WO2013051552A1 - Method for manufacturing flat panel displays, bonding method, and photocurable composition for bonding flat panel displays - Google Patents

Abstract

The purpose of the present invention is to provide: a photocurable liquid composition for bonding flat panel displays that can be rapidly cured by light, and that cures easily and quickly even in dark spaces; and flat panel displays with good quality of appearance in designed sections. This method for manufacturing flat panel displays uses a two-component photocurable composition for bonding flat panel displays, which comprises a curable composition (I) containing a compound (A) having, on average, at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a peroxide-base polymerization initiator (C), and a curing accelerator (II) containing a reducing agent (D). Said method is achieved by applying the curing accelerator (II) only to dark spaces that are not reached by light.

Description

[Replenishment based on Rule 26 19.10.2012] FPD manufacturing method, bonding method, and photocurable composition for FPD bonding

The present invention relates to a two-part photocurable composition comprising a curable composition (I) and a curing accelerator (II), an FPD manufacturing method using the curable composition, an FPD bonding method, and the curing The present invention relates to an electric / electronic device equipped with an FPD obtained by applying and curing an adhesive 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 providing design to mobile phones and touch panels, the area where UV light, which is a trigger for curing, does not transmit increases, and there is an unreacted part. There is a problem that you can As a specific example of the defective part, decoration is applied to the periphery of the protective cover when a flat panel display (FPD) 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 when 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 other countermeasures, a combination of a UV curing initiator and a redox type curing initiator is known (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. Usually, a composition component containing an organic peroxide and a composition component containing a curing reaction accelerator are prepared separately, and both are mixed immediately before curing and then supplied to the required location. The advantage of this method is that the curing time can be arbitrarily adjusted by combining a suitable organic oxide and a curing reaction accelerator, but the cured product obtained by redox curing often exhibits strong coloration or whitening. There has been a problem that it is practically impossible to use in applications where high quality is required for appearance such as bonding of FPDs.

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

The present invention is directed to overcoming the problems set forth above. That is, an FPD that uses a method of laminating an FPD with a two-component photocurable composition that uses a UV curing initiator and a redox type curing initiator in combination, provides high appearance quality, and cures dark areas quickly at room temperature. The manufacturing method of this, the photocurable composition for FPD bonding, and the provision of the electric / electronic device carrying FPD obtained by apply | coating and hardening it are aimed at.

In view of the above circumstances, as a result of intensive studies by the present inventors, the above-described two-part photocurable composition was obtained by averaging the polymerizable carbon-carbon double bonds in one molecule of the photocurable composition. A curable composition (I) containing at least one compound (A), a photopolymerization initiator (B), a peroxide polymerization initiator (C), and a curing accelerator containing a reducing agent (D) A method for producing an FPD using a two-component photocurable composition comprising (II), wherein the curing accelerator (II) is used as a translucent protective cover and / or a translucent protective cover of an image display module. It has been found that the above problem can be solved by using a method of manufacturing an FPD having a process of applying to a dark part where light does not reach when an image display module is bonded, and the present invention has been completed.

The curable composition (I) of the present invention has a photopolymerization initiator (B) that initiates a curing reaction upon irradiation with active energy rays and a peroxide polymerization initiator that initiates a curing reaction by acting a reducing agent. It contains an agent (C). Further, in FPD laminating with the above-described two-component photocurable composition, the curable composition (I) is supplied in a state where the curing accelerator (II) containing the reducing agent (D) is previously present in the dark part. The part where the light reaches by light irradiation is a photopolymerization reaction by a photopolymerization initiator, and the dark part is contained in each of the curable composition (I) and the curing accelerator (II) in contact with each other. In the redox polymerization reaction that generates radical active species from the peroxide polymerization initiator by the oxidation-reduction reaction that occurs between the peroxide polymerization initiator and the reducing agent, and initiates the curing reaction, It became possible to harden not only the reaching part but also the dark part easily and quickly.

Furthermore, as described above, the redox polymerization reaction tends to cause coloration of the cured product, and if the colored cured product is present on the design surface such as the display screen of the FPD, it causes problems such as poor appearance. By using the precise amount of curing accelerator (II) locally only in the dark part, which is a non-design part, and by limiting the location of the redox polymerization reaction, the colored cured product does not reach the design part. It came to provide a way to.

