JP2014202916A - Image display apparatus, and electric and electronic apparatus equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image display apparatus having no display unevenness in which transparent resin layer is filled between at least two types of members selected from a transparent cover board, a touch sensor, a flat panel display module and a backlight, and an electric and electronic apparatus equipped with the image display apparatus.SOLUTION: There is provided an image display apparatus in which a transparent resin layer is filled between at least two types of members selected from a transparent cover board, a touch sensor, a flat panel display module and a backlight. Elongation at break of the resin layer at a tensile test specified by JISK6251 is 500% or more, and the resin layer is a cured product obtained by curing a curable composition (B) containing acrylic polymer (A).

Description

  The present invention relates to an image display device in which at least two kinds of members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight are filled with a transparent resin layer, and an electric device equipped with the image display device -Related to electronic equipment.

  Conventionally, an air gap is provided between the liquid crystal module, organic EL module, or organic TFT module in the image display part of a mobile phone, smartphone or touch panel, and the uppermost transparent cover (PET film, tempered glass, acrylic plate, etc.). Thus, even when the cover is broken by an external impact, the module is not affected (air gap structure). Recently, some urethane acrylates and epoxy acrylates with photopolymerizable functional groups have been used as binder polymers for the purpose of improving the visibility of flat panel displays, impact resistance, and reducing the effects of noise from display modules on touch sensors. An optical elastic resin curable composition curable with light (UV) is being used.

  However, the display module such as liquid crystal and organic EL and the transparent protective cover, touch sensor, and touch sensor integrated transparent protective cover were bonded and cured with the optical elastic resin curable composition that can be cured by the light (UV). In this case, there is a problem that display unevenness due to light leakage from the display module occurs.

  There are examples (Patent Documents 1 to 5) in which the resin is filled between the uppermost transparent cover board and the touch sensor to improve the visibility and impact resistance, but the reactive acrylic has good heat resistance and flexibility. The description about the display nonuniformity improvement at the time of the display module bonding by the adhesive agent using an oligomer or a polymer is not shown yet.

WO2005 / 073333 JP-A-11-130931 JP 2005-315901 A JP 2009-186963 A WO2010 / 027041

  The present invention relates to a transparent cover board, a touch sensor, a flat panel display display module, and an image display device having no display unevenness filled with a transparent resin layer between at least two members selected from a backlight and the image display device Providing electrical and electronic equipment equipped with

A curable composition containing an acrylic polymer (A) having an elongation at break of 500% or more between at least two members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight. By using a cured product obtained by curing the product (B), the present inventors have found that the above problems can be solved, and have completed the present invention.
That is, the present invention
An image display device that is filled with a transparent resin layer between at least two kinds of members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight,
Cured product obtained by curing a curable composition (B) containing an acrylic polymer (A) having an elongation at break of 500% or more in a tensile test specified by JISK6251 of the resin layer The present invention relates to an image display device.

  The acrylic polymer (A) is preferably a polymer produced by mainly polymerizing a monomer selected from (meth) acrylic monomers containing an ester structure of C6 or higher.

  The strength at break defined by JISK6251 of the resin layer is preferably 20 KPa or more.

  The curable composition (B) is preferably cured by UV.

  It is preferable that the curable composition (B) is heat-cured.

  The curable composition (B) is preferably cured at 0 to 30 ° C.

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

  The curable composition (B) preferably contains a polymerization initiator (C).

  It is preferable that the polymerization initiator (C) is at least one selected from a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator.

  The polymerization initiator (C) is preferably a photopolymerization initiator.

The polymerizable carbon-carbon double bond 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)
It is preferable that it is group represented by these.

  It is preferable that the curable composition (B) further contains a monomer (D) having a (meth) acryloyl group.

  The molecular weight distribution of the acrylic polymer (A) is preferably less than 1.8.

  It is preferable that the main chain of the acrylic polymer (A) is produced by a living radical polymerization method.

  The present invention relates to an electric / electronic device equipped with the image display device described above.

  According to the present invention, it can be quickly cured by light, and has excellent visibility, impact resistance, heat resistance, light resistance, and display efficiency. From a transparent cover board, a touch sensor, a flat panel display display module, and a backlight. Provided are an image display device that is filled with a transparent resin layer between at least two selected members and has no display unevenness when a backlight is lit, and an electric / electronic device equipped with the image display device.

It is the figure which filled the liquid crystal module with a backlight, and a protective cover with transparent resin. It is the figure which apply | coated liquid transparent resin to the protective cover. It is a figure of the comparative example of the state which the optical nonuniformity generate | occur | produced.

