JP2014047291A - Photocurable composition for fpd lamination with improved dark part hardening - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can cure fast by an active energy ray and that can insure hardening even of the black coated part of FPD where an active energy ray does not reach, by allowing scattered light to penetrate thereinto, and further a method of curing an active energy ray curable composition, of which liquid crystal display shimmering caused by resin moisture absorption under conditions of high temperature and high humidity, is improved.SOLUTION: An active energy ray curable composition for FPD lamination is characterized to contain: compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule; photoinitiator (B); and silica particles (C) with the surface treated with silane coupling agent having (meth)acryloyl group.

Description

  The present invention relates to a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a silane coupling having a (meth) acryloyl group on the surface. The present invention relates to an FPD (flat panel display) laminating photocurable composition characterized by containing silica particles (C) treated with an agent, and an FPD obtained by coating and curing the curable composition.

  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, in part, it can be cured with light (UV) using urethane acrylate or epoxy acrylate having an active energy ray polymerizable functional group as a binder polymer for the purpose of improving the visibility and impact resistance of liquid crystal displays. Optical elastic resin curable compositions are beginning to be used. 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. However, although this improvement method can ensure curability, there is a concern of causing thermal damage to the liquid crystal module.

  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 obtained by active energy rays. Even a portion that can be rapidly cured and is not exposed to active energy rays does not become uncured (Patent Document 1). 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 2).

  However, when the reaction rate of the moisture-curing component of the curable composition filled between the liquid crystal module and the transparent cover board is low, there is a problem that the black coating portion that is not exposed to the active energy ray is not sufficiently cured and needs to be solved. It was.

WO2008 / 041768 JP 2010-248347 A

  The present invention is directed to overcoming the problems set forth above. That is, it is a curable composition that can be quickly cured by active energy rays and that can transmit the scattered light to the black coating portion of the FPD that is not exposed to active energy rays to ensure the curability. An object of the present invention is to provide a method for curing an active energy ray-curable composition in which unevenness of liquid crystal display due to moisture absorption of a resin is improved even in a high humidity environment, 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 has been found that the above problem can be solved by using silica particles (C) whose surface is treated with a silane coupling agent having a (meth) acryloyl group. The invention has been completed.

  That is, the present invention relates to a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a silane having a (meth) acryloyl group on the surface. The present invention relates to an active energy ray-curable composition for FPD laminating, which contains silica particles (C) treated with a coupling agent.

  The component (A) is preferably an organic polymer or oligomer.

  The organic polymer or oligomer of the component (A) is preferably at least one selected from polysiloxane, polyether, and vinyl polymer.

  The organic polymer or oligomer of the component (A) is preferably a (meth) acrylic polymer.

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 an oligomer having a (meth) acryloyl group polymerizable group and a number average molecular weight of 3000 or less, and / or a monomer (D).

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

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

  The main chain of the vinyl polymer (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.

  Silica particles treated with a silane coupling agent having a (meth) acryloyl group on the surface with 0.001 to 10 parts by weight of the photopolymerization initiator (B) added per 100 parts by weight of the component (A) (C ) Is preferably 5 to 100 parts by weight per 100 parts by weight of the total amount of component (A).

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

  The active energy ray-curable composition for FPD laminating described above is applied to a substrate having a portion where the active energy ray does not reach directly, and the active energy ray is irradiated directly. The present invention relates to a method of curing a part of the curable composition that does not reach.

  According to the present invention, it is a method of curing a curable composition that can be quickly cured by an active energy ray and that can ensure the curability even in a portion that is not exposed to an active energy ray, and further, a high temperature / high humidity environment after curing. Even underneath, an active energy ray-curable composition with improved liquid crystal display unevenness due to moisture absorption of the resin can be obtained. Moreover, it aims at provision of FPD obtained by apply | coating and hardening it.

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

  The active energy ray-curable composition of the present invention comprises a compound (A) having an average of at least one polymerizable carbon-carbon double bond in one molecule, a photopolymerization initiator (B), and a surface (meta). It contains silica particles (C) treated with a silane coupling agent having an acryloyl group.