That is, the present invention relates to a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a peroxide polymerization initiator (C). A translucent protective cover and an image display module using a two-pack photocurable composition comprising a curable composition (I) containing a reducing agent (D) and a curing accelerator (II) containing a reducing agent (D) A method of manufacturing an FPD for bonding
A step of applying the curing accelerator (II) only to a portion of the translucent protective cover and / or image display module that becomes a dark part where light does not reach when the translucent protective cover and the image display module are bonded together. The present invention relates to a method for manufacturing an FPD characterized by comprising:

Furthermore, it is preferable to have the process of apply | coating curable composition (I) to the part which does not contact with hardening accelerator (II) of a translucent protective cover and / or an image display module.

After the curable composition (I) and the curing accelerator (II) are applied to the translucent protective cover and / or the image display module, the translucent protective cover and the image display module are bonded together to form the curable composition (I ) And the curing accelerator (II) are preferably contacted.

It is preferable to include a step of performing light irradiation after the translucent protective cover and the image display module are bonded together.

It is preferable to apply the curable composition (I) and the curing accelerator (II) only to one of the translucent protective cover or the image display module.

It is preferable to apply the curable composition (I) to one of the translucent protective cover or the image display module and to apply the curing accelerator (II) to the other.

It is preferable to apply the curable composition (I) and the curing accelerator (II) to both the translucent protective cover and the image display module.

The compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule is preferably an organic polymer.

It is preferable that the organic polymer is a (meth) acrylic polymer.

Curable composition containing compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) Affixing an FPD that bonds a translucent protective cover and an image display module through a two-component curable composition comprising a product (I) and a curing accelerator (II) containing a reducing agent (D) The curing accelerator (II) becomes a dark portion where light does not reach when the translucent protective cover and / or the image display module are bonded to each other. The curable composition (I) is applied to a part of the light-transmitting protective cover and / or the image display module which is not in contact with the curing accelerator (II), and the light-transmitting protective cover and the image display module are applied. Bonded and curable composition To a method of bonding the FPD, characterized in that contacting (I) and a curing accelerator and (II).

Contains acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) The present invention relates to a two-component FPD laminating composition comprising a curable composition (I) and a curing accelerator (II) containing a reducing agent (D).

The polymerizable carbon-carbon double bond of the component (A) is represented by 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)
It is preferable that it is group represented by these.

It is preferable that the peroxide-based polymerization initiator of component (C) is cumene hydroxy peroxide.

(D) It is preferable that the reducing agent of a component is a 4th period transition metal compound and / or an amine compound.

The present invention also relates to an electric / electronic device equipped with a flat panel display obtained by applying and curing the photocurable composition for FPD bonding described above.

According to the present invention, it is possible to obtain a photocurable composition for FPD laminating which can be rapidly cured by light and can be easily and quickly cured even in a dark part. Further, even if the cured product is colored by the redox polymerization reaction by the peroxide-based polymerization initiator in the dark portion by the method of laminating the FPD of the present invention with the same photocurable composition, the place of the redox polymerization reaction Can be specified as a dark part which is a non-design part, and an FPD with good appearance quality of the design part can be provided.

It is a figure which shows the example of supply of the curable composition component (I) and hardening accelerator component (II) of one Embodiment of this invention. It is a figure which shows the specific example of the method of FPD bonding which concerns on FIG. 1 of one Embodiment of this invention. It is a figure which shows the specific example of the FPD bonding method concerning FIG. 1 and 2 of one Embodiment of this invention. FIG. 4 is a diagram showing a specific example of an FPD bonding method according to FIGS. 1 to 3 according to an embodiment of the present invention.

The two-part photocurable liquid composition of the present invention and the method for producing FPD using the liquid composition will be described in detail below.

Two-pack composition A two-pack composition for FPD bonding used in the present invention comprises a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator. (B), comprising a curable composition (I) containing a peroxide-based polymerization initiator (C) and a curing accelerator (II) containing a reducing agent (D), and is cured by light. And
First, the curable composition (I) in the two-component composition will be described in detail.

<< Compound (A) >>
The polymerizable carbon-carbon double bond of the compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule is not particularly limited.
—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 (meth) acryloyl group represented by these is preferable.