The present invention is an image display device that is filled with a transparent resin layer between at least two kinds of members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight,
Cured product obtained by curing a curable composition (B) containing an acrylic polymer (A) having an elongation at break of 500% or more in a tensile test specified by JISK6251 of the resin layer This is an image display device characterized by that.

  The resin layer is a cured product obtained by curing the curable composition (B) containing the acrylic polymer (A).

<< Acrylic polymer (A) >>
The main chain of the acrylic polymer (A) is preferably produced mainly by polymerizing a (meth) acrylic monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the acrylic polymer (A) is the above monomer, and preferably 70 mol% or more.

  (Meth) acrylic monomers include: (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n-butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid phenyl, (meth) acrylic acid tolyl, (meth) acrylic acid benzyl, (meta 2-methoxyethyl acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate , (Meth) acrylic acid 2-aminoethyl, 3- (methacryloyloxypropyl) trimethoxysilane, 3- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyl Dimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acrylic acid 2 Trifluoromethylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trimethaacrylate Fluoromethyl, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, (meth) acrylic And (meth) acrylic acid ester monomers such as 2-perfluorodecylethyl acid and 2-perfluorohexadecylethyl (meth) acrylate.

  Among these, from the physical properties of the product, (meth) acrylic acid ester monomers are preferable, acrylic acid ester monomers are more preferable, and acrylic acid alkyl ester monomers are more preferable.

  Among the (meth) acrylic monomers, it is a polymer produced mainly by polymerizing a monomer selected from (meth) acrylic monomers containing an ester structure of C6 or more. Mechanical properties (strength of elongation and strength at break) The polymer is preferably a polymer produced by polymerizing a monomer selected from (meth) acrylic monomers containing an ester structure of C6 or higher. Specifically, hexyl acrylate, heptyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, acrylic Dodecyl acid, tridecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate.

  In the present invention, these preferable monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, it is preferable that these preferable monomers are contained in an amount of 50 mol% or more.

  The molecular weight distribution of the acrylic polymer (A) in the present invention (ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC)) is not particularly limited, Preferably it is less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, most preferably 1.3 or less.

  In the GPC measurement in the present invention, a polystyrene gel column is usually used with chloroform or tetrahydrofuran as a mobile phase, and the molecular weight value is obtained in terms of polystyrene.

  The number average molecular weight of the acrylic polymer (A) in the present invention is not particularly limited, but it is preferably in the range of 500 to 1,000,000 when measured by GPC, and 3,000 to 100,000. Is more preferable, 5,000 to 80,000 is more preferable, and 8,000 to 50,000 is even more preferable. If the molecular weight is too low, the original properties of the acrylic polymer tend to be difficult to be expressed, while if it is too high, handling tends to be difficult.

  The acrylic polymer (A) in the present invention is preferably cured by UV, heat or the like. The curable composition can be cured even at a room temperature of 0 to 30 ° C. The curing form at normal temperature is not particularly limited, and examples thereof include moisture and redox curing. For that purpose, it preferably has a functional group, and examples of the functional group include an alkenyl group, a polymerizable carbon-carbon double bond, and a hydrolyzable silyl group. A double bond is more preferred.

As the polymerizable carbon-carbon double bond, 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.

Specific examples of R ^{a in} the general formula (1) include a hydrogen atom; an alkyl group such as a methyl group and an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as a benzyl group. Can be mentioned. In these, a hydrogen atom or a methyl group is preferable from the availability of a raw material, and also a hydrogen atom is more preferable from the high polymerization reactivity.

<Synthesis Method of Acrylic Polymer (A)>
The acrylic polymer used in the present invention can be obtained by various polymerization methods, and is not particularly limited, but is preferably a radical polymerization method from the viewpoints of versatility of the monomer, ease of control, etc. 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 that allows easy control of the molecular weight and molecular weight distribution of the resulting acrylic polymer is more preferred, and atom transfer radical polymerization is particularly preferred from the standpoint of availability of raw materials and ease of introduction of functional groups at the ends of the polymer. 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 the preferred methods for synthesizing the acrylic polymer 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 an acrylic polymer having two or more functional groups in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,

Etc.

  There is no restriction | limiting in particular as a (meth) acrylic-type monomer used in atom transfer radical polymerization, All the (meth) acrylic-type monomers mentioned above can be used suitably.

  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.

<Method of introducing hydrolyzable silyl group into acrylic polymer>
The method of Paragraph [0102]-[0112] of Unexamined-Japanese-Patent No. 2004-210858 is mentioned. Among these methods, from the point that control is easier, by a method of converting an alkenyl group of a polymer having a terminal alkenyl group into a hydrolyzable silyl group by a hydrosilylation reaction with a hydrosilane compound having a hydrolyzable silyl group. It is preferable that it is manufactured.