<< (A) component >>
The component (A) may be any of a low molecular weight compound, an oligomer and a polymer, but is preferably an oligomer or an organic polymer in terms of a balance of flexibility, durability and curability. An organic polymer is particularly preferable.

  The organic polymer refers to a compound having a repeating unit of an organic compound and comprising 100 or more repeating units. An oligomer refers to a compound having a repeating unit of an organic compound and comprising 2 to 100 repeating units. The low molecular weight compound is a compound having a structure other than an oligomer or an organic polymer and basically having no repeating unit.

  As said organic polymer or oligomer, polysiloxane, polyether, and vinyl polymer are preferable, and vinyl polymer is more preferable.

  As the polysiloxane, alkyl polysiloxane is preferable.

  The polyether is preferably an oxyalkylene polymer, and more preferably polyoxyethylene or polyoxypropylene.

  Examples of the vinyl polymer include hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, and fluorine-containing vinyls. A polymer produced mainly by polymerizing a monomer selected from the group consisting of a system monomer and a silicon-containing vinyl monomer is preferred. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more. Further, the vinyl polymer is preferably a (meth) acrylic polymer produced by mainly polymerizing polyisobutylene and a (meth) acrylic monomer, more preferably an acrylic polymer, and an acrylic ester monomer. An acrylic ester polymer produced mainly by polymerization is more preferred.

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

  The oligomer, the main chain of the organic polymer, the production method, etc. will be described below.

<Polysiloxane>
Known methods for producing organopolysiloxanes by hydrolyzing organochlorosilane, Japanese Patent No. 2599517, Japanese Patent Laid-Open No. 56-151731, Japanese Patent Laid-Open No. 59-66422, Japanese Patent Laid-Open No. 59-68377 Can be obtained by a known method such as a hydrolysis method in the presence of a basic catalyst or an acid catalyst. Examples of the terminal functional group of the polymer include an alkoxysilyl group, a silanol group, and a hydroxyl group.

  The number average molecular weight of the polysiloxane in the present invention is not particularly limited, but is 500 to 1,000,000, more preferably 3,000 to 100,000, when measured by GPC. If the molecular weight is too low, the elongation and flexibility tend to be insufficient, and if it is too high, the viscosity tends to increase and workability such as coating tends to decrease.

<Polyether>
The method for synthesizing the polyether (oxyalkylene polymer) is not particularly limited. For example, it can be obtained by ring-opening polymerization of a monoepoxide in the presence of an initiator and a catalyst.

  Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Examples thereof include dihydric alcohols such as glycol, polypropylene triol, polypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, trimethylol propane, and pentaerythritol, polyhydric alcohols, and various oligomers having a hydroxyl group.

  Specific examples of the monoepoxide include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide, and other alkylene oxides, methyl glycidyl ether, ethyl Examples thereof include alkyl glycidyl ethers such as glycidyl ether, isopropyl glycidyl ether, and butyl glycidyl ether, and allyl glycidyl ethers.

  As the catalyst and polymerization method, for example, a polymerization method using an alkali catalyst such as KOH, for example, a transition metal compound such as a complex obtained by reacting an organoaluminum compound and porphyrin disclosed in JP-A-61-215623 Polymerization using a porphyrin complex catalyst, for example, a polymerization method using a double metal cyanide complex catalyst, a polymerization method using a cesium catalyst, a polymerization method using a phosphazene catalyst, and the like disclosed in Japanese Patent Publication Nos. 46-27250 and 59-15336. However, it is not particularly limited. Among these, a polymerization method using a double metal cyanide complex catalyst is preferable from the viewpoint of easily obtaining a polymer having a high molecular weight and little coloring.

In addition, the main chain skeleton of the oxyalkylene-based polymer is a hydroxyl group-terminated oxyalkylene polymer in the presence of a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH ₃ or the like, and a bifunctional or higher alkyl halide such as CH It can also be obtained by chain extension with ₂ Cl ₂ , CH ₂ Br ₂ or the like.