Further, the number of (meth) acryloyl groups present in one molecule of compound (A) is not particularly limited, but is preferably more than 1 and not more than 6. (Meth) acrylic polymer (A) When the number of (meth) acryloyl groups present in one molecule is 1 or less, the curable composition tends to be insufficiently cured. There is a tendency that the structure becomes incomplete and a good molded article cannot be obtained. Further, when the (meth) acryloyl group present in one molecule of the (meth) acrylic polymer (A) increases, the resulting cured product tends to be too dense and the molded product tends to be hard and brittle. . In particular, when the number exceeds 6, the tendency becomes remarkable.

In the case of an organic polymer, the polymerizable carbon-carbon double bond of 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) 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 organic polymer is at least one selected from (saturated) hydrocarbon polymers, polyoxyalkylene polymers, liquid silicone polymers, liquid urethane polymers, and (meth) acrylic polymers. The (meth) acrylic polymer is more preferable from the viewpoint of heat resistance and light resistance.

Examples of (saturated) hydrocarbon polymers include (1) polymerizing olefinic compounds having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like as main components, (2) butadiene, isoprene, etc. 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 mention | raise | lifted. Specifically, 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).
R1 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 is preferable. The alkylene group is more preferable. The repeating unit described in the general formula (5) 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 as measured by GPC.

There is no restriction | limiting in particular as a liquid silicone type polymer, A well-known thing is mention | raise | lifted. 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 as measured by GPC.

There is no restriction | limiting in particular as a liquid polyurethane-type polymer, A well-known thing is mention | raise | lifted. 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-silane 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. 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 is preferably 3,000 to 200,000, which is in the range of 500 to 1,000,000 when measured by GPC. 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, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acryl Isobutyl acid, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (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, 2- (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 Fluoromethyl methyl, 2-methacrylic acid (meth) acrylate 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 alkyl acrylate monomers, and specifically include 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 such as: 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 an average of at least one (meth) acryloyl group in one molecule may be used alone or in combination of two or more.

The (meth) acrylic polymer (A) 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. Controlled radical polymerization is more preferred. 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 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 the 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. For example,

Etc.

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. When a copper compound is used, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine or the like is used 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. The type of the solvent is not particularly limited, and examples thereof include a solvent described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more. Polymerization can also be carried out in an emulsion system or a system using supercritical fluid CO2 as a medium. The polymerization temperature is not limited, but can be carried out in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.

As a method for introducing a polymerizable carbon-carbon double bond into the (meth) acrylic polymer, a known method can be used. Examples thereof include the methods described in paragraphs [0080] to [0091] of JP-A No. 2004-203932, and the following methods are preferable.

(Introduction method 1)
A method in which the terminal halogen group of the (meth) acrylic polymer of the general formula (3) is replaced 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 represent a group bonded to an ethylenically unsaturated group of the (meth) acrylic monomer, and 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.

The compound represented by the general formula (4) is not particularly limited, but specific examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n Represents an integer of 2 to 19), —C ₆ H ₅ , —CH ₂ OH, —CN, etc., 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, dimethylpiperidinium ion, and the like, preferably sodium ion and potassium ion. The amount of the oxyanion of the general formula (4) used is preferably 1 to 5 equivalents, more preferably 1.0 to 1.2 equivalents relative to the halogen group of the general formula (3). 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. The temperature at which the reaction is carried out is not limited, but is generally from 0 to 150 ° C., preferably from room temperature to 100 ° C. in order to retain the polymerizable terminal group.

(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, ^Ra 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)
(Wherein 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, benzoy Methyl 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.

Of 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.

The addition amount of the photopolymerization initiator (B) is not particularly limited, but is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of curability and storage stability.

<< Peroxide-based polymerization initiator (C) >>
Although it does not necessarily limit as a peroxide type initiator of (C) component used by 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 butyl peroxy-3,3,5-trimethylcyclohexane; ketone peroxides such as ethyl acetoacetate; and 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.

The amount of component (C) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A), from the viewpoints of curability and storage stability. Part.

Hereinafter, the curing accelerator (II) will be described in detail.