<Method of introducing polymerizable carbon-carbon double bond into acrylic polymer>
As a method for introducing a polymerizable carbon-carbon double bond into the 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 acrylic polymer of the general formula (2) is substituted with a compound having a polymerizable carbon-carbon double bond of the general formula (3).
-CR ¹ R ² X (2)
(In the formula, R ¹ and R ² are groups bonded to an ethylenically unsaturated group of an acrylic monomer. X represents chlorine, bromine, or iodine.)
M ^{+ −} OC (O) C (R) ═CH ₂ (3)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

  The acrylic polymer having a terminal structure represented by the general formula (2) is a method of polymerizing an acrylic monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or Although it is produced by a method of polymerizing an 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 (3), specific examples of R, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is 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 (3) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (2), 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 (4) with an acrylic polymer having a hydroxyl group at the terminal.
YC (O) C (R) = CH ₂ (4)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. Y represents chlorine, bromine, or a hydroxyl group.)

(Introduction method 3)
A method in which a diisocyanate compound is reacted with an acrylic polymer having a hydroxyl group at the terminal, and a residual isocyanate group is reacted with a compound represented by the following general formula 5.
HO—R′—OC (O) C (R) ═CH ₂ (5)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. R ′ 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.

<< Curable composition (B) >>
The curable composition (B) contains the acrylic polymer (A) and is cured by UV, heat, etc., but is preferably cured by UV. Further, the curable composition can be cured even at a room temperature of 0 to 30 ° C. The curing form at normal temperature is not particularly limited, and examples thereof include moisture and redox curing.

  When the acrylic polymer (A) has a polymerizable carbon-carbon double bond, the curable composition (B) may contain a polymerization initiator (C).

  When the acrylic polymer (A) has a hydrolyzable silyl group, the curable composition (B) may contain a curing catalyst.

<Polymerization initiator (C)>
Although it does not specifically limit to the curable composition (B) of this invention, It is preferable to use a polymerization initiator (C) in order to make it harden | cure quickly or to obtain the hardened | cured material of sufficient property. The polymerization initiator (C) is not particularly limited, and examples thereof include a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator, and among them, a photopolymerization initiator is preferable. The photopolymerization initiator, the thermal polymerization initiator, and the redox initiator may be used alone or as a mixture of two or more. When used as a mixture, various initiators are used. It is preferable that the usage-amount of an agent exists in each below-mentioned range.

  As a photoinitiator, a photoradical initiator, a photoanion initiator, a near-infrared photoinitiator, etc. are mentioned, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly 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 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl A phosphine oxide etc. are mentioned.

  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 2,4,6-trimethylben Yl - diphenyl - phosphine oxide, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide are preferred.

  Examples of the photoanion initiator include 1,10-diaminodecane, 4,4′-trimethylenedipiperazine, carbamates and derivatives thereof, cobalt-amine complexes, aminooxyiminos, ammonium borates and the like. .

As the near infrared photopolymerization initiator, a near infrared light absorbing cationic dye or the like may be used. As the near-infrared light absorbing cationic dye, near-infrared light which is excited by light energy in the region of 650 to 1500 nm, for example, disclosed in JP-A-3-111402, JP-A-5-194619, etc. An absorptive cationic dye-borate anion complex or the like is preferably used, and a boron sensitizer is more preferably used in combination.
These photopolymerization initiators may be used alone or in combination of two or more, or may be used in combination with other compounds.

  Specific examples of combinations with other compounds include combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, and combinations with iodonium salts such as diphenyliodonium chloride, methylene blue, and the like. Examples include those combined with a dye and an amine.

  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.

  When using a photoinitiator, the addition amount does not have a restriction | limiting in particular, However, 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.

  Further, the thermal polymerization initiator is not particularly limited, and examples thereof include azo initiators, peroxide initiators, persulfate initiators and the like.

  Suitable azo initiators include, but are not limited to, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (VAZO 33), 2,2′-azobis (2- Amidinopropane) dihydrochloride (VAZO 50), 2,2′-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2′-azobis (isobutyronitrile) (VAZO 64), 2, 2′-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,2′-azobis (2- Cyclopropylpropionitrile) and 2,2′-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries, Ltd.) Etc. The.

  Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t-butylcyclohexyl). Peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), t-butyl per Oxy-2-ethylhexanoate (Trigonox 21-C50) (available from Akzo Nobel), dicumyl peroxide, and the like.

  Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.

  A preferable thermal polymerization initiator is selected from the group consisting of an azo initiator and a peroxide initiator. More preferred are 2,2'-azobis (methyl isobutyrate), t-butyl peroxypivalate, di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

  A thermal polymerization initiator may be used independently or may use 2 or more types together.

