable carbon-carbon double bond of the compound (A) having at least one polymerizable carbon-carbon double bond in one molecule is not particularly limited, the compound represented by the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is preferable, and a (meth) acryloyl group is more preferable.

  Moreover, the number of carbon-carbon double bonds present in one molecule of the compound (A) is not particularly limited, but is preferably 1 or more and 6 or less. If the number of carbon-carbon double bonds present in one molecule increases, the resulting cured product has a network structure that is too dense, and the molded product tends to be hard and brittle. In particular, when the number is 6 or more, the tendency becomes remarkable.

  In the case of an organic polymer, the polymerizable carbon-carbon double bond of the component (A) may be at either the main chain or the molecular chain terminal, but is preferably at the molecular chain terminal. .

  The compound (A) of the present invention may be either a low molecular weight compound or an organic polymer, but is preferably an organic polymer in terms of a balance between flexibility, durability and curability.

  The organic polymer refers to a compound having a repeating unit of an organic compound and comprising two or more repeating units. A low molecular weight compound is a compound having a structure other than an organic polymer and basically having no repeating unit.

  The low molecular weight compound is not particularly limited as long as it has a polymerizable carbon-carbon double bond, but a (meth) acrylate monomer or (meth) acrylate ester described later. Examples include monomers described as other monomer components that can be copolymerized with the monomers, and those described in paragraphs [0123] to [0131] of JP-A-2006-265488.

  The organic polymer is at least one selected from (saturated) hydrocarbon polymers, polyoxyalkylene polymers, liquid silicone polymers, liquid urethane polymers, and (meth) acrylic polymers. It is preferable that a (meth) acrylic polymer is more preferable.

  Examples of (saturated) hydrocarbon polymers include (1) polymerizing olefinic compounds having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as main components, and (2) butadiene, isoprene and the like. Can be obtained by a method such as homopolymerizing a diene compound such as the above, a method of copolymerizing the olefin compound and the diene compound, or a method of hydrogenating the obtained polymer. In view of easy introduction of functional groups at the terminals, easy control of molecular weight, and increase in the number of terminal functional groups, isobutylene polymers, (hydrogenated) polybutadiene polymers, or (hydrogenated) A polyisoprene polymer is preferred.

  The saturated hydrocarbon polymer preferably has a number average molecular weight of about 500 to 50,000, and particularly preferably has a liquid or fluidity of about 1,000 to 20,000 because it is easy to handle.

There is no restriction | limiting in particular as a polyoxyalkylene type polymer, A well-known thing is mentioned. Specific examples include those in which the main chain skeleton of the polymer has a repeating unit represented by the general formula (2).
-R ¹ -O- (2)
(Wherein R ¹ is a divalent alkylene group).

R ¹ in the general formula (2) is not particularly limited as long as it is a divalent alkylene group. Among them, an alkylene group having 1 to 14 carbon atoms is preferable, and a linear or branched chain having 2 to 4 carbon atoms. The alkylene group is more preferable. The repeating unit described in the general formula (2) is not particularly limited. For example, —CH ₂ O—, —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H ₅ ) O—, —CH ₂ C (CH ₃ ) ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O— and the like.

  The number average molecular weight of the polyoxyalkylene polymer is not particularly limited, but is 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC.

There is no restriction | limiting in particular as a liquid silicone type polymer, A well-known thing is mentioned.
Examples of the molecular structure of such a liquid silicone polymer include linear, cyclic, branched, and three-dimensional network polymers whose main chain is composed of repeating diorganosiloxane units. The molecular structure of the liquid silicone polymer is usually linear, but it may be cyclic, branched, or three-dimensional network.

  The number average molecular weight of the liquid silicone polymer is not particularly limited, but is 500 to 1,000,000, more preferably 3,000 to 100,000 when measured by GPC.

There is no restriction | limiting in particular as a liquid polyurethane-type polymer, A well-known thing is mentioned.
Examples of the molecular structure of such a liquid polyurethane polymer include those in which polyisocyanate and an active hydrogen-containing compound are used as constituent components and both are polymerized by (thio) urethane bond or urea bond.

  The polyisocyanate is not particularly limited, and examples thereof include aliphatic, alicyclic, araliphatic and aromatic polyisocyanates. More specifically, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3- Butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3- Cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-si Rhohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate, 1,3- or 1,4-xylylene diisocyanate , Ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 ′ -Diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,4 ' Examples include diphenyl ether diisocyanate, polymethylene poly (phenyl isocyanate), or those obtained by chemically modifying these polyisocyanates, and reactants such as these isocyanate compounds and polyols. You may use above.

  Moreover, there is no restriction | limiting in particular as an active hydrogen containing compound, For example, polyether polyol or polyester polyol, polyamine, polythiol etc. can be mentioned. More specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, 1,5-dimercapto-3-thiapentane, 1,8-dimercapto-3,6-dioxa Examples include octane, 1,3-ethanedithiol, (±) -dithiothreitol, dithioerythritol, 3,4-dimercaptotoluene, and two or more of these active hydrogen-containing compounds may be used.

  The molecular structure of the liquid polyurethane polymer is usually linear, but it may be cyclic, branched, or three-dimensional network.

  The number average molecular weight of the liquid polyurethane polymer is not particularly limited, but is 500 to 1,000,000, more preferably 3,000 to 100,000, when measured by GPC.

  The (meth) acrylic polymer is an organic polymer mainly composed of (meth) acrylic acid ester monomers. Here, “mainly” means that, in the monomer units constituting the (meth) acrylic polymer, 50 mol% or more is a (meth) acrylic acid ester monomer, preferably 70 mol% or more. is there.