<< Reducing agent (D) >>
The reducing agent of component (D) of the present invention acts on the peroxide-based initiator of component (C) described above, and from the peroxide-based polymerization initiator by an oxidation-reduction reaction occurring between the two. It generates radical active species and is used as a reaction initiator for a redox polymerization reaction that initiates a curing reaction. Although it does not necessarily limit as a reducing agent which is (D) component of this invention, A well-known thing can be used arbitrarily. Although the specific example of these reducing agents is explained in full detail below, you may use individually and may use 2 or more types together. For example, copper, zinc, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, etc., metal compounds containing transition metals in the fourth period, triethylamine, tripropylamine, tributylamine, ethylenediethanolamine, N, N, Amine compounds such as N ', N'-tetramethyl-1,6-hexanediamine, N-methyldiethanolamine, N, N-dimethylaniline, N, N-dimethyltoluidine, methylthiourea, diethylthiourea, acetylthiourea, tetra Thiourea compounds such as methylthiourea and ethylenethiourea, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mer Hept propionate) thiol compound such as and the like. Among these, from the viewpoint of curability, solubility, and storage stability, a metal compound containing a transition metal in the fourth period and an amine compound are preferable. Moreover, you may add a component (A) and another compounding agent to said hardening accelerator (II) as needed.

The blending amount of component (D) is preferably 0.1 to 50% by weight, more preferably 0.5 to 50% by weight in the curing accelerator (II) from the viewpoints of curability and storage stability. is there. If it is less than 0.1% by weight, sufficient curability cannot be obtained, and if it exceeds 50% by weight, the storage stability of the curing accelerator (II) tends to be lowered.

<< Compounding agent >>
In the two-component curable 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.

<< Oligomer and / or Monomer Having Polymerizable Group >>
In the curable composition (I) and / or the curing accelerator (II) in the present invention, an oligomer having a polymerizable group and / or a monomer may be added as long as the effects of the present invention are not impaired. . A monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferred from the viewpoint of curability.

Examples of the radical polymerizable group include (meth) acryloyl group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, chloride A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Examples of the anionic polymerizable group include (meth) acryloyl groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, and vinyl ketone groups. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Specific examples of the monomer include those described in paragraphs [0123] to [0131] of JP-A-2006-265488.

Examples of the oligomer include those described in paragraph [0132] of JP-A-2006-265488.

Of the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. In addition, the number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is 3000 or less. Further, in order to improve the surface curability and reduce the viscosity for improving workability, the monomer is used. When used, it is more preferable that the molecular weight is 1000 or less because the compatibility is good.

The total amount of the polymerizable monomer and / or oligomer used in the curable composition (I) and / or the curing accelerator (II) is the curable composition (I) from the viewpoint of a decrease in the curing shrinkage rate. 200 parts or less are preferable and 100 parts or less are more preferable with respect to 100 parts by weight (hereinafter also simply referred to as “parts”) of the component (A) contained in the curing accelerator (II).

<Filler>
In the curable composition (I) and / or the curing accelerator (II) of the present invention, a filler may be used as necessary. The filler is not particularly limited, and examples thereof include those described in paragraph [0158] of JP-A-2005-232419. 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 included in the curable composition (I) and / or the curing accelerator (II) (A ) The filler is preferably used 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 components. 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 antioxidants, amine antioxidants, hindered phenol antioxidants, secondary antioxidants such as phosphorus antioxidants, sulfur antioxidants, etc. Is mentioned.

Although the total amount of antioxidant when added to the curable composition (I) and / or the curing accelerator (II) is not particularly limited, 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 Paragraph [0173] of Unexamined-Japanese-Patent No. 2005-232419 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.

The polymer plasticizer has a number average molecular weight of 500 to 15,000, preferably 800 to 10,000, and more preferably 1000 to 8,000. 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 use when a plasticizer is used for 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 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 (A). 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). The total amount of component (A) is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and still more preferably 1 to 50 parts by weight, relative to 100 parts by weight.

<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” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242) published by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.

Although not particularly limited, among the light stabilizers, ultraviolet absorbers are preferable. Specifically, TINUVIN P, TINUVIN 234, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 329, and TINUVIN 213 (all of these are Ciba Geigy Japan) 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 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) ( The range of 0.1 to 10 parts by weight per 100 parts by weight of the total component A) is preferred. If the amount is less than 0.1 parts by weight, the effect of improving the weather resistance is small.