  Further, the main chain skeleton of the oxyalkylene polymer may contain other components such as a urethane bond component as long as the characteristics of the oxyalkylene polymer are not significantly impaired.

  The number average molecular weight of the polyether in the present invention is not particularly limited, but is 500 to 1,000,000, more preferably 1,000 to 100,000 when measured by GPC. If the molecular weight is too low, the elongation and flexibility tend to be insufficient, and if it is too high, the viscosity tends to increase and workability such as coating tends to decrease.

<Vinyl polymer>
(Hydrocarbon polymer)
The hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring. For example, 1,2-polybutadiene, 1,4-polybutadiene, polyethylene, polypropylene, polyisobutylene , Hydrogenated polybutadiene, hydrogenated polyisoprene, and the like.

  The polymer constituting the main chain skeleton of the hydrocarbon polymer used in the present invention is (1) having 1 to 1 carbon atoms such as ethylene, propylene, 1,2-butadiene, 1,4-butadiene, 1-butene and isobutylene. After homopolymerizing or copolymerizing 6 olefinic compounds as main components, or (2) homopolymerizing or copolymerizing diene compounds such as butadiene and isoprene, or after copolymerizing the above olefinic compounds It can be obtained by a method such as hydrogenation.

  Among these, polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene are preferable because it is easy to introduce a functional group at the terminal, easily control the molecular weight, and increase the number of terminal functional groups. Furthermore, since polyisobutylene has liquid or fluidity, it is easy to handle, and since it does not contain any carbon-carbon unsaturated bonds other than aromatic rings in the main chain, there is no need for hydrogenation and it is particularly excellent in weather resistance. preferable. In the polyisobutylene, all of the monomer units may be formed from isobutylene units, or the monomer units copolymerizable with isobutylene are preferably 50 wt% or less, more preferably 30 wt% in polyisobutylene. % Or less, particularly preferably 10% by weight or less.

  Examples of such monomer components for hydrocarbon polymerization include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. For example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene , Α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane , Divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allyl Examples include methyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane. .

  In the hydrogenated polyisoprene, hydrogenated polybutadiene, and other hydrocarbon polymers, as in the case of the above polyisobutylene, other monomer units may be contained in addition to the main monomer unit. Good.

  The number average molecular weight of the hydrocarbon polymer, preferably polyisobutylene, hydrogenated polyisoprene, or hydrogenated polybutadiene is preferably about 500 to 50,000, and particularly liquid or fluidity of about 1,000 to 20,000. It is preferable from the viewpoint of easy handling.

(Vinyl polymers other than hydrocarbon polymers)
The vinyl polymer other than the hydrocarbon polymer in the present invention is not particularly limited as the vinyl monomer constituting the main chain, and various types can be used. Specifically, (meth) acrylic acid; (meth) methyl acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ( T) 3-methoxybutyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryl 2-aminoethyl acid, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (Meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, Dimethafluoromethyl methyl (meth) acrylate, (meth) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecyl (meth) acrylate (Meth) acrylic acid ester monomers such as ethyl; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid Ter and dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitriles such as acrylonitrile and methacrylonitrile Group-containing vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; vinyl chloride, vinylidene chloride, chloride Examples include allyl and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  The main chain of the vinyl polymer other than the hydrocarbon polymer used in the curable composition of the present invention is a (meth) acrylic monomer such as (meth) acrylic acid or a (meth) acrylic acid ester monomer, acrylonitrile It is preferable that the polymer is produced mainly by polymerizing at least one monomer selected from the group consisting of a series monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and a silicon-containing vinyl monomer. Here, “mainly” means that 50 mol% or more of the monomer units constituting the vinyl polymer is the above monomer, and preferably 70 mol% or more. Among these, from the physical properties of the product, a (meth) acrylic polymer obtained by polymerizing a (meth) acrylic monomer is preferable, and an acrylic polymer is more preferable. An acrylate polymer obtained by polymerizing an acrylate monomer is more preferable. Particularly preferred acrylic ester monomers include alkyl acrylate monomers, specifically ethyl acrylate, 2-methoxyethyl acrylate, stearyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid. 2-methoxybutyl.

