JP2015010207A - Active energy ray-curable dam composition for fpd lamination - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable dam composition which can cure rapidly by active energy rays, can prevent undesirable outflow of an adhesive, and further does not show unevenness in liquid crystal display and a dam/fill interface even when kept under an environment of high temperature and high humidity after curing, and to provide an FPD obtained by coating and curing the same.SOLUTION: Provided is an active energy ray-curable dam composition for an FPD lamination dam/fill method comprising: a (meth)acrylic polymer (A) having on average at least one polymerizable carbon-carbon double bond in one molecule; a photoinitiator (B); and silica particles (C) having surfaces thereof modified with alkylsilyl groups.

Description

  The present invention relates to an active energy ray-curable dam composition used for an FPD (flat panel display) bonded dam fill method.

Conventionally, an air gap was provided between the liquid crystal module of the image display part of a mobile phone or touch panel and the uppermost transparent cover (PET film, tempered glass, acrylic plate, etc.), and the cover was broken by an impact from the outside. Even in this case, the liquid crystal module has a structure (air gap structure) that does not affect the liquid crystal module. In recent years, optical elasticity that can be cured by light (UV) using photopolymerizable functional group urethane acrylate and epoxy acrylate as binder polymer for the purpose of improving visibility and impact resistance of liquid crystal displays. Resin curable compositions are beginning to be used (Patent Document 1).
However, due to the complexity of the design of the outermost surface cover for the purpose of imparting design properties to mobile phones and touch panels, the area where UV light, which is a trigger for curing, does not transmit increases, resulting in unreacted parts. There is a problem. 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 a UV curing initiator has been proposed (Patent Document 2).

  However, although this improvement method can achieve curability, it has factors that cause thermal damage to the liquid crystal element and cause device malfunction. Further, after the liquid crystal panel and the protective cover are bonded together, a heating process is required, and the number of steps for manufacturing the liquid crystal display device increases. As the number of manufacturing steps increases, a large oven or the like for heating is required, and the configuration of the manufacturing apparatus becomes complicated and large.

  A curable composition containing a compound having an average of at least one crosslinkable silyl group in one molecule and a compound having an average of at least one polymerizable carbon-carbon double bond in one molecule is rapidly cured by light. Even if it is possible and not exposed to light, it does not become uncured. Therefore, a curable composition for filling between the liquid crystal module / transparent cover board having excellent visibility, impact resistance, heat resistance, and light resistance can be obtained (Patent Document 3).

  There is also what is commonly called the dam and fill method. As a first step, a thixotropic material (dam material) is deposited around the interface of the electronic component to be protected to form the barrier layer. The dam material remains immobile by UV irradiation or the like. Subsequently, as a second step, a less liquid material (fill material) with less thixotropic properties is placed over the electronic component in the barrier formed of the dam material. The fill material preferably has very high fluidity. Usually, it is preferable that both the dam material and the fill material are cured by UV irradiation or the like. Encapsulants that are commercially available at present provide similar formulations for both dam materials and fill materials (US Pat. No. 6,057,049).

  Also, in the same method, before and during bonding, a dam for containing an adhesive is provided in a predetermined area to bond the base material to the LCD, and the dam is bonded at a predetermined position. Methods are known to prevent unwanted adhesive spillage. The photocured dam produced during the performance of this method serves as a spacer to maintain a fixed distance between the display and substrate of the display / cure adhesive / substrate bond product. It is known that having this spacer results in an essentially constant level of cured adhesive within the bonded product (US Pat. No. 6,057,049).

  Also, in the dam fill method for sealing semiconductor devices, it is possible to mold and apply on the substrate with a high aspect ratio, and it is possible to completely infiltrate the gaps between elements without protruding the fill material from the substrate, A method of providing a dam material composition or the like that has a high adhesion to a fill material and can form a tough cured product is known (Patent Document 6).

  However, the dam material and the fill material often have different viscosities, so the refractive index is not always the same after curing by UV irradiation or the like, and when the liquid crystal is turned on and viewed from the transparent cover board In addition, there is a problem that the boundary line between the dam agent and the fill agent can be visually recognized, and a solution has been required.