<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 an atom other than a carbon atom and a hydrogen atom 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 or salts thereof. Can be mentioned. Further, the phosphoric acid group-containing monomer includes 2-((meth) acryloyl cyethyl 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 resin, phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin , Coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin sulfur, alkyl titanates, aromatic polyisocyanate and the like.

The above-mentioned adhesion-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight with respect to 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. The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight. 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.

Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. Is 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. Can be given. These various additives may be used alone or in combination of two or more. Specific examples of such additives include, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, etc. 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

FPD manufacturing method The FPD manufacturing method of the present invention uses a curing accelerator (II) when the light-transmitting protective cover and / or image display module of the light-transmitting protective cover and / or image display module are bonded together. However, specifically, for example, as shown in FIGS. 1 to 4, it is applied onto a bonded substrate (translucent protective cover, image display module, etc.). It is preferable to include the steps of applying the two-part photocurable composition, overlaying the laminated substrates, curing by light and redox polymerization reaction.

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.

<< Application of two-component curable composition onto bonded substrate >>
As a coating method of said curable composition (I) and hardening accelerator (II) when using the two-pack type photocurable composition of this invention as a filler for FPD bonding, hardening accelerator (II) is used. Is applied to the part of the light-transmitting protective cover and / or image display module that is the base material to be bonded to the dark part where light does not reach when the light-transmitting protective cover and the image display module are bonded. The composition (I) may be applied to any part of the translucent protective cover and / or the image display module, but is preferably applied to a part that is not in contact with the curing accelerator (II).

The order of applying each of the curable composition (I) and the curing accelerator (II) is not particularly limited, and after applying the curable composition (I) or the curing accelerator (II), the other is applied. Alternatively, both components may be applied simultaneously.

The base material to which the curable composition (I) and the curing accelerator (II) are applied is not particularly limited, and only one of the two target base materials (transparent cover and image display module) is used as necessary. The curable composition (I) and the curing accelerator (II) may be applied, or the curable composition (I) and the curing accelerator (II) may be separately applied to both of the two substrates. Further, only the curable composition (I) may be applied to one of the substrates, and only the curing accelerator (II) may be applied to the other substrate.

The application method to a bonding base material is not particularly limited, and various commonly used application methods can be used. For example, there are a method using a dispenser, a method using a coater, a method using a spray, and the like. A robot-controlled dispenser is preferred in terms of anti-sagging after application of the liquid composition and application accuracy for supplying a specific amount of the liquid composition to a specific site such as a dark part.

<The process of apply | coating hardening accelerator (II)>
The curing accelerator (II) is a part of the translucent protective cover and / or the image display module that is the bonding base material that becomes a dark part where light does not reach when the translucent protective cover and the image display module are bonded together. Apply to.

The dark area where light does not reach when the translucent protective cover and the image display module are bonded together is, for example, a black frame (black print) applied to the periphery of the translucent protective cover for the purpose of decoration, an electrode of a touch panel, an FPD This is a portion that is shaded when light is applied from the outside when the translucent protective cover and the image display module are bonded to each other by a flexible printed circuit board (FPC) or the like.

Specifically, when the translucent protective cover and the image display module are overlapped, a portion sandwiched between the black print and the image display module on the translucent protective cover becomes a dark part where light does not reach.

The method of applying the curing accelerator (II) to the dark portion by the black print is exemplified by the method shown in FIG. 1, and the curing accelerator (II) is applied to the black print portion of the translucent protective cover. Apply. As another method, it may be applied to a dark part by black printing of the image display module, or may be applied to a dark part of both the translucent protective cover and the image display module.

<The process of apply | coating curable composition (I)>
The curable composition (I) may be applied to any part of the translucent protective cover and / or the image display module, but is preferably applied to a part that does not come into contact with the curing accelerator (II).

The application method for applying the curable composition (I) to a portion that does not come into contact with the curing accelerator (II) includes, for example, the method shown in FIG. 1, and the curing accelerator (II) on the translucent protective cover is applied. Apply to areas not covered. As another method, the curable composition (I) can also be applied to the image display module. In this case, the application range does not need to be limited. You may apply | coat to any part including the part which overlaps with the part of a print. Furthermore, you may apply | coat to both the part which does not apply | coat the hardening accelerator (II) on a translucent protective cover, and an image display module.