  The molecular weight distribution of the (meth) acrylic polymer, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is not particularly limited. , Preferably less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, even more preferably 1.5 or less, particularly preferably 1.4 or less. Most preferably, it is 1.3 or less. When the molecular weight distribution is 1.8 or more, the viscosity increases and the handling tends to be difficult. In addition, GPC measurement in this invention uses chloroform as a mobile phase, a measurement is performed with a polystyrene gel column, and a number average molecular weight etc. can be calculated | required by polystyrene conversion.

  The number average molecular weight of the (meth) acrylic polymer is not particularly limited, but when measured by GPC, 3,000 to 200,000, which is in the range of 500 to 1,000,000, is more preferable. 000 to 160,000 is more preferred, and 8,000 to 100,000 is even more preferred. If the molecular weight is too low, the original characteristics of the (meth) acrylic polymer tend to be difficult to be expressed, while if it is too high, handling tends to be difficult.

  The (meth) acrylic polymer is preferably a (co) polymer of one or more types of (meth) acrylate monomers, but can be copolymerized with (meth) acrylate monomers. Other monomer components may be copolymerized. The (meth) acrylic acid ester monomer component is not particularly limited, and various types can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate isopropyl, (meth) acrylate-n-butyl, (meth) acryl Isobutyl acid, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, (meta ) Toluyl acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid-3 Methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf Fluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, and the like.

  Particularly preferred (meth) acrylic acid ester monomers include acrylic acid alkyl ester monomers, specifically, ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate. 2-methoxybutyl acrylate.

  Moreover, the other monomer component which can be copolymerized with a (meth) acrylic acid ester monomer is not particularly limited, and various types can be used. Specifically, aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Maleimide monomers: nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Vinyl esters such as ethylene; alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These may be used alone or a plurality of these may be copolymerized.

  These (meth) acrylic polymers having at least one polymerizable carbon-carbon double bond in one molecule may be used alone or in combination of two or more.

  The (meth) acrylic polymer can be obtained by various polymerization methods, and is not particularly limited, but is preferably a radical polymerization method from the viewpoint of versatility of the monomer, ease of control, etc. Among the radical polymerizations, controlled radical polymerization Is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method” which is a kind of living polymerization. Living radical polymerization, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Application Publication No. 2006-291073.

  The atom transfer radical polymerization, which is one of preferred synthesis methods in the present invention, will be briefly described below.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is preferably used as an initiator. Specific examples include compounds described in paragraphs [0040] to [0064] of JP-A-2005-232419.

  In order to obtain a vinyl polymer having two or more alkenyl groups capable of hydrosilylation in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. preferable.

  There is no restriction | limiting in particular as a vinyl-type monomer used in atom transfer radical polymerization, All the vinyl-type monomers mentioned above can be used conveniently.

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium. Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

  As a method for introducing a polymerizable carbon-carbon double bond into the (meth) acrylic polymer, a known method can be used. For example, the method described in paragraphs [0080] to [0091] of JP-A-2004-203932 can be mentioned, and the following method is preferable.

(Introduction method 1)
A method in which the terminal halogen group of the (meth) acrylic polymer of the general formula (3) is substituted with a compound having a polymerizable carbon-carbon double bond of the general formula (4).
-CR ² R ³ X (3)
(In the formula, R ² and R ³ are groups bonded to the ethylenically unsaturated group of the (meth) acrylic monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ^a ) = CH ₂ (4)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

  The (meth) acrylic polymer having a terminal structure represented by the general formula (3) is prepared by using the above-described organic halide or sulfonyl halide compound as an initiator and a (meth) acrylic monomer as a transition metal complex as a catalyst. Although it is produced by a polymerization method or a method of polymerizing a (meth) acrylic monomer using a halogen compound as a chain transfer agent, the former is preferred.

Formula is not particularly restricted but includes compounds represented by (4), specific examples of R ^a are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (4) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (3), More preferably, it is 1.0-1.2 equivalent. The solvent for carrying out this reaction is not particularly limited but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric Triamide, acetonitrile, etc. are used. Although the temperature which performs reaction is not limited, Generally it is 0-150 degreeC, In order to hold | maintain a polymeric terminal group, Preferably it carries out at room temperature-100 degreeC.

(Introduction method 2)
A method of reacting a compound represented by the general formula (5) with a (meth) acrylic polymer having a hydroxyl group at the terminal.
XC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

(Introduction method 3)
A method of reacting a diisocyanate compound with a (meth) acrylic polymer having a hydroxyl group at the terminal, and reacting a residual isocyanate group with a compound represented by the following general formula (6).
HO—R ^b —OC (O) C (R ^a ) ═CH ₂ (6)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. R ^b represents a divalent organic group having 2 to 20 carbon atoms.)

  Among these methods, (Introduction method 1) is most preferable because it is easy to control.

<Photoinitiator (B)>
In the curable composition of the present invention, a photopolymerization initiator (B) is used in order to cure quickly or to obtain a cured product having sufficient properties.

  Examples of the photopolymerization initiator (B) include a photoradical initiator, a photoanion initiator, a near-infrared photopolymerization initiator, and the like. A photoradical initiator and a photoanion initiator are preferred, and a photoradical initiator is particularly preferred. preferable.

  Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoin Tyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- Examples include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl and the like.

  Among these, α-hydroxy ketone compounds (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone, etc.), phenyl ketone derivatives (for example, acetophenone, propiophenone, benzophenone, 3-methyl) Acetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4-chloro-4′-benzylbenzophenone, bis (4-dimethylaminophenyl) ketone, etc.) are preferred.