  When a thermal polymerization initiator is used, the thermal polymerization initiator is present in a catalytically effective amount, and the amount of addition is not particularly limited, but is preferred when the component (A) of the present invention is 100 parts by weight. Is 0.01 to 5 parts by weight, more preferably 0.025 to 2 parts by weight.

  Further, usable redox (redox) initiators can be used in a wide temperature range. In particular, the following initiator species can be advantageously used at room temperature.

  Suitable redox initiators include, but are not limited to, combinations of the above persulfate initiators and reducing agents (sodium metabisulfite, sodium bisulfite, etc.); organic peroxides and tertiary amines. Combinations such as a combination of benzoyl peroxide and dimethylaniline, a combination of cumene hydroperoxide and anilines; a combination of organic peroxide and transition metal, such as a combination of cumene hydroperoxide and cobalt naphthate, and the like.

  Preferred redox initiators are a combination of organic peroxide and tertiary amine, a combination of organic peroxide and transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide. And cobalt naphthate. A redox initiator may be used independently or may use 2 or more types together.

  When a redox initiator is used, the redox initiator is present in a catalytically effective amount, and its addition amount is not particularly limited, but is preferred when the component (A) of the present invention is 100 parts by weight. Is 0.01 to 5 parts by weight, more preferably 0.025 to 2 parts by weight. Considering that the curable composition for filling between the flat panel display display module / transparent cover board is temporarily fixed with light such as UV, a photopolymerization initiator is mainly used among the above initiators. It is preferable.

<Curing catalyst>
The curable composition (B) of the present invention is not particularly limited when it contains an acrylic polymer having a hydrolyzable silyl group, but it is preferable to use a curing catalyst. The acrylic polymer having a hydrolyzable silyl group used in the present invention has a siloxane bond in the presence or absence of various conventionally known condensation catalysts (also referred to as a curing catalyst or “curing agent”). Is crosslinked and cured. As the properties of the cured product, a wide range from rubbery to resinous can be prepared depending on the molecular weight and main chain skeleton of the polymer.

  Examples of such condensation catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin Diisooctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate Dialkyltin dicarboxylates such as dibutyltin dimethoxide, dialkyltin alkoxides such as dibutyltin diphenoxide, such as dibutyltin diacetylacetonate, dibutyl Intramolecular coordination derivatives of dialkyltin such as diethyl acetoacetate, for example, reaction products of dialkyltin oxide such as dibutyltin oxide and dioctyltin oxide and ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate , A tin compound obtained by reacting a dialkyltin oxide, a carboxylic acid and an alcohol compound, for example, a reaction product of a dialkyltin oxide and a silicate compound such as dibutyltin bistriethoxysilicate, dioctyltin bistriethoxysilicate, and the dialkyltin compounds Tetravalent tin compounds such as oxy derivatives (stannoxane compounds) of the above; for example, divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin felzatic acid, or the like And reaction products and mixtures of amine compounds such as laurylamine described below; for example, monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide, and monoalkyltins such as monooctyltin compounds; Titanic acid esters such as tetrabutyl titanate, tetrapropyl titanate, tetra (2-ethylhexyl) titanate, isopropoxytitanium bis (ethylacetoacetate); aluminum trisacetylacetonate, aluminum trisethylacetoacetate, di-isopropoxyaluminum ethylacetate Organoaluminum compounds such as acetate; bismuth carboxylate, iron carboxylate, titanium carboxylate, lead carboxylate, vanadium carboxylate, zirconium carboxylate, carboxylate carbonate Carboxylic acid (2-ethylhexanoic acid, neodecanoic acid, versatic acid, such as lucium, potassium carboxylate, barium carboxylate, manganese carboxylate, cerium carboxylate, nickel carboxylate, cobalt carboxylate, zinc carboxylate, aluminum carboxylate, Oleic acid, naphthenic acid, etc.) Metal salts, or reaction products and mixtures of these with amine compounds such as laurylamine described later; zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, dibutoxyzirconium diacetylacetonate, zirconium Chelate compounds such as acetylacetonate bis (ethylacetoacetate) and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine, isopropylamine, butyrate Aliphatic primary amines such as amine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine , Diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, etc. Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; Aliphatics such as triallylamine and oleylamine Saturated amines; aromatic amines such as lauryl aniline, stearyl aniline, triphenylamine; and other amines such as monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzyl Amine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4 -Amine compounds such as methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or amine compounds thereof Salts of carboxylic acids, etc .; reaction products and mixtures of amine-based compounds such as laurylamine and tin octylate and organic tin compounds; low molecular weight obtained from excess polyamines and polybasic acids Polyamide resin; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ- Aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N -(Β-aminoethyl) aminopropylmethyl Ethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane and the like can be mentioned. Silanol condensation such as silane coupling agents having amino groups such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc., which are derivatives of these modified Examples thereof include known silanol condensation catalysts such as catalysts, further acidic catalysts such as fatty acid such as ferrous acid, organic acidic phosphate compounds, and basic catalysts.