On the other hand, when the curing accelerator (II) is applied to the image display module, it may be applied to the entire transparent protective cover regardless of the black print, and the portion of the image display module where the curing accelerator (II) is not applied. It may be applied to both, or may be applied to both.

Further, when the curing accelerator (II) is applied to both the translucent protective cover and the image display module, the translucent protective cover and the image display module are excluded except for the portion where the curing accelerator (II) is applied. You may apply to any one or both.

<< Step of superimposing bonded substrates >>
After applying an appropriate amount of the curable composition (I) and the curing accelerator (II) of the two-part photocurable composition to a predetermined portion of the base material to be bonded, the liquid composition as shown in FIG. Overlay so that is on the inside. In superposition, the thickness of the liquid composition layer is controlled (Z-axis control) and the superposition position is controlled (alignment). At that time, it is necessary to take care not to entrap bubbles or the like in the composition. There is. The method for superimposing is not particularly limited, and a known method can be arbitrarily used. In the superposition, the time required for the curable composition (I) to diffuse to a predetermined site, by the light and redox polymerization reaction while maintaining the Z-axis control and alignment state of the substrates to be bonded. Move on to curing. There is no particular limitation on the holding time, and the curable composition (I) is not necessarily in complete contact with the dark portion accelerator (II), but the curable composition (I) diffuses into the dark portion. It is preferable that a part of the curable composition (I) is in contact with the curing accelerator (II) present in the dark part. Although details of the curing method by photopolymerization reaction will be described later, the base material is temporarily fixed by irradiating a part or the whole surface with light so that the base material to be bonded is not shifted at the stage of holding the overlap. May be.

<< Curing method by redox polymerization reaction >>
When the two-component photocurable composition is present in a dark part where light is not transmitted, the redox polymerization reaction proceeds by contacting the curable composition (I) and the curing accelerator (II) as described above. And can be cured (see FIG. 3). The redox polymerization reaction can be cured at room temperature, but in order to proceed the curing more rapidly, a treatment such as heating may be performed. The temperature during heating is preferably 5 to 100 ° C, more preferably 10 to 80 ° C.

<< Curing method by photopolymerization reaction >>
The two-component photocurable composition is cured by light irradiation. The method for curing by the photopolymerization reaction is not particularly limited. By using the photopolymerization initiator (B), the two-part photocurable composition can be cured by irradiation with light or an electron beam from an active energy ray source (see FIG. 4). The active energy ray source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light-emitting diode, a semiconductor laser, and a metal halide lamp depending on the properties of the photopolymerization initiator used. . The curing temperature is preferably 0 ° C. to 150 ° C., more preferably 5 ° C. to 120 ° C.

<< Usage >>
There are no particular restrictions on the site where the FPD bonding filler is used, but there are no particular limitations on the touch panel, mobile phone liquid crystal, organic EL or organic TFT screen, computer liquid crystal, organic EL or organic TFT screen, car navigation liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, etc.

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. In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<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) were used, and chloroform was used as the GPC solvent.

<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 and 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, and cuprous bromide and a part of the total acrylic ester (described as the 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 acrylic ester (described as an additional monomer in Table 1) was added sequentially 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 gas phase part of the reaction vessel. 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 crudely purified butyl acetate was used as a diluent solvent for the polymer. The concentrate of (2) is diluted with about 100 to 150 kg of butyl acetate with respect to 100 kg of the polymer, and a filter aid (Radiolite R900, manufactured by Showa Chemical Industry Co., Ltd.) and / or an adsorbent (KYOWARD 700SEN, KYOWARD 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added. After introducing an 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) The second crudely purified filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and an adsorbent (KYOWARD 700SEN, KYOWARD 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was 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 the terminal Br group), heat stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (KYOWARD 700SEN, manufactured by Kyowa Chemical Industry Co., Ltd.) are added and heated at about 70 ° C. for several hours. Stir. 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.