  In addition, when using the said photoinitiator, polymerization inhibitors, such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, para tertiary butyl catechol, can also be added as needed.

  Although the addition amount of a photoinitiator (B) does not have a restriction | limiting in particular, 0.001-10 weight part is preferable with respect to 100 weight part of (A) component from the point of sclerosis | hardenability and storage stability. 01-5 weight part is more preferable.

<Peroxide polymerization initiator (C)>
Although it does not necessarily limit as a peroxide type initiator (C) of this invention, A well-known peroxide can be used arbitrarily. These peroxide-based initiators may be used alone or in combination of two or more. For example, inorganic peroxide initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate, and organic peroxide initiators such as t-butyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, Hydroperoxides such as diisopropylbenzene hydroperoxide; Peroxyesters such as t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxydecanoate; 1,5-di-t- Examples include peroxyketals such as butylperoxy-3,3,5-trimethylcyclohexane; ketone peroxides such as ethyl acetoacetate; diacyl peroxides such as benzoyl peroxide. Of these, from the viewpoint of curability and storage stability, organic peroxide initiators are preferred, hydroperoxides are more preferred, and cumene hydroperoxide is particularly preferred.

  (C) As a compounding quantity of a component, from a viewpoint of sclerosis | hardenability and storage stability, Preferably it is 0.01-20 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.1-10 weight Part.

<< Curing Accelerator (II) >>
Hereinafter, the curing accelerator (II) will be described in detail.

<Reducing agent (D)>
The reducing agent (D) of the present invention acts on the peroxide-based initiator (C) described above, and radical active species are generated from the peroxide-based polymerization initiator by an oxidation-reduction reaction that occurs between the two. It is generated and used as a reaction initiator for a redox polymerization reaction that initiates a curing reaction. The reducing agent (D) of the present invention uses a fourth-period transition metal compound (E) and an amine compound (F) in combination.

  The amount of the reducing agent (D) is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the component (A). The weight ratio of the transition metal compound (E) in the fourth period to the amine compound (F) in the reducing agent (D) (transition metal compound in the fourth period / amine compound) is 1/5 to 1/30. It is preferable.

(4th period transition metal compound (E))
Examples of the metal of the transition metal compound (E) in the fourth period include copper, zinc, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, and the like. Among these, a metal compound containing vanadium Is preferred.

  The transition metal compound (E) in the fourth period is preferably at least one selected from cobalt, copper, naphthenic acid or octylic acid metal soap of vanadium, and acetylacetone complex of vanadium, and the acetylacetone complex of vanadium is Particularly preferred.

(Amine compound (F))
As the amine compound (F), triethylamine, tripropylamine, tributylamine, ethylenediethanolamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N-methyldiethanolamine, N, N-dimethylaniline N, N-dimethyltoluidine, selected from tributylamine, N, N-dimethyltoluidine, N, N, N′N′-tetramethyl-1,6-hexanediamine, N-methyldiethanolamine At least one of them is preferable, and among them, tributylamine is particularly preferable from the viewpoint of curing speed.

<< Other ingredients >>
In the two-component curable liquid composition of the present invention, various compounding agents are added to the curable composition (I) and / or the curing accelerator (II), which are the components, according to the intended physical properties. It doesn't matter.

<Filler>
In the curable composition (I) and / or the curing accelerator (II) of the present invention, a filler may be used as necessary. Although it does not specifically limit as a filler, The filler of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0158] is mentioned. Of these fillers, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

  The said filler may be used independently according to the objective and necessity, and may use 2 or more types together. The total amount of addition when a filler is used for the curable composition (I) and / or the curing accelerator (II) is contained in the curable composition (I) and / or the curing accelerator (II) (A ) It is preferable to use the filler in the range of 5 to 1000 parts by weight, more preferably in the range of 20 to 500 parts by weight, and in the range of 40 to 300 parts by weight with respect to 100 parts by weight of the total component. It is particularly preferred to use it. If the blending amount is less than 5 parts by weight, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts by weight, the work of the curable composition May decrease.

<Antioxidant>
In the curable composition (I) and / or the curing accelerator (II) of the present invention, various antioxidants may be used as necessary. These antioxidants include p-phenylenediamine-based antioxidants, amine-based antioxidants, hindered phenol-based antioxidants, secondary antioxidants such as phosphorus-based antioxidants, sulfur-based antioxidants, etc. Is mentioned.

  The total amount of the antioxidant when added to the curable composition (I) and / or the curing accelerator (II) is not particularly limited, but the curable composition (I) and / or the curing accelerator (II). The total amount of component (A) contained in 100) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

<Plasticizer>
A plasticizer can be mix | blended with curable composition (I) and / or hardening accelerator (II) of this invention as needed.
Although it does not specifically limit as a plasticizer, For example, the plasticizer of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0173] is mentioned by the objectives, such as adjustment of a physical property and adjustment of a property. Among these, polyester plasticizers and vinyl polymers are preferable because the effect of reducing the viscosity is remarkable and the volatilization rate during the heat resistance test is low. Further, by adding a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15000, the viscosity of the curable composition and the tensile strength and elongation of the cured product obtained by curing the curable composition are added. The mechanical properties such as the above can be adjusted, and the initial physical properties can be maintained over a long period of time as compared with the case where a low molecular plasticizer which is a plasticizer not containing a polymer component in the molecule is used. Although not limited, the polymer plasticizer may or may not have a functional group.

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out over time when exposed to heat or in contact with a liquid, and the initial physical properties may not be maintained over a long period of time. Moreover, when molecular weight is too high, a viscosity will become high and there exists a tendency for workability | operativity to fall.