Examples of the organic acidic phosphoric acid ester compound of the acidic catalyst include (CH ₃ O) ₂ —P (═O) (— OH), (CH ₃ O) —P (═O) (— OH) ₂ , (C ₂ H _{5 O) 2 -P (= O} ) (- OH), (C 2 H 5 O) -P (= O) (- OH) 2, (C 3 H 7 O) 2 -P (= O) (- _{OH), (C 3 H 7} O) -P (= O) (- OH) 2, (C 4 H 9 O) 2 -P (= O) (- OH), (C 4 H 9 O) -P _{(= O) (- OH)} 2, (C 8 H 17 O) 2 -P (= O) (- OH), (C 8 H 17 O) -P (= O) (- OH) 2, (C _{10 H 21 O) 2 -P (} = O) (- OH), (C 10 H 21 O) -P (= O) (- OH) 2, (C 13 H 27 O) 2 -P (= O) _{(-OH), (C 13 H} 27 O) -P (= O) (- _{H) 2, (C 16 H} 33 O) 2 -P (= O) (- OH), (C 16 H 33 O) -P (= O) (- OH) 2, (HO-C 6 H 12 O _{) 2 -P (= O) (} - OH), (HO-C 6 H 12 O) -P (= O) (- OH) 2, (HO-C 8 H 16 O) -P (= O) ( _{-OH), (HO-C 8} H 16 O) -P (= O) (- OH) 2, [(CH 2 OH) (CHOH) O] 2 -P (= O) (- OH), [( _{CH 2 OH) (CHOH) O} ] -P (= O) (- OH) 2, [(CH 2 OH) (CHOH) C 2 H 4 O] 2 -P (= O) (- OH), [( CH ₂ OH) (CHOH) C ₂ H ₄ O] —P (═O) (— OH) _{2 and the} like are exemplified, but are not limited to the exemplified substances.
These catalysts may be used alone or in combination of two or more.

  When a curing catalyst is used, the amount added is not particularly limited, but preferably 0 when the acrylic polymer component having a hydrolyzable silyl group in the component (B) is 100 parts by weight. 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight.

<Other ingredients>
In the curable composition (B) of the present invention, various compounding agents may be added according to the intended physical properties.

(Monomer (D) having (meth) acryloyl group)
The monomer (D) which has a (meth) acryloyl group can be added to the curable composition of this invention in the range which does not impair the effect of this invention.

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

  The amount of the monomer (D) having a (meth) acryloyl group is 100 parts by weight of the component (A) from the viewpoint of improving surface curability, improving base material adhesion, imparting toughness, and workability by reducing viscosity. The amount is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.

(Filler)
The filler is not particularly limited, and examples include fillers described in paragraph [0158] of JP-A-2005-232419, but UV curing is possible, that is, a transparent material is preferable even when added to the curable composition. Of these fillers, crystalline silica, fused silica, and the like are preferable. In particular, when it is desired to obtain a cured product having high strength with these fillers, mainly crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay and activity A filler selected from zinc oxide and the like can be added. Among them, the specific surface area (according to BET adsorption method) of ^{50 m} 2 / g or more, usually 50 to 400 m ² / g, is preferably 100 to 300 m ² / g approximately ultrafine powdery silica preferred. Further, silica whose surface has been previously hydrophobically treated with an organosilicon compound such as organosilane, organosilazane, diorganopolysiloxane, etc. is more preferred.

  Moreover, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like can be added. In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength and breaking elongation of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the breaking strength and breaking elongation of the cured product.

  Furthermore, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When surface-treated calcium carbonate is used, the workability of the curable composition of the present invention is improved as compared with the case where calcium carbonate that is not surface-treated is used, and the storage stability effect of the curable composition is improved. It is thought that it will improve further.

  As the surface treatment agent, known ones can be used, and examples include surface treatment agents described in paragraph [0161] of JP-A-2005-232419. The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight and more preferably in the range of 1 to 5% by weight with respect to calcium carbonate. When the treatment amount is less than 0.1% by weight, the workability improving effect may not be sufficient, and when it exceeds 20% by weight, the storage stability of the curable composition may be lowered. Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is preferably used when the effect of improving the thixotropy of the blend, the breaking strength of the cured product, the elongation at break and the like is particularly expected. On the other hand, those described in paragraph [0163] of JP-A-2005-232419 in which heavy calcium carbonate is sometimes added for the purpose of increasing the amount of the compound, reducing costs, or the like can be used.