JP 2005-55641 A JP 2008-281997 A JP 2010-248347 A JP 2005-217393 A Special table 2011-503662 gazette JP 2011-014885 A

  The present invention can prevent the adhesive from flowing out undesirably, and after curing, the liquid crystal display unevenness as well as the dam / fill interface is not seen even under high temperature and high humidity environment. An object is to provide an energy ray curable dam composition and an FPD obtained by coating and curing the composition.

  In view of the above circumstances, as a result of intensive studies by the present inventors, it was found that the above problems can be solved by using silica particles (C) whose surfaces are modified with alkylsilyl groups, and the present invention has been completed. .

  That is, the present invention provides a (meth) acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, a photopolymerization initiator (B), and an alkylsilyl surface. The present invention relates to an active energy ray-curable dam composition for FPD-laminated dam-fill method, which contains silica particles (C) modified with a group.

  The alkylsilyl group is preferably a trimethylsilyl group or an octylsilyl group.

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

  The number average molecular weight of the component (A) is preferably more than 3000.

  It is more preferable to further contain a monomer (D) having a polymerizable group and having a number average molecular weight of 3000 or less.

  It is more preferable to further contain an oligomer (E) having a polymerizable group and having a number average molecular weight of 3000 or less.

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

  The main chain of the component (A) is preferably produced by a living radical polymerization method.

  The main chain of component (A) is preferably produced by an atom transfer radical polymerization method.

  The polymerizable carbon-carbon double bond of component (A) is preferably at the end of the molecular chain.

  (A) With respect to 100 parts by weight of component, the addition amount of photopolymerization initiator (B) is 0.001 to 10 parts by weight, and the addition amount of silica particles (C) whose surface is modified with an alkylsilyl group is 5 to 10 parts by weight. The amount is preferably 100 parts by weight.

  The present invention relates to an FPD obtained by applying and curing the active energy ray-curable dam composition for FPD bonding dam fill method described above.

  Use as a fill material a composition containing (meth) acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule and a photopolymerization initiator (B). Is preferred.

  It is preferable that the (A) component and the (B) component of the fill material are the same as those of the dam material.

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

  According to the present invention, it can be quickly cured by an active energy ray, can prevent an undesired outflow of the adhesive, and after being cured, even in a high temperature and high humidity environment, liquid crystal display unevenness, An active energy ray-curable dam composition having no dam / fill interface, and an FPD obtained by coating and curing the composition can be provided.

  The active energy ray-curable composition for FPD-laminated dam-fill method of the present invention is a (meth) acrylic polymer (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, light It contains a polymerization initiator (B) and silica particles (C) whose surface is modified with an alkylsilyl group.

  The active energy ray-curable dam composition of the present invention is described in detail below.

<< (A) component >>
The main chain of the (meth) 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.

  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 (meth) 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 particularly limited. Preferably less than 1.8, more preferably not more than 1.7, still more preferably not more than 1.6, particularly preferably not more than 1.5, particularly preferably not more than 1.4, most preferably not more than 1.3. It is.

  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 (meth) 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 is preferably 3,000 to 100,000 is more preferred, 5,000-80,000 is more preferred, and 8,000-50,000 is even more preferred. In particular, it is preferably over 3000 from the viewpoints of flexibility and elongation at break. 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 (meth) acrylic polymer (A) in the present invention has an average of at least one polymerizable carbon-carbon double bond in one molecule.

As the polymerizable carbon-carbon double bond, the general formula (1)
—OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ 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 ^{1 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.

  The (meth) 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 viewpoint of versatility of the monomer, ease of control, and the like. Among these, controlled radical polymerization is more preferable. This controlled radical polymerization method can be classified into a “chain transfer agent method” and a “living radical polymerization method” which is a kind of living polymerization. Living radical polymerization, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Publication No. 2006-291073.

  The atom transfer radical polymerization, which is one of the preferred methods for synthesizing the (meth) 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.

  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.

<Polymerizable carbon-carbon double bond introduction method (method for synthesizing component (A))>
The polymerizable carbon-carbon double bond of component (A) is preferably at the end of the molecular chain.