  Of these polymer plasticizers, those compatible with the vinyl polymer are preferred. Of these, vinyl polymers are preferred from the viewpoints of compatibility, weather resistance, and heat aging resistance. Among the vinyl polymers, (meth) acrylic polymers are preferable, and acrylic polymers are more preferable. Examples of the method for synthesizing the acrylic polymer include those obtained by conventional solution polymerization and solvent-free acrylic polymers. The latter acrylic plasticizer does not use a solvent or a chain transfer agent, and is a high-temperature continuous polymerization method (USP 4414370, JP 59-6207, JP-B-5-58005, JP 1-331522, USP 5010166). It is more preferable for the purpose of the present invention. Examples thereof include, but are not limited to, Toagosei UP series and the like (see the Industrial Materials October 1999 issue). Of course, the living radical polymerization method can also be mentioned as another synthesis method. According to this method, the molecular weight distribution of the polymer is narrow and the viscosity can be lowered, and the atom transfer radical polymerization method is more preferable, but it is not limited thereto.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.8. 1.7 or less is more preferable, 1.6 or less is still more preferable, 1.5 or less is more preferable, 1.4 or less is especially preferable, and 1.3 or less is the most preferable.

  The plasticizer containing the above-mentioned polymer plasticizer may be used alone or in combination of two or more, but is not necessarily required. Further, if necessary, a high molecular plasticizer may be used, and a low molecular plasticizer may be further used in a range that does not adversely affect the physical properties. These plasticizers can also be blended at the time of polymer production.

  The total amount of the plasticizer used in the curable composition (I) and / or the curing accelerator (II) is not limited, but is included in the curable composition (I) and / or the curing accelerator (II). The amount of the component (A) is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total component. If the amount is less than 1 part by weight, the effect as a plasticizer tends to be hardly exhibited, and if it exceeds 100 parts by weight, the mechanical strength of the cured product tends to be insufficient.

<Reactive diluent>
In addition to the plasticizer, a reactive diluent described below may be used in the present invention. If a low-boiling compound that can be volatilized during curing is used as a reactive diluent, it will change shape before and after curing, or it may adversely affect the environment due to volatiles. An organic compound having a boiling point of 100 ° C. or higher is particularly preferable.

  Specific examples of the reactive diluent include 1-octene, 4-vinylcyclohexene, allyl acetate, 1,1-diacetoxy-2-propene, methyl 1-undecenoate, 8-acetoxy-1,6-octadiene and the like. However, it is not limited to these.

  The total addition amount when a reactive diluent is used for the curable composition (I) and / or the curing accelerator (II) is included in the curable composition (I) and / or the curing accelerator (II). (A) Preferably it is 0.1-100 weight part with respect to 100 weight part of total components, More preferably, it is 0.5-70 weight part, More preferably, it is 1-50 weight part.

<Light stabilizer>
If necessary, a light stabilizer may be added to the curable composition (I) and / or the curing accelerator (II) of the present invention. Various types of light stabilizers are known, and are described in, for example, “Antioxidant Handbook” issued by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

  Although it is not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable, and specifically, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 Benzotriazole compounds such as Tinuvin 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as Tinuvin 120 (manufactured by Ciba Geigy Japan).

  Further, hindered amine compounds are also preferable, and specific examples of such compounds include those described in JP-A-2006-274084, but are not limited thereto. Furthermore, since the combination of the ultraviolet absorber and the hindered amine compound may exhibit more effect, it is not particularly limited, but may be used in combination, and it is preferable to use in combination.

  The light stabilizer may be used in combination with the above-described antioxidant, and it is particularly preferable because the effect is further exhibited and the weather resistance may be improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Ciba Geigy Japan, Inc.) in which a light stabilizer and an antioxidant are mixed in advance may be used.

  The total amount of the light stabilizer added when used in the curable composition (I) and / or the curing accelerator (II) is contained in the curable composition (I) and / or the curing accelerator (II). (A) It is preferable that it is the range of 0.1-10 weight part with respect to 100 weight part of total components. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 10 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Adhesive agent>
An adhesiveness-imparting agent can be added to the curable composition (I) and / or the curing accelerator (II) of the present invention for the purpose of further improving the substrate adhesion. A silyl group-containing compound and a vinyl monomer having a polar group are preferred, and a silane coupling agent and an acidic group-containing vinyl monomer are more preferred. Specific examples thereof include the adhesion-imparting agent described in paragraph [0184] of JP-A-2005-232419.

  As silane coupling agents, other than carbon atoms and hydrogen atoms, such as epoxy groups, isocyanate groups, isocyanurate groups, carbamate groups, amino groups, mercapto groups, carboxyl groups, halogen groups, (meth) acryl groups, etc. in the molecule. A silane coupling agent having both an organic group having an atom and a crosslinkable silyl group can be used.

  Specific examples thereof include a silane coupling agent having both a crosslinkable silyl group and an organic group having atoms other than carbon atoms and hydrogen atoms described in paragraph [0185] of JP-A-2005-232419. Among these, alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are more preferable from the viewpoint of curability and adhesiveness.

  As a vinyl monomer having a polar group, as a carboxyl group-containing monomer, (meth) acrylic acid, acryloxypropionic acid, citraconic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid or esters thereof, And maleic anhydride and derivatives thereof. Examples of the ester of the galboxyl group-containing monomer include 2- (meth) acryloyloxyethyl succinic acid and 2- (meth) acryloyloxyethyl hexahydrophthalic acid. Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, (meth) acryl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido-2-methylpropane sulfone, and salts thereof. Can be mentioned. Furthermore, as the phosphoric acid group-containing monomer, 2-((meth) acryloylcyethyl phosphate), 2- (meth) acryloyloxypropyl phosphate, 2- (meth) acryloyloxy-3-chloropropyl phosphate, 2 -(Meth) acryloyloxyethyl phenyl phosphate and the like. Of these, phosphate group-containing monomers are preferred. The monomer may have two or more polymerizable groups.