  The said filler may be used independently according to the objective and necessity, and may use 2 or more types together. When the filler is used, the addition amount is preferably 5 to 1000 parts by weight, and preferably 20 to 500 parts by weight with respect to 100 parts by weight of component (A). It is more preferable to use in the range of 40 to 300 parts by weight. 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.

(Micro hollow particles)
For the purpose of reducing the weight and cost without causing a significant decrease in physical properties, fine hollow particles can be added in combination with these reinforcing fillers. Such fine hollow particles (hereinafter sometimes referred to as “balloons”) are not particularly limited, but have a diameter as described in “Latest Technology for Functional Fillers” (CMC). Examples thereof include hollow bodies (inorganic balloons and organic balloons) made of inorganic or organic materials of 1 mm or less, preferably 500 μm or less, more preferably 200 μm or less. In particular, it is preferable to use a micro hollow body having a true specific gravity of 1.0 g / cm ³ or less, and more preferably to use a micro hollow body having a specific gravity of 0.5 g / cm ³ or less. Moreover, a glass balloon is more preferable from the need to be transparent even if it is added to the curable composition.

  As the inorganic balloon and the organic balloon, balloons described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used. The balloons may be used alone or in combination of two or more. Furthermore, the surface of these balloons is made of fatty acid, fatty acid ester, rosin, rosin acid lignin, silane coupling agent, titanium coupling agent, aluminum coupling agent, polypropylene glycol, etc. to improve dispersibility and workability of the compound. Those processed in the above can also be used. These balloons are used for weight reduction and cost reduction without impairing flexibility and elongation / strength among physical properties when the compound is cured.

  Although the addition amount of a balloon is not specifically limited, Preferably it is 0.1-50 weight part with respect to 100 weight part of (A) component, More preferably, it can be used in 0.1-30 weight part. If the amount is less than 0.1 parts by weight, the effect of reducing the weight is small. If the amount is more than 50 parts by weight, a decrease in tensile strength may be observed among the mechanical properties when the compound is cured. Moreover, when the specific gravity of a balloon is 0.1 or more, the addition amount is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight.

(Antioxidant)
Various antioxidants may be used in the curable composition of the present invention 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.

(Plasticizer)
A plasticizer can be mix | blended with the curable composition 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 with 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.

  Although the usage-amount in the case of using a plasticizer is not limited, Preferably it is 1-100 weight part with respect to 100 weight part of (A) component, More preferably, it is 5-50 weight part. 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 addition amount of the reactive diluent is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and further preferably 1 to 50 parts by weight with respect to 100 parts by weight of the component (A). .

(Light stabilizer)
You may add a light stabilizer to the curable composition of this invention as needed. 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 not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable. Specifically, TINUVIN P, TINUVIN 234, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 329, 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.

  It is preferable that the usage-amount of a light stabilizer is 0.1-10 weight part with respect to 100 weight part of (A). 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.

(Adhesiveness imparting agent)
An adhesiveness-imparting agent can be added to the curable composition of the present invention for the purpose of further improving the substrate adhesion. Examples of the adhesiveness-imparting agent include a crosslinkable silyl group-containing compound and a vinyl group having a polar group. A monomer is preferable, and further, a silane coupling agent and an acidic group-containing vinyl monomer are preferable. 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 phosphoric acid group-containing monomers, 2-((meth) acryloyl cyethyl phosphate), 2- (meth) acryloyloxypropyl phosphate, 2- (meth) acryloyloxy-3-chloropropyl phosphate, 2- Examples include (meth) acryloyloxyethyl phenyl phosphate. 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 per 100 parts by weight of the total component (A). If the amount 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 decrease. 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)
A solvent can be mix | blended with the curable composition of this invention as needed. 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)
Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or its cured product. 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, 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.

  The curable composition of the present invention can be prepared as a one-pack type in which all blending components are blended and sealed in advance, and the A liquid from which only the initiator is removed and the initiator is mixed with a filler, a plasticizer, a solvent, and the like. It can also be prepared as a two-component type in which the prepared B solution is mixed immediately before molding.

<< Curing method >>
The method for curing the curable composition is not particularly limited.

  When a thermal polymerization initiator is used as the component (C), the curing temperature varies depending on the type of the thermal polymerization initiator to be used, the component (A), other compounds to be added, etc., but usually 50 ° C to 250 ° C. Preferably, 70 ° C to 250 ° C is more preferable.