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

(Introduction method 1)
A method in which the terminal halogen group of the (meth) acrylic polymer of the general formula (2) is replaced with a compound having a polymerizable carbon-carbon double bond of the general formula (3).
-CR ² R ³ X (2)
(In the formula, R ² and R ³ are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ¹ ) ═CH ₂ (3)
(In the formula, R ¹ represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)
The vinyl polymer having a terminal structure represented by the general formula (2) is a method of polymerizing a vinyl 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 a vinyl 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 1} include, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (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 a vinyl polymer having a hydroxyl group at the terminal. XC (O) C (R ¹ ) = CH ₂ (4)
(In the formula, R ¹ 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 in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal, and a residual isocyanate group is reacted with a compound represented by the following general formula (5).
HO—R ⁴ —OC (O) C (R ¹ ) ═CH ₂ (5)
(In the formula, R ⁴ represents hydrogen or an organic group having 1 to 20 carbon atoms. R ⁴ 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, the photopolymerization initiator (B) is used in order to quickly cure the component (A) or obtain a cured product having sufficient properties.

  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 Examples include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl and the like.

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

  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. It is preferable to use an absorbing cationic dye-borate anion complex or the like, and it is more preferable to use a boron sensitizer together.

  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.

  Although the addition amount of a photoinitiator (B) does not have a restriction | limiting in particular, 0.001-10 weight part is preferable with respect to 100 weight part of (A) component from the point of sclerosis | hardenability and storage stability. 1 to 5 parts by weight is more preferable.

<< Silica particle (C) whose surface is modified with an alkylsilyl group >>
The shape of the silica particles (C) whose surfaces used in the present invention are modified with an alkylsilyl group is not particularly limited, and may be spherical, elliptical, flat, rod-like, or fibrous. (Hereafter, it may be abbreviated as “silica particles (C)”.)
The average particle diameter of the silica particles (C) is preferably 1 to 1000 nm, more preferably 3 to 100 nm, and particularly preferably 5 to 20 nm. When the average particle diameter of the inorganic fine particles is within the above range, the dispersibility in the monomer having a photopolymerizable group is improved, and the transparency of the material for forming the three-dimensional pattern of the present invention is further improved. can do. These average particle diameters are determined by a method of observing the particles with an electron microscope or a method of measuring the particle diameter of a sol in which the particles are dispersed in a liquid by a dynamic light scattering method.

The silica particles (C) have a specific surface area (according to the BET adsorption method) of 50 m ² / g or more, usually 50 to 400 m ² / g, preferably about 100 to 300 m ² / g of ultrafine powdered silica.

  As the surface of the silica particles (C) used in the present invention, those whose surfaces are modified with alkylsilyl groups are used. As the alkylsilyl group, a monoalkylsilyl group, a dialkylsilyl group, or a trialkylsilyl group can be used.

  Examples of the monoalkylsilyl group include methyltrimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, and decyltrimethoxysilane.

  Examples of the dialkylsilyl group include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

  Examples of the trialkylsilyl group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

  Among the alkylsilyl groups, a trimethylsilyl group and an octylsilyl group are preferable in that the dam material and the fill material have the same refractive index.

  The content of the silica particles (C) is preferably 5 to 100 parts by weight, more preferably 5 to 80 parts by weight, particularly preferably 5 to 60 parts by weight, based on 100 parts by weight of the component (A). Particularly preferred is 5 to 30 parts by weight. If the content of silica particles (C) is too large, the flexibility is impaired, stress propagation to the liquid crystal module and the like becomes prominent, and there is a tendency to cause display unevenness of the liquid crystal. The adhesive for display panels sometimes leaked from the edge of the pasted sample.

<< Compounding agent >>
In the curable composition of the present invention, various compounding agents may be added according to the intended physical properties.

<Monomer (D) and oligomer (E) having a polymerizable group and a number average molecular weight of 3000 or less>
When the number average molecular weight of the component (A) exceeds 3000, the curable composition of the present invention has a polymerizable group within a range not impairing the effects of the present invention, and the number average molecular weight is 3000 or less. (D) can be added. In addition or in place of (D), an oligomer (E) having a polymerizable group and having a number average molecular weight of 3000 or less can be added. 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 groups such as (meth) acrylic groups, styrene groups, acrylonitrile groups, vinyl ester groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketone groups, and vinyl chloride. Groups and the like. Especially, what has the (meth) acryloyl group similar to the vinyl polymer used for this invention is 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. Especially, what has the (meth) acryloyl group similar to the vinyl polymer used for this invention is 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.