  In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in this case, these preferred monomers may be contained in a weight ratio of 40% by weight or more. preferable.

  The number average molecular weight of the vinyl polymer other than the hydrocarbon polymer in the present invention is not particularly limited, but it is in the range of 500 to 1,000,000 when measured by GPC, 3,000 to 100,000. 000 is more preferred, 5,000 to 80,000 is more preferred, and 8,000 to 50,000 is even more preferred. If the molecular weight is too low, the original characteristics of vinyl polymers other than hydrocarbon polymers tend to be difficult to be expressed. On the other hand, if the molecular weight is too high, handling tends to be difficult.

  The vinyl 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, 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, in which the molecular weight and molecular weight distribution of the resulting vinyl polymer can be easily controlled, is further preferred, and atom transfer radical polymerization is particularly preferred from the viewpoint of availability of raw materials and ease of introduction of a functional group at the polymer terminal. The above radical polymerization, controlled radical polymerization, chain transfer agent method, living radical polymerization method, and atom transfer radical polymerization are known polymerization methods. For example, JP-A-2005-232419 and Reference can be made to the description in Japanese Unexamined Patent Application Publication No. 2006-291073.

  Atom transfer radical polymerization, which is one of the preferred methods for synthesizing vinyl polymers other than hydrocarbon polymers in the present invention, will be briefly described below.

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

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

Etc.

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

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. 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 (synthesis method of component (A)) >>
The polymerizable carbon-carbon double bond of the component (A) is not particularly limited, but 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 (meth) acryloyl group represented by these is preferable.

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

<Introduction method to polysiloxane>
Although there is no particular limitation, for example, a hydrolyzable silyl group-containing vinyl compound, a hydrolyzable silyl group-containing (meth) acryloyl compound can be prepared by using an organometal or the like as a terminal silanol-terminated polysiloxane described in Japanese Patent No. 3193866. Examples include a method of hydrolytic condensation reaction.

<Introduction method to polyether>
The method for introducing a polymerizable carbon-carbon double bond into the oxyalkylene polymer is not particularly limited, but <1> a polyoxyalkylene having a hydroxyl terminal is reacted with an acid chloride compound of the general formula (1). <2> a method of reacting a compound of the general formula (1) containing an isocyanate group with a polyoxyalkylene having a hydroxyl terminal, <3> a polyfunctional isocyanate with a polyoxyalkylene having a hydroxyl terminal, and A method of reacting a vinyl monomer containing a hydroxyl group, <4> a polysilyl group having a hydrosilylation capable double bond terminal (for example, allyl group terminal) polyoxyalkylene, and a polyfunctional type hydrosilyl compound, and further reacting with allyl (meth) acrylate, etc. There is a method of reacting a compound capable of hydrosilylation. The methods <2>, <3>, and <4> are preferable from the viewpoint of the simplicity of the reaction, and the methods <2> and <3> are more preferable from the viewpoint of the stability of the reaction.

<Introduction method to vinyl polymer>
As a method for introducing a polymerizable carbon-carbon double bond into the vinyl 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 of replacing the terminal halogen group of the vinyl polymer of the general formula (2) 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, benzoin Tyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl- Examples include 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, dibenzoyl and the like.