  (C) When using a photoinitiator as a component, it can be hardened by irradiating light or an electron beam with an active energy ray source. Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example. (C) When using a photoinitiator as a component, 0 to 150 degreeC is preferable, and 5 to 120 degreeC is more preferable.

  When a redox initiator is used as the component (C), the curing temperature is preferably −50 ° C. to 250 ° C., more preferably 0 ° C. to 180 ° C.

  The curable composition of the present invention can be cured by moisture curing. The relative humidity during moisture curing is preferably 5 to 95%, and more preferably 10 to 80%.

  The curable composition of the present invention can be cured by photocuring, heat curing, or room temperature curing at 0 ° C. to 30 ° C. depending on the type of the polymerization initiator (C), along with moisture curing. . (C) When using 2 or more types of mixtures as a component, according to the kind of initiator, hardening conditions are combined suitably. The curable composition of the present invention can be cured by photo-curing and heat-curing or a combination of photo-curing and room-temperature curing by using two or more kinds of initiators together, so that it is rapidly cured by light. Also, it does not become uncured even in the part not exposed to light.

<< Molding method >>
The application method when the curable composition of the present invention is used as a filler between at least two kinds of members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight is particularly limited. Instead, various commonly used coating methods can be used. For example, there are a method using a dispenser, a method using a coater, a method using a spray, etc., but those using a dispenser in terms of sagging prevention after application and prevention of mixing at the time of bonding with a transparent cover board (film). preferable.

<< cured product >>
The resin layer filled between at least two types of members selected from the transparent cover board, touch sensor, flat panel display display module, and backlight of the present invention is a composition (B) containing an acrylic polymer (A). ) Is cured. This cured product has an elongation at break of 500% or more at the time of a tensile test specified by JISK6251. When the elongation at break is 500% or more, there is no occurrence of optical unevenness of the module when the object other than the display module is bonded and cured.

  The strength at break specified by JISK6251 of the resin layer used in the present invention is preferably 20 KPa or more from the viewpoint of preventing the display module and the protective cover or the touch sensor from being bonded to each other.

<< Usage >>
There are no particular restrictions on the location where this image display device is used, but there are no particular limitations on the liquid crystal of touch panels and mobile phones, organic EL or organic TFT screens, computer liquid crystals, organic EL or organic TFT screens, car navigation liquid crystals, organic EL or organic A TFT screen, a liquid crystal, an organic EL, an organic TFT television display, etc. are mentioned.

  The present invention provides an electrical / electronic device equipped with an image display device that is filled with a transparent resin layer between at least two kinds of members selected from the transparent cover board, touch sensor, flat panel display display module, and backlight. Include.

  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 following examples, “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). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; Showa Denko KK) and chloroform as a GPC solvent were used.

¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 (400 MHz) and deuterated chloroform as a solvent.

In the following examples, “number of (meth) acryloyl groups introduced per molecule of polymer” was calculated from the number average molecular weight determined by ¹ H-NMR analysis and GPC.
In the following examples and comparative examples, “part” and “%” are “part by weight” and “% by weight”, respectively.
".

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Examples 1, 2, 3, 4)
Table 1 shows the amount of each raw material used.
(1) Polymerization process The acrylic ester (premixed acrylic ester) 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 2-bromobutyrate (EBB) was added and mixed as an initiator, and the temperature of the mixture was adjusted to about 80 ° C. At that stage, pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 2) 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 the polymerization is shown in Table 1 as a triamine for polymerization. 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) 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, 1 kg of KYOWARD 500SH) 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) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and an adsorbent (Kyoward 700SEN, Kyoward 500SH, 1 kg each) 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 terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl), an adsorbent (Kyoward 700SEN) and 0.4 kg 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], [P2], [P3] and [P4] 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) 20 parts of the polymer [P1] obtained in Production Example 1 as a component, [P2] 10 parts, [P4] 70 parts, (C) As a component, DAROCUR1173 (2-hydroxy-2-methyl-1- 0.8 parts of phenyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) and LUCIRIN TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) (Ciba Specialty Chemicals) 0.1 parts, HOA (2-hydroxyethyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 7 parts, ISTA (isostearyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.) 33 parts, JP308E (Tris ( A curable composition 1 was prepared by sufficiently stirring and mixing 1 part of 2-ethylhexyl) phosphite). The results of measuring the viscosity of the obtained curable composition 1 are shown in Table 2. A predetermined amount of the curable composition 1 is applied to a cover glass with a black printing of 3 inches so that the film thickness is 200 μm as shown in the coating pattern of FIG. After being fixed with a spot irradiation device (LC-8 (manufactured by Hama Photonics) for 10 seconds at 100 mW / cm ² ), a conveyor type irradiation device (light hammer 6; Fusion UV system, integration) It was fully cured at a light intensity of 6000 mJ / cm ² . Furthermore, after curing for one month under the condition of 23 ° C x 55%, the LCDM backlight was turned on, and the optical unevenness (which looks yellow) was observed in the White mode. It was.