  Specific examples of the adhesion-imparting agent other than the silane coupling agent and the polar group-containing vinyl monomer are not particularly limited. For example, epoxy resins, phenol resins, modified phenol resins, cyclopentadiene-phenol resins, xylene resins , Coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin sulfur, alkyl titanates, aromatic polyisocyanate and the like.

  The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total component (A) contained in the curable composition (I) and / or the curing accelerator (II). . If it is less than 0.01 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, the physical properties of the cured product tend to be lowered. Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

  The adhesiveness-imparting agent may be used alone or in combination of two or more.

<Solvent>
The curable composition (I) and / or the curing accelerator (II) of the present invention can be mixed with a solvent as necessary. Solvents that can be blended include, for example, aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone A solvent etc. are mentioned. These solvents may be used during production of the polymer.

<Other additives>
In the curable composition (I) and / or the curing accelerator (II) of the present invention, various additives are added as necessary for the purpose of adjusting the physical properties of the curable composition or its cured product. Also good. Examples of such additives include, for example, flame retardants, anti-aging agents, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, etc. Is given. These various additives may be used alone or in combination of two or more. Specific examples of such additives include, for example, each specification of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. It is described in.

<< Applying amount of curable composition (I) and curing accelerator (II) >>
The ratio of the coating amount when the curable composition (I) and the curing accelerator (II) are respectively applied to a bonded base material (translucent protective cover, image display module, etc.) is as follows. The weight ratio of the curable composition (I) to the curing accelerator (II), that is, the curable composition (I) / the curing accelerator (II) is preferably 0.1 to 100, more preferably 1 to 50. It is preferable to apply the curable composition component (I) and the curing accelerator (II) to the bonded substrate so that

Photocurable composition for FPD bonding The two-part photocurable composition of the present invention can be used for FPD bonding. Specifically, for example, as shown in FIGS. 3 to 6, the FPD bonding method is performed by adding a curing accelerator (II) to the translucent protective cover and / or the translucent protective cover of the image display module. Apply only to the dark areas where light does not reach when the image display module is bonded, and apply the curable composition (I) onto the bonded substrate (translucent protective cover, image display module, etc.) It is preferable to include a process of superimposing the bonded substrates, a curing process by redox polymerization reaction, and a curing process by light.

  The bonding substrate is a translucent protective cover and an image display module, but the translucent protective cover is not particularly limited, but is disposed on the screen display module, for example, a polyester resin, an acrylic resin, The cover is made of a resin such as polycarbonate resin or glass, and has a function of protecting the screen display module surface from scratches and damage when dropped, and also has a design function. The shape and structure of the translucent protective cover are not particularly limited. For example, the translucent protective cover may have a multilayer structure made of several kinds of resins, or a single layer structure formed of a single material. In addition, if necessary, the protective cover surface may be coated with a film or a film to prevent fingerprint adhesion, light reflection prevention, reflection and glare prevention, and the protective cover is provided with a touch panel function. Or a protective cover and a touch panel may be bonded together. Although it does not specifically limit with an image display module, A well-known thing can be used widely, For example, they are a liquid crystal module, an organic EL module, a plasma display module etc. Further, if necessary, the image display module may be provided with a touch panel, or the image display module may be attached with a touch panel.

<< Usage >>
The site where the two-part photocurable composition of the present invention is used is not particularly limited. However, the liquid crystal of a touch panel or a mobile phone, the organic EL or organic TFT screen, the liquid crystal of a computer, the organic EL or organic TFT screen, car navigation system Liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, and the like.

  The present invention includes an electric / electronic device on which a flat panel display obtained by applying and curing the curable composition for FPD bonding is mounted.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

<Method for measuring number average molecular weight and molecular weight distribution>
“Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). As the GPC column, those filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; Showa Denko KK) and chloroform as the GPC solvent were used.

<Method for measuring the number of functional groups per molecule of polymer>
The number of functional groups per molecule of the polymer was calculated by analyzing the functional group concentration by ¹ H-NMR.

<Method of judging curability by photopolymerization reaction>
After injecting the curable composition (I) into a polyethylene container having a diameter of 25 mm so that the liquid height is about 5 mm, integration at 365 nm using a UV irradiation device (Light Hammer 6, Fusion UV system Japan). After irradiating UV light so that the amount of light was 6000 mJ / cm ² , it was confirmed whether the curable composition (I) was cured. An electrodeless lamp bulb (H bulb, manufactured by Fusion UV system Japan) was used as a UV light irradiation lamp.

<Method of judging curability by redox polymerization reaction>
The curable composition (I) and the curing accelerator (II) were poured into a polyethylene container having a diameter of 25 mm at an arbitrary ratio, and then stirred and mixed, and the time until curing was measured.