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

  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 particles treated with a silane coupling agent having a (meth) acryloyl group on the surface (C) >>
The shape of the silica particles (C) obtained by treating the surface used in the present invention with a silane coupling agent having a (meth) acryloyl 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 surface of the silica particles (C) used in the present invention is preferably surface-modified with a hydrolyzable silane compound having an active energy ray reactive group, and a silane coupling agent having a (meth) acryloyl group is used. The

  Specific examples of the silane coupling agent having a (meth) acryloyl group include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltrichlorosilane, and γ-methacryloxypropyl. Methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropylmethyldichlorosilane, γ-methacryloxypropyldimethylmethoxysilane, γ-methacryloxypropyldimethylethoxysilane, γ-methacryloxypropyldimethylchlorosilane, γ -Acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropyltrichlorosilane, γ-acryloxypropylmethyldimethoxy Lan, γ-acryloxypropylmethyldiethoxysilane, γ-acryloxypropylmethyldichlorosilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyldimethylethoxysilane, γ-acryloxypropyldimethylchlorosilane, γ-acrylic Loxymethyltrimethoxysilane, gamma-acryloxymethyltriethoxysilane, gamma-acryloxymethyltrichlorosilane, gamma-acryloxymethylmethyldimethoxysilane, gamma-acryloxymethylmethyldiethoxysilane, gamma-acryloxymethylmethyldichlorosilane Γ-acryloxymethyldimethylmethoxysilane, γ-acryloxymethyldimethylethoxysilane, and γ-acryloxymethyldimethylchlorosilane.

  For example, γ-acryloxypropyltrimethoxysilane is commercially available as “KBM-5103 (trade name)” from Shin-Etsu Chemical Co., Ltd., and many silane coupling agents are commercially available. I can do it.

  The surface modification amount of the hydrolyzable silane compound having an active energy ray reactive group is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and particularly preferably 1 to the particle. ˜5 mass%.

  The silica particles (C) may or may not be dispersed in a solvent. Colloidal silica dispersed in an organic solvent is commercially available as an organosilica sol, such as “organosilica sol” (trade name, manufactured by Nissan Chemical Industries, Ltd.). Examples of the organic solvent include methanol, ethanol, isopropanol, butanol, propyl cellosolve, dimethylacetamide, toluene, xylene, ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone.

  The content of the silica particles (C) is preferably 5 to 100 parts by weight, more preferably 5 to 80 parts by weight, and particularly preferably 10 to 60 parts by weight with respect to 100 parts by weight of the total component (A). Particularly preferred is 15 to 40 parts by weight. If there is too much content of silica particles (C), flexibility is impaired, stress propagation to the liquid crystal module, etc. becomes remarkable, and at the interface between the black coating part where UV irradiation does not reach and the part where irradiation reaches , Liquid crystal display unevenness tends to occur, and if it is too small, the amount of light scattering medium will be too small, and the amount of scattered light will be insufficient at the black coating area where light does not hit, making it difficult to ensure practical curability. .

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

<Oligomer having a polymerizable group and a number average molecular weight of 3000 or less, and / or monomer (D)>
When the number average molecular weight of the component (A) exceeds 3000, the curable composition of the present invention has an oligomer having a polymerizable group within a range not impairing the effects of the present invention, and the number average molecular weight is 3000 or less. And / or monomer (D) 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, crystalline silica, fused silica, dolomite, carbon black, calcium carbonate, titanium oxide, talc 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 it is more preferable to use a micro hollow body having a true 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 it is not particularly limited, among the light stabilizers, an ultraviolet absorber is preferable, and specifically, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 Benzotriazole compounds such as Tinuvin 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as Tinuvin 120 (manufactured by Ciba Geigy Japan).

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

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

  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 be lowered. Preferably it is 0.1-10 weight part, More preferably, it is 0.5-5 weight part.

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

<Solvent>
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 B liquid is mixed immediately before molding.

Active energy ray curable composition for FPD bonding The active energy ray curable composition of the present invention can be rapidly cured by active energy rays, and the scattered light is transmitted through the black coating portion of the FPD not exposed to active energy rays. It is a curable composition that can secure curable properties and is preferably used for FPD bonding, but there is no particular limitation on the site, and there is no particular limitation on the liquid crystal of a touch panel, a mobile phone, an organic EL or organic TFT screen, a liquid crystal of a computer, an organic EL or organic TFT screen, car navigation liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, and the like.

<< 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.

<< Molding 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.

<< Usage >>
There are no particular limitations on the site when the active energy ray curable composition is used for FPD, 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 systems. Liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, and the like.