  Further, the curable composition 1 is poured into a mold of 100 mm × 100 mm × 2 mm (thickness), a cured product is produced using the conveyor type irradiation device, and the dumbbell physical properties (at the time of breakage) are prepared according to the method described in JISK6251. The results of measuring the elongation and tensile strength are shown in Table 2. Furthermore, Table 2 shows the results of measurement of the curing shrinkage and hardness by the following methods.

(viscosity)
Measurement was carried out at 25 ° C. using a B-type (BL type) viscometer.

(Curing shrinkage)
The specific gravity of the liquid was measured with a specific gravity bottle, and the specific gravity of the cured product was measured in water. Then, the curing shrinkage was calculated according to the following formula.
Curing shrinkage calculation formula = (cured material specific gravity−liquid specific gravity) / cured material specific gravity * 100

(hardness)
According to the method of JIS6253-3, measurements were performed in a 1 kg load, a load dropping speed of 2.8 mm / sec, and an atmosphere of 23 ° C. × 55% using a cured product having a thickness of 6 mm or more (measuring device; constant pressure loader CL- 150 / Hardness meter DuroE meter (manufactured by Polymer Instruments))

(Examples 2 and 3)
(A) Component, (C) polymerization initiator, (D) component (meth) acryloyl group-containing monomer and heat stabilizer are added in predetermined amounts as shown in Table 2, and the same method as in Example 1 Then, a curable composition was prepared, and the curable composition was applied to a cover glass, bonded to LCDM, and UV cured to prepare a sample for evaluation (image display device). Thereafter, after curing under the same conditions as in Example 1, the state of occurrence of optical unevenness was confirmed by the same method.

(Comparative Example 1)
A curable composition and an image display device were produced in the same manner as in Example 1 using the predetermined amounts shown in Table 2. Optical unevenness occurred in the portion shown in FIG.

  According to the present invention, when the display module such as liquid crystal or organic EL and the transparent protective cover, touch sensor, and touch sensor integrated transparent protective cover are filled with the transparent resin layer of the present invention, light leakage from the display module may occur. It is possible to provide an image display device that does not cause display unevenness and an electric / electronic device equipped with the image display device.

1. Cover glass (protective cover)
2. Black printing part (printing part)
3. Bonding resin layer 4. LCDM (Liquid Crystal Module)
5. Backlight 6. Optical unevenness occurrence part

Claims (15)

An image display device that is filled with a transparent resin layer between at least two kinds of members selected from a transparent cover board, a touch sensor, a flat panel display display module, and a backlight,
Cured product obtained by curing a curable composition (B) containing an acrylic polymer (A) having an elongation at break of 500% or more in a tensile test specified by JISK6251 of the resin layer An image display device characterized by that. The image display according to claim 1, wherein the acrylic polymer (A) is a polymer produced mainly by polymerizing a monomer selected from (meth) acrylic monomers containing an ester structure of C6 or higher. apparatus. The image display device according to claim 1 or 2, wherein the resin layer has a breaking strength defined by JIS K6251 of 20 KPa or more. The image display apparatus according to claim 1, wherein the curable composition (B) is cured with UV. The image display device according to claim 1, wherein the curable composition (B) is heat-cured. The image display device according to any one of claims 1 to 3, wherein the curable composition (B) is cured at 0 to 30 ° C. The acrylic polymer (A) is an acrylic polymer having an average of at least one polymerizable carbon-carbon double bond in one molecule. Image display device. The image display device according to claim 1, wherein the curable composition (B) contains a polymerization initiator (C). 9. The image display device according to claim 8, wherein the polymerization initiator (C) is at least one selected from a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator. The image display device according to claim 9, wherein the polymerization initiator (C) is a photopolymerization initiator. The polymerizable carbon-carbon double bond 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 image display device according to claim 7, wherein the image display device is a group represented by: The image display apparatus in any one of Claims 1-11 in which the curable composition (B) further contains the monomer (D) which has a (meth) acryloyl group. The image display device according to claim 1, wherein the molecular weight distribution of the acrylic polymer (A) is less than 1.8. The image display device according to claim 1, wherein the main chain of the acrylic polymer (A) is produced by a living radical polymerization method. An electrical / electronic device equipped with the image display device according to claim 1.