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Examples 1-2)
Table 1 shows the amount of each raw material used.
(1) Polymerization process n-butyl acrylate was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, cuprous bromide and a part of all n-butyl acrylate (described as initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1), diethyl-2,5-dibromoadipate (DBAE) or ethyl α-bromobutyrate (EBB) as an initiator are added and mixed, and the temperature of the mixture is brought to about 80 ° C. At the adjusted stage, pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining n-butyl acrylate (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during polymerization is shown in Table 2 as polymerization triamine. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.
(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the reaction vessel gas phase. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.
(3) First crude purification Butyl acetate was used as a diluent solvent for the polymer. The concentrate of (2) was diluted with about 100 to 150 kg of butyl acetate with respect to 100 kg of the polymer, and a filter aid (Radiolite R900, Showa Chemical Industry Co., Ltd.) was added. After introducing oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.
(4) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), potassium acrylate (about 2 molar equivalents relative to terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P1] and [P2] having Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
(A) 50 g of the polymer [P1] obtained in Production Example 1 as the component, 50 g of the polymer [P2] obtained in Production Example 2, 2-hydroxyethyl acrylate (trade name: Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd. ) 10 g, tetrahydrofurfuryl acrylate (trade name Light Ester THF-A, manufactured by Kyoeisha Chemical Co., Ltd.) 10 g, dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 10 g, (B ) DAROCUR1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.8 g and Lucirin TPO (2,4,6-trimethyl) Benzoyl-diphenylphosphine oxide, Ciba Specialty Chemicals 0.15 g, as a component (C), 0.65 g of cumene hydroxy peroxide (trade name Park Mill H, manufactured by NOF Corporation) was sufficiently stirred and mixed to prepare a curable composition (I). . In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 10 g of tributylamine (TBA, manufactured by Wako Pure Chemical Industries, Ltd.), and dimethylacrylamide as other components (DMAA, manufactured by Kojin Co., Ltd.) 9 g, polymer [P1] 40 g obtained in Production Example 1, polymer [P2] 60 g obtained in Production Example 2, light ester HOA 10 g, light ester THF-A 5 g, A curing accelerator (II) was prepared by sufficiently stirring and mixing 5 g of FA-513M. When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 5 minutes.

  The obtained curable composition (I) was applied to the center of the ITO glass, and the curable composition (II) was applied to the ITO glass and bonded together (FIG. 1). After standing at room temperature for 24 hours, the resistance value of ITO glass was measured with a tester as shown in Fig. 2 and when exposed to an environment with a temperature of 65 ° C and a humidity of 90% for one week, the resistance value hardly changed from 283Ω to 286Ω. It was. The results are shown in Table 2.

(Example 2)
Using the curable composition (I) obtained in Example 1, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , produced by Sigma-Aldrich), N, N, N′N '-Tetramethylhexanediamine (manufactured by Wako Pure Chemical Industries, Ltd.) 10 g, as other components, 9 g of dimethylacrylamide (DMAA, manufactured by Kojin Co., Ltd.), 40 g of the polymer [P1] obtained in Production Example 1, A curing accelerator (II) was prepared by sufficiently stirring and mixing 60 g of the polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A, and 5 g of FA-513M.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 5 minutes. The results are shown in Table 2.

(Example 3)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 10 g of N-methyldiethanolamine (manufactured by Wako Pure Chemical Industries), dimethylacrylamide (as other components) DMAA (manufactured by Kojin Co., Ltd.) 9 g, polymer [P1] 40 g obtained in Production Example 1, polymer [P2] 60 g obtained in Production Example 2, light ester HOA 10 g, light ester THF-A 5 g, FA-513M 5 g Was sufficiently mixed with stirring to prepare a curing accelerator (II).

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 5 minutes. The results are shown in Table 2.

Example 4
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 10 g of N, N′-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.), 9 g of dimethylacrylamide (DMAA, manufactured by Kojin Co., Ltd.), 40 g of the polymer [P1] obtained in Production Example 1, 60 g of the polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A, A curing accelerator (II) was prepared by sufficiently stirring and mixing 5 g of FA-513M.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10 to 1, and cured in 15 minutes. The results are shown in Table 2.

(Example 5)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 10 g of dimethyl-p-toluidine (manufactured by Wako Pure Chemical Industries), and dimethylacrylamide as other components (DMAA, manufactured by Kojin Co., Ltd.) 9 g, polymer [P1] 40 g obtained in Production Example 1, polymer [P2] 60 g obtained in Production Example 2, light ester HOA 10 g, light ester THF-A 5 g, FA- A curing accelerator (II) was prepared by sufficiently stirring and mixing 513M5g.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 30 minutes. The results are shown in Table 2.

(Example 6)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich) 1 g, ethylenethiourea (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g, and as other components, dimethylacrylamide (DMAA, 9 g, polymer [P1] 40 g obtained in Production Example 1, polymer [P2] 60 g obtained in Production Example 2, 10 g light ester HOA, 5 g light ester THF-A, 5 g FA-513M By stirring and mixing, a curing accelerator (II) was prepared.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 5 minutes. The results are shown in Table 2.

(Comparative Example 1)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 9 g of dimethylacrylamide (DMAA, manufactured by Kojin Co.) as other components, obtained in Production Example 1 40 g of the obtained polymer [P1], 60 g of the polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A, and 5 g of FA-513M were prepared by sufficiently stirring and preparing a curing accelerator (II). did.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. Further, when the curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1, the viscosity only increased. The results are shown in Table 2.

(Comparative Example 2)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). Further, as component (D), 10 g of tributylamine (TBA, manufactured by Wako Pure Chemical Industries, Ltd.) and 40 g of polymer [P1] obtained in Production Example 1 as the other components, and polymer obtained in Production Example 2 [ P2] 60 g, light ester HOA 10 g, light ester THF-A 5 g, and FA-513M 5 g were sufficiently stirred and mixed to prepare a curing accelerator (II).

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. Further, when the curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1, they were not cured. The results are shown in Table 2.