<Manufacture of two-pack photocurable composition for FPD bonding>
Example 1
Table 2 shows the amount of each raw material used.
50 g of the polymer [P1] obtained in Production Example 1 as component (A), 50 g of the polymer [P2] obtained in Production Example 2, and DAROCUR1173 (2-hydroxy-2-methyl-1) as component (B) -0.8 g of phenyl-1-propan-1-one (Ciba Specialty Chemicals) and Lucirin TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Ciba Specialty Chemicals)) ) 0.1 g, as component (C), 0.65 g of cumene hydroxy peroxide (trade name Park Mill H, manufactured by NOF Corporation), in addition to components (A) to (C), 2-hydroxyethyl acrylate ( Product name Light Ester HOA, manufactured by Kyoeisha Chemical Co., Ltd. 10 g, Tetrahydrofurfuryl acrylate (Product name Light Ester T HF-A (manufactured by Kyoeisha Chemical Co., Ltd.) 10 g and dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 10 g were sufficiently stirred and mixed to prepare a curable composition (I). . Further, 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), dimethylacrylamide ( 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 the 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, the mixture was cured in about 5 minutes. The color tone of the obtained cured product is also shown in Table 2.

(Example 2)
As shown in FIG. 1, the curing accelerator (II) obtained in 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). After applying 0.03 g to the black frame coating portion (dark portion) of the glass plate with black print), 0.7 g of the curable composition (I) was applied to the portion not coated with black frame, as shown in FIG. 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 a 3.5 inch liquid crystal module are overlaid so as to have a specific thickness (FIG. 3), the UV irradiation device (Light Hammer 6, 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. 4). 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.

The above-mentioned bonded sample was cured at 23 ° C. and 50% relative humidity for 24 hours, and after confirming that the curable composition (I) and the curing accelerator (II) in the dark part were cured, various environmental exposure tests Went. The test was conducted after exposure to the environment at 85 ° C. for 240 hours in a thermostatic oven (Perfact Oven), or for 240 hours at 65 ° C. and 90% relative humidity at a constant temperature and humidity chamber (LH30-11P, manufactured by Nagano Scientific Machinery Co., Ltd.). The appearance of the part not painted with a black frame was visually observed.

(Comparative Example 1)
Only 0.7 g of the curable composition (I) obtained in Example 1 was applied to a glass plate with a black print, and then superimposed on a 3.5-inch liquid crystal module. UV curing and redox curing of the dark part were performed. The obtained bonded sample was subjected to various environmental exposure tests in the same manner as in Example 1, and the appearance of the part not coated with the black frame was visually observed.
Although the curable composition (I) in the translucent part was cured after UV light irradiation, it was uncured under the dark part, so it was uncured during curing for 24 hours at 23 ° C. and 50% relative humidity. Of the liquid material leaked from the periphery of the glass plate.

(Comparative Example 2)
0.63 g of the curable composition (I) obtained in Example 1 was applied to a glass plate with a black print, and 0.07 g of a curing accelerator (II) was applied to a 3.5 inch liquid crystal module, followed by a black print. Glass and a 3.5-inch liquid crystal module were overlapped, and UV curing of the light transmitting portion and redox curing of the dark portion were performed in the same manner as in Example 1.
After UV light irradiation, the curable composition (I) in the translucent part was cured but colored yellow. In the dark, curing was confirmed after 24 hours at 23 ° C. and 50% relative humidity. After the 240-hour environmental exposure test, the color of the cured product in the translucent part was changed to deep yellow.

(Comparative Example 3)
0.63 g of the curable composition (I) obtained in Example 1 and 0.07 g of the curing accelerator (II) were stirred and mixed, and then applied to a glass plate with a black print and superimposed on a 3.5 inch liquid crystal module. Then, UV curing and dark area redox curing were performed in the same manner as in Example 2. After UV light irradiation, the curable composition (I) in the translucent part was cured but colored yellow. In the dark, curing was confirmed after 24 hours at 23 ° C. and 50% relative humidity. After the 240-hour environmental exposure test, the color of the cured product in the translucent part was changed to deep yellow.
Table 3 shows the evaluation results of Examples and Comparative Examples.