  Among the above, monomers and / or oligomers having a (meth) acryloyl group are preferred. The number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is 3000 or less, and the monomer is used for further improving the surface curability and reducing the viscosity for improving workability. In this case, it is more preferable that the molecular weight is 1000 or less because the compatibility is good.

  The amount of the polymerizable monomer and / or oligomer used is 1 to 200 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of improving surface curability, imparting toughness, and workability due to viscosity reduction. Preferably, 5 to 100 parts by weight is more preferable.

<Filler>
Although it does not specifically limit as a filler, The filler of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0158] is mentioned. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

  In particular, 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.

  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.

  Although the addition amount of antioxidant is not specifically limited, Preferably it is 0.1-10 weight part with respect to 100 weight part of (A) component, More preferably, it can be used in 0.5-5 weight part.

<Plasticizer>
In the curable composition of the present invention, a plasticizer can be blended as necessary within a range where liquid crystal display unevenness due to moisture absorption of the resin does not occur.

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

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

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

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

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

  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) component. If it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 10 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Adhesive agent>
An adhesiveness-imparting agent can be added to the curable composition 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 the phosphoric acid group-containing monomer, 2-((meth) acryloylcyethyl phosphate), 2- (meth) acryloyloxypropyl phosphate, 2- (meth) acryloyloxy-3-chloropropyl phosphate, 2 -(Meth) acryloyloxyethyl phenyl phosphate and the like. Of these, phosphate group-containing monomers are preferred. The monomer may have two or more polymerizable groups.

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

  The adhesiveness-imparting agent is preferably blended in an amount of 0.01 to 20 parts by weight per 100 parts by weight of 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.

<< Active energy ray-curable dam composition >>
The active energy ray-curable dam composition of the present invention can be prepared as a one-pack type in which all the ingredients are pre-blended and sealed, and the A liquid from which only the initiator is removed and the initiator as a filler, a plasticizer, It can also be prepared as a two-component type in which the liquid B mixed with a solvent or the like is mixed immediately before molding. Since the active energy ray-curable dam composition of the present invention can be quickly cured by active energy rays, it is a spacer for maintaining a fixed distance between the substrates by being applied to the outer periphery of the substrate and then cured. Also useful as. Further, when used for FPD bonding, it is an active energy ray-curable dam composition in which liquid crystal display unevenness and dam / fill boundaries are not observed even in a high temperature and high humidity environment after curing.

<< Damfill method >>
It is generally called dam and fill, and the dam is formed from a low-viscosity fill material that has been made highly viscous with a filler, etc., and the dam process is very outside the part to be dispensed. This is an operation of forming a limit line using a highly viscous sealing material. The filling process is an operation of substantially sealing the surface of the base material by filling a liquid sealing material having a viscosity relatively lower than that of the dam material inside the dam process. Normally, the same composition is used for the fill material and the dam material except for fillers. The composition of the present invention is a dam composition used for dam materials.

  As the fill material in the present invention, any active energy ray-curable composition can be used, but polymerizable carbon is not contained in one molecule in that no liquid crystal display unevenness and dam / fill interface are observed. -It is preferable to use a composition containing a (meth) acrylic polymer (A) having at least one carbon double bond on average and a photopolymerization initiator (B). In particular, the (A) component and the (B) component of the fill material are preferably the same as the dam material. In other words, it is preferable to use a material obtained by removing the silica particles (C) from the composition of the present invention.

<Application method>
The method for applying the curable composition of the present invention to the FPD 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, 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.

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

  By using the photopolymerization initiator (B), the curable composition can be cured by irradiation with light or an electron beam from an active energy ray source. 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 limitations on the site when the active energy ray-curable dam composition is used for FPD, but there are no particular limitations, such as touch panel and mobile phone liquid crystals, organic EL or organic TFT screens, computer liquid crystals, organic EL or organic TFT screens, Car navigation liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, and the like.

  The present invention includes an FPD obtained by applying and curing the curable composition for FPD bonding, and an electric / electronic device equipped with the FPD.

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.