(Comparative Example 3)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). Further, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 1 g of copper naphthenate (manufactured by Kanto Chemical Co., Ltd.) and other components are obtained in Production Example 1. Curing accelerator (II) was prepared by sufficiently stirring and mixing 40 g of polymer [P1], 60 g of polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A and 5 g of FA-513M. .

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. Further, when the curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1, they were not cured. The results are shown in Table 2.

(Comparative Example 4)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 1 g of L (+)-ascorbic acid (Wako Pure Chemical Industries, Ltd.) 40 g of the polymer [P1] obtained in Example 1, 60 g of the polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A, and 5 g of FA-513M were mixed sufficiently with a curing accelerator ( II) was prepared.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. Further, when the curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1, they were not cured. The results are shown in Table 2.

(Comparative Example 5)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). In addition, as component (D), vanadium acetylacetonate complex (V (acac) ₃ , Sigma-Aldrich) 1 g, pentaerythritol tetrakis (3-mercaptopropionate) (SC Organic Chemical) 1 g Other components As described above, 40 g of the polymer [P1] obtained in Production Example 1, 60 g of the polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A, and 5 g of FA-513M were cured with sufficient stirring. Accelerator (II) was prepared.

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10: 1 and cured in 10 minutes. The obtained curable composition (I) was applied to the center of the ITO glass, and the curable composition (II) was applied to the ITO glass and bonded together (FIG. 1). After standing at room temperature for 24 hours and measuring the resistance value of ITO glass with a tester as shown in Fig. 2 and exposing it to an environment with a temperature of 65 ° C and a humidity of 90% for one week, the resistance value was measured again. Rose to a value above the measurement limit. The results are shown in Table 2.

(Comparative Example 6)
The curable composition (I) obtained in Example 1 was used as the curable composition (I). Further, as component (D), 1 g of vanadium acetylacetonate complex (V (acac) ₃ , manufactured by Sigma-Aldrich), 5 g of dodecyl mercaptan (manufactured by Tokyo Chemical Industry Co., Ltd.) and other components are obtained in Production Example 1. Curing accelerator (II) was prepared by sufficiently stirring and mixing 40 g of polymer [P1], 60 g of polymer [P2] obtained in Production Example 2, 10 g of light ester HOA, 5 g of light ester THF-A and 5 g of FA-513M. .

  When only the curable composition (I) was irradiated with UV, it was confirmed that it cured without problems. The curable composition (I) and the curing accelerator (II) were stirred and mixed at a weight ratio of 10 to 1, and cured in 10 minutes. The obtained curable composition (I) was applied to the center of the ITO glass, and the curable composition (II) was applied to the ITO glass and bonded together (FIG. 1). After standing at room temperature for 24 hours and measuring the resistance value of ITO glass with a tester as shown in Fig. 2 and exposing it to an environment with an air temperature of 65 ° C and a humidity of 90% for one week, the resistance value was measured again. It rose to a value above the measurement limit of the tester. The results are shown in Table 2.

(Example 7)
As shown in FIG. 3, the curing accelerator (II) obtained in Example 1 was a glass plate of 50 mm × 70 mm × 0.7 mm (a black frame coating having a width of 5 mm as a dark portion blocking light at a peripheral portion and a thickness of about 30 μm). As shown in FIG. 4, 0.03 g was applied to the black frame coated portion (dark portion) of the glass plate with black print, and then 0.7 g of the curable composition (I) was applied to the portion not coated with black frame. And a 3.5 inch liquid crystal module (model number: LQ035QDG01, manufactured by Sharp Corporation). After the above-mentioned glass plate with black print and the 3.5 inch liquid crystal module are overlaid so as to have a specific thickness (FIG. 5), the UV irradiation device (Light Hammer 6, made by Fusion UV system Japan) is left for 10 minutes. ) Was irradiated with UV light so that the integrated light quantity at 365 nm was 6000 mJ / cm 2 (FIG. 6). Immediately after UV light irradiation, the glass plate with black print and the 3.5-inch liquid crystal module are peeled off, and the curable composition (I) present in the light transmitting part (translucent part) is cured. It was confirmed. Note that an electrodeless lamp bulb (H bulb, manufactured by Fusion UV system Japan) was used as a UV light irradiation lamp.

  After the bonded sample is cured at 23 ° C. and 50% relative humidity for 1 hour, a toothpick is inserted from the edge of the glass, and the curable composition (I) and the curing accelerator (II) in the dark part are cured. It was confirmed. The results are shown in Table 3.

(Comparative Example 7)
As shown in FIG. 3, the curing accelerator (II) obtained in Comparative Example 1 is a 50 mm × 70 mm × 0.7 mm glass plate (a black frame coating having a width of 5 mm and a thickness of about 30 μm as a dark portion that blocks light at the periphery). As shown in FIG. 4, 0.03 g was applied to the black frame coated portion (dark portion) of the glass plate with black print, and then 0.7 g of the curable composition (I) was applied to the portion not coated with black frame. And a 3.5 inch liquid crystal module (model number: LQ035QDG01, manufactured by Sharp Corporation). After the above-mentioned glass plate with black print and the 3.5 inch liquid crystal module are overlaid so as to have a specific thickness (FIG. 5), the UV irradiation device (Light Hammer 6, made by Fusion UV system Japan) is left for 10 minutes. ) Was irradiated with UV light so that the integrated light quantity at 365 nm was 6000 mJ / cm 2 (FIG. 6). Immediately after UV light irradiation, the glass plate with black print and the 3.5-inch liquid crystal module are peeled off, and the curable composition (I) present in the light transmitting part (translucent part) is cured. It was confirmed. Note that an electrodeless lamp bulb (H bulb, manufactured by Fusion UV system Japan) was used as a UV light irradiation lamp.