From the comparison between Example 2 and Comparative Examples 1 to 3, as described in Example 2, after the curing accelerator (II) was applied in a limited manner in the dark part, the curable composition (I) was accelerated. It is applied so that it does not come into contact with the agent (II), and the curable composition (I) is diffused to come into contact with the curing accelerator (II). In addition, it is possible to provide an FPD laminating method and a two-pack type photocurable composition for FPD laminating that can solve the problem of coloring the design portion.

According to the present invention, it is a photocurable composition that can be quickly cured by light and that also quickly cures even a dark part that is not exposed to light, and even if the cured product of the dark part is colored, the appearance of the design part FPD manufacturing method that does not adversely affect, FPD bonding method, two-part photocurable composition for FPD bonding, and electric / electronic device equipped with FPD obtained by coating and curing the same Can be provided.

1. Cover glass 2. Liquid crystal module Dark part 4. Curable composition (I)
5. Curing accelerator (II)
6). Redox curing part 7. Photocuring part

Claims (15)

1. Curable composition containing compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) Flat panel display using a two-component photocurable composition comprising a product (I) and a curing accelerator (II) containing a reducing agent (D) to bond a translucent protective cover and an image display module A manufacturing method of
   A step of applying the curing accelerator (II) only to a portion of the translucent protective cover and / or image display module that becomes a dark part where light does not reach when the translucent protective cover and the image display module are bonded together. A method for manufacturing a flat panel display, comprising:
2. Furthermore, it has the process of apply | coating curable composition (I) to the part which does not contact with hardening accelerator (II) of a translucent protective cover and / or an image display module. Flat panel display manufacturing method.
3. After the curable composition (I) and the curing accelerator (II) are applied to the translucent protective cover and / or the image display module, the translucent protective cover and the image display module are bonded to each other and the curable composition (I And a curing accelerator (II). The method for producing a flat panel display according to claim 1, further comprising a step of contacting the curing accelerator (II).
4. The method for producing a flat panel display according to any one of claims 1 to 3, further comprising a step of irradiating light after bonding the translucent protective cover and the image display module.
5. 5. The flat panel display according to claim 1, wherein the curable composition (I) and the curing accelerator (II) are applied only to one of the light-transmitting protective cover and the image display module. Manufacturing method.
6. 5. The flat panel according to claim 1, wherein the curable composition (I) is applied to one of the translucent protective cover and the image display module, and the curing accelerator (II) is applied to the other. Display manufacturing method.
7. The flat panel display according to any one of claims 1 to 4, wherein the curable composition (I) and the curing accelerator (II) are respectively applied to both the translucent protective cover and the image display module. Production method.
8. The production of a flat panel display according to any one of claims 1 to 7, wherein the compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule is an organic polymer. Method.
9. The method for producing a flat panel display according to claim 8, wherein the organic polymer is a (meth) acrylic polymer.
10. Curable composition containing compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) A flat panel for bonding a translucent protective cover and an image display module through a two-component curable composition comprising a product (I) and a curing accelerator (II) containing a reducing agent (D) A method for pasting displays,
    A curing accelerator (II) is applied to the light-transmitting protective cover and / or image display module on the dark portion where light does not reach when the light-transmitting protective cover and the image display module are bonded together. The product (I) is applied to a portion of the light-transmitting protective cover and / or image display module that does not come into contact with the curing accelerator (II), and the light-transmitting protective cover and the image display module are bonded together to form a curable composition ( A method for laminating a flat panel display, comprising contacting I) and a curing accelerator (II).
11. Contains acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and peroxide polymerization initiator (C) A photocurable composition for laminating two-component flat panel displays, comprising a curable composition (I) and a curing accelerator (II) containing a reducing agent (D).
12. The polymerizable carbon-carbon double bond of the component (A) is represented by 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 photocurable composition for laminating two-component flat panel displays according to claim 11, wherein the photocurable composition is a group represented by the formula:
13. The photo-curable composition for laminating two-component flat panel displays according to claim 11 or 12, wherein the peroxide-based polymerization initiator of component (C) is cumene hydroxy peroxide.
14. 14. The photo-curing property for laminating a two-component flat panel display according to claim 11, wherein the reducing agent of component (D) is a transition metal compound and / or an amine compound in the fourth period. Composition.
15. An electric / electronic device equipped with a flat panel display obtained by applying and curing the photocurable composition for bonding a two-component flat panel display according to any one of claims 11 to 14.

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