The “number of acryloyl groups introduced per polymer molecule” was calculated from the number average molecular weight determined by ¹ H-NMR analysis and GPC. (However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 (400 MHz) and deuterated chloroform as a solvent.)
In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Examples 1, 2, and 3)
Table 1 shows the amount of each raw material used.
(1) Polymerization step n-butyl acrylate (premixed n-butyl acrylate) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, cuprous bromide and a part of all n-butyl acrylate (described as initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1) and diethyl-2,5-dibromoadipate (DBAE) or ethyl 2-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 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, Showa Chemical Industry Co., Ltd.) and an adsorbent (KYOWARD 700SEN (KW700SEN)) , Kyoward 500SH (KW500SH)) 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 adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.
(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), potassium acrylate (about 2 molar equivalents relative to terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P1], [P2] and [P3] 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
20 parts of the polymer [P1] obtained in Production Examples 1, 2, and 3 as component (A), 10 parts of [P2], 70 parts of [P3], and HOA (acrylic acid-2 as component (D)) 7 parts of hydroxylethyl (manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of ISTA (isostearyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.)), DAROCUR1173 (2-hydroxy-2-methyl-1-phenyl-1-) as component (B) Propane-1-one (manufactured by Ciba Specialty Chemicals) 0.8 parts and Lucirin TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide (manufactured by Ciba Specialty Chemicals)) 0.1 Part, (C) component, Aerosil R812 (surface treatment: trimethylsilyl group) (Evonik) 12.5 parts, and further, as a plasticizer , 15 parts of dibutoxyethoxyethyl adipate (trade name Adeka Sizer RS107S, Kao Co., Ltd.), which is an adipate ether ester plasticizer, and an ultralight rosin derivative (Arakawa Chemical Industries, trade name Pine Crystal) as a tackifier resin A curable dam composition was prepared by sufficiently stirring and mixing 10 parts of KE-100 Hazen color tone of 200 or less.
Subsequently, components except for the component (C) were sufficiently stirred and mixed in the same manner as the curable dam composition to obtain a curable fill composition.
The obtained curable dam composition and curable fill composition were evaluated according to the following evaluation methods.

<Evaluation method>
(viscosity)
The active energy ray-curable composition was placed in a sample bottle and allowed to stand for 24 hours or more at 25 ° C. in a sealed state, and then the viscosity was measured. The measuring instrument was measured at a rotational speed of 60 rpm using a BL type viscometer (manufactured by Toki Sangyo). The rotor is no. 4 was used.

(Dam / fill composition boundary)
First, a curable dam composition is applied along a 5 mm wide outer peripheral region defined in advance from four corners of an alkali glass having a thickness of 1 mm and a width of 50 mm square, and UV light is irradiated to form a cured dam composition. did. UV light irradiation is performed by irradiating UV light with an integrated light quantity of 3000 mJ / cm ² using a UV irradiation device (Light Hammer 6; manufactured by Fusion UV system Japan), and the thickness of the cured layer of the dam composition adhesive is 200 μm. It adjusted so that it might become.

  Subsequently, an appropriate amount of the fill composition, which is an adhesive composition for display panels, is dropped on another glass of the same size, and the glass is turned over to bring it closer to the glass on which the cured dam composition is applied. The product was spread uniformly and adjusted so that the thickness of the cured layer was 200 μm. After confirming that the fill composition contacted and fused with the dam composition, the film was allowed to stand for 20 seconds, and then irradiation with UV light was started to obtain a bonded sample. The dam / fill interface of the obtained sample was visually confirmed after being left at 25 ° C. for 24 hours or more. The appearance after the wet heat resistance test was visually confirmed after being left for 7 days at 65 ° C. and 90% RH.

(LCD uneven display)
A dam / fill composition was prepared in the same manner as described above except that a liquid crystal module was used instead of the alkali glass to which the curable dam composition for evaluation of the presence / absence of a dam / fill material was applied. The display unevenness of the liquid crystal display surface was judged to be uneven if the liquid crystal module was turned on after 7 days at 65 ° C. and 90% RH, and even a slight unevenness could be visually confirmed.