  After the bonded sample is cured at 23 ° C. and 50% relative humidity for 1 hour, the toothpick is inserted from the edge of the glass, and the dark portion of the curable composition (I) and the curing accelerator (II) are not cured. It was confirmed. The results are shown in Table 3.

(Comparative Example 8)
As shown in FIG. 3, the curing accelerator (II) obtained in Comparative Example 2 is a 50 mm × 70 mm × 0.7 mm glass plate (a black frame coating having a width of 5 mm and a thickness of about 30 μm as a dark portion that blocks light at the periphery). As shown in FIG. 4, 0.03 g was applied to the black frame coated portion (dark portion) of the glass plate with black print, and then 0.7 g of the curable composition (I) was applied to the portion not coated with black frame. And a 3.5 inch liquid crystal module (model number: LQ035QDG01, manufactured by Sharp Corporation). After the above-mentioned glass plate with black print and the 3.5 inch liquid crystal module are overlaid so as to have a specific thickness (FIG. 5), the UV irradiation device (Light Hammer 6, made by Fusion UV system Japan) is left for 10 minutes. ) Was irradiated with UV light so that the integrated light quantity at 365 nm was 6000 mJ / cm 2 (FIG. 6). Immediately after UV light irradiation, the glass plate with black print and the 3.5-inch liquid crystal module are peeled off, and the curable composition (I) present in the light transmitting part (translucent part) is cured. It was confirmed. Note that an electrodeless lamp bulb (H bulb, manufactured by Fusion UV system Japan) was used as a UV light irradiation lamp.

  After the bonded sample is cured at 23 ° C. and 50% relative humidity for 1 hour, the toothpick is inserted from the edge of the glass, and the dark portion of the curable composition (I) and the curing accelerator (II) are not cured. It was confirmed. The results are shown in Table 3.

  From comparison between Examples 1 to 6 and Comparative Examples 1 and 2, the transition metal compound (E) in the fourth period and the amine compound (F) are used together as the reducing agent (D), so that it is rapidly cured even at room temperature. A resin composition can be provided. From the comparison between Examples 1 to 6 and Comparative Examples 3 to 4, the combination of the transition metal compound and the amine in the fourth period is particularly effective in terms of the curing rate among the combinations of the reducing agents. The combination was shown to be ineffective.

  Further, from comparison between Example 1 and Comparative Examples 5 and 6, mercaptans are also effective in increasing the curing rate, but it is shown that the resin composition containing them corrodes the ITO glass and increases the resistance value, On the other hand, tributylamine has been shown to increase only the cure rate without affecting the corrosion of the ITO glass. Further, from the comparison between Example 7 and Comparative Examples 7 and 8, after limitedly applied in advance to the dark part, the curable composition (I) was applied so as not to come into contact with the curing accelerator (II). In the FPD laminating method in which light is irradiated after the product (I) is diffused to come into contact with the curing accelerator (II), a transition metal compound of the fourth period (as a reducing agent (D) of the curing accelerator (II) ( By using both E) and the amine compound (F), it is possible to provide a two-pack type photocurable composition for FPD laminating that can be rapidly cured in the dark part.

  According to the present invention, a two-part photocurable composition that can be rapidly cured by light, has no fear of affecting FPD operability, and quickly cures even in a dark part that is not exposed to light. An electric / electronic device equipped with an FPD obtained by coating and curing can be provided.

1. Curable composition (I)
2. Raw glass 3. Curing accelerator (II)
4). ITO glass Resistance measurement point Cover glass 7. Dark part 8. Liquid crystal module 9. Redox curing part 10. Photocuring part

Claims (7)

Curable composition (I) containing compound (A) having at least one polymerizable carbon-carbon double bond in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) And a curing accelerator (II) containing a reducing agent (D), a two-part photocurable composition comprising:
Containing both the transition metal compound (E) and amine compound (F) of the fourth period as the reducing agent (D) ,
The transition metal compound (E) is at least one selected from cobalt, copper, vanadium naphthenic acid or octylate metal soap and vanadium acetylacetone complex,
The amine compound (F) is at least one selected from tributylamine, N, N-dimethyltoluidine, N, N, N′N′-tetramethyl-1,6-hexanediamine and N-methyldiethanolamine. A two-component photocurable composition characterized by the above. The polymerizable carbon-carbon double bond of the component (A) has the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein (R ^a ) represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The two-component photocurable composition according to claim 1, wherein the two-component photocurable composition is represented by the formula: The two-part photocurable composition according to claim 1 or 2 , wherein the peroxide-based polymerization initiator (C) is cumene hydroxyperoxide. The amount of the photopolymerization initiator (B) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the component (A), and the amount of the peroxide polymerization initiator (C) is 100 parts by weight of the component (A). The content is 0.01 to 20 parts by weight with respect to parts by weight, and the reducing agent (D) is 0.01 to 10 parts by weight with respect to 100 parts by weight of component (A). The two-component photocurable composition according to any one of to 3 . The weight ratio of the transition metal compound (E) in the fourth period to the amine compound (F) (transition metal compound in the fourth period / amine compound) is 1/5 to 1/30. 5. The two-component photocurable composition according to any one of 4 above. The two-component photocurable composition according to any one of claims 1 to 5 , wherein the two-component photocurable composition is for FPD bonding. An electric / electronic device equipped with an FPD obtained by applying and curing the two-pack type photocurable composition for FPD bonding according to claim 6 .