(Example 2, Comparative Examples 1 and 2)
A curable dam composition was obtained in the same manner as in Example 1 with the blending ratio shown in Table 2. Evaluation similar to Example 1 was performed using the obtained curable dam composition. The evaluation results are shown in Table 2. The component (C) used in Example 2 was Aerosil R805 (surface treatment: octylsilyl group) (Evonik), and the silica components other than (C) used in Comparative Example 1 were Aerosil R7200 (surface treatment). : Methacryloxysilyl group (Evonik) and silica component other than (C) used in Comparative Example 2 are Aerosil RY200S (surface treatment: surface coating with dimethylpolysiloxane) (Evonik).
The evaluation results are shown in Table 2.

(Comparative Example 3)
Comparative Example 3 is a base composition before adding the silica component, and is the same component as Example 1 except that silica is not blended. The evaluation results are shown in Table 2.

  From the comparison between Examples 1-2 and Comparative Examples 1-2, the refractive index of the filler of Comparative Example 3 after UV irradiation is almost the same by using silica particles whose surfaces are modified with alkylsilyl groups. After leaving the pasted sample at 25 ° C. for 24 hours or more and 65 ° C., 90% RH for 7 days, the boundary line of the dam / fill material and the display unevenness on the liquid crystal display surface could not be confirmed by visual observation. Has been. Therefore, this hardened | cured material is suitable as a filler for FPD bonding.

According to the present invention, by using an active energy ray-curable dam composition containing specific silica particles, no dam / fill boundary and liquid crystal display unevenness are observed even in a high temperature and high humidity environment. An FPD and an electric / electronic device equipped with the FPD can be provided.

Claims (15)

(Meth) acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, photopolymerization initiator (B), and silica whose surface is modified with an alkylsilyl group An active energy ray-curable dam composition for an FPD-bonded dam-fill method characterized by containing particles (C). The active energy ray-curable dam composition for FPD-laminated dam-fill method according to claim 1, wherein the alkylsilyl group is a trimethylsilyl group or an octylsilyl group. The polymerizable carbon-carbon double bond of the component (A) has the general formula (1)
—OC (O) C (R ¹ ) ═CH ₂ (1)
(Wherein R ¹ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The active energy ray-curable dam composition for FPD-laminated dam-fill method according to claim 1 or 2, wherein The number average molecular weight of (A) component is over 3000, The active energy ray-curable dam composition for FPD bonding dam fill method according to any one of claims 1 to 3. The active energy ray-curable dam composition for an FPD-bonded dam-fill method according to claim 4, further comprising a monomer (D) having a polymerizable group and having a number average molecular weight of 3000 or less. The active energy ray-curable dam composition for FPD bonding dam fill method according to claim 4 or 5, further comprising an oligomer (E) having a polymerizable group and having a number average molecular weight of 3000 or less. (A) The molecular weight distribution of a component is less than 1.8, The active energy ray-curable dam composition for FPD bonding dam fill construction methods in any one of Claims 1-6 characterized by the above-mentioned. The active energy ray-curable dam composition for FPD-laminated dam-fill method according to any one of claims 1 to 7, wherein the main chain of the component (A) is produced by a living radical polymerization method. The active energy ray-curable dam composition for FPD-laminated dam-fill method according to any one of claims 1 to 7, wherein the main chain of component (A) is produced by an atom transfer radical polymerization method. . 10. The active energy ray-curable dam composition for FPD-laminated dam-fill method according to claim 1, wherein the polymerizable carbon-carbon double bond of component (A) is at the molecular chain end. . (A) With respect to 100 parts by weight of component, the addition amount of photopolymerization initiator (B) is 0.001 to 10 parts by weight, and the addition amount of silica particles (C) whose surface is modified with an alkylsilyl group is 5 to 10 parts by weight. The active energy ray-curable dam composition for an FPD-bonded dam-fill method according to any one of claims 1 to 10, wherein the composition is 100 parts by weight. FPD obtained by apply | coating and hardening the active energy ray-curable dam composition for FPD bonding dam fill construction method in any one of Claims 1-11. Use as a fill material a composition containing (meth) acrylic polymer (A) having at least one polymerizable carbon-carbon double bond on average in one molecule and a photopolymerization initiator (B). The FPD according to claim 12, wherein: 14. The FPD according to claim 13, wherein the (A) component and the (B) component of the fill material are the same as those of the dam material. An electric / electronic device equipped with the FPD according to claim 12.