  This invention includes FPD obtained by apply | coating and hardening the said curable composition for FPD bonding.

  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; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.

In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, from the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
(However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 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 and 2)
Table 1 shows the amount of each raw material used.

(1) Polymerization process n-butyl acrylate was deoxygenated. The inside of the stainless steel reaction vessel with a stirrer was deoxygenated, and cuprous bromide and a part of all n-butyl acrylate (described as initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1), diethyl 2,5-dibromoadipate (DBAE) or ethyl 2-bromobutyrate as an initiator were added and mixed, and the temperature of the mixture was adjusted to about 80 ° C. Pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining n-butyl acrylate (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during 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.

(2) Oxygen treatment step When the monomer conversion rate (polymerization reaction rate) was about 95% or more, an oxygen-nitrogen mixed gas was introduced into the gas phase part of the reaction vessel. While maintaining the internal temperature at about 80 ° C. to about 90 ° C., the reaction solution was heated and stirred for several hours to bring the polymerization catalyst in the reaction solution into contact with oxygen. Acetonitrile and unreacted monomer were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer. The concentrate was markedly colored.

(3) First crude purification Butyl acetate was used as a diluent solvent for the polymer. Dilute the concentrate of (2) with about 100-150 kg of butyl acetate per 100 kg of polymer, and add a filter aid (Radiolite R900, Showa Chemical Industry Co., Ltd.) and an adsorbent (Kyoward 700 SEN, Kyoward 500 SH). 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), heat stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P1] and [P2] having Table 1 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
30 parts of the polymer [P1] obtained in Production Examples 1 and 2 as component (A), 70 parts of [P2], and DAROCUR1173 (2-hydroxy-2-methyl-1-phenyl-) as component (B) 0.8 parts of 1-propan-1-one (Ciba Specialty Chemicals) and Lucirin TPO (2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Ciba Specialty Chemicals)) 0 .2 parts, (C) 20 parts of silica particles (manufactured by Nissan Chemical Industries, trade name: MEK-AC-4101) whose surface was treated with a silane coupling agent having a (meth) acryloyl group were sufficiently stirred. The curable composition was prepared by mixing.

The obtained curable composition was bonded between a liquid crystal module and a glass plate having a UV non-transmitting part on the periphery so as to have a film thickness of 200 μm, and a UV irradiation device (Light Hammer 6; made by Fusion UV system Japan) was used. After curing by irradiation with an integrated light amount of 3000 mJ / cm ² , the curing depth (curing penetration depth) from the irradiated surface is measured with a vernier caliper one day after UV curing with respect to the curability of the part that does not transmit UV. It was measured. The display unevenness of the liquid crystal display surface was determined to be uneven if the liquid crystal module was turned on after 7 days at 65 ° C. and 90% relative humidity and the unevenness could be confirmed by visual observation. The evaluation results are shown in Table 2.

(Comparative Example 1)
A curable composition was prepared in the same manner as in Example 1 except that 20 parts of silica particles (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST-L) were used instead of the component (C) in Example 1. did. Table 2 shows the evaluation results of the curability (curing penetration depth) and display unevenness of the site where UV does not transmit.

(Comparative Example 2)
A curable composition was prepared in the same manner as in Example 1 except that 20 parts of silica particles (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST-ZL) were used instead of the component (C) in Example 1. did. Table 2 shows the evaluation results of the curability (curing penetration depth) and display unevenness of the site where UV does not transmit.

(Comparative Example 3)
A curable composition was prepared in the same manner as in Example 1 except that the component (C) in Example 1 was not added. Table 2 shows the evaluation results of the curability (curing penetration depth) and display unevenness of the site where UV does not transmit.

  From the comparison between Example 1 and Comparative Examples 1 to 3, by using silica particles whose surface was treated with a silane coupling agent having a (meth) acryloyl group, the curability of the part where UV did not pass one day after UV irradiation. A considerable amount of (curing penetration depth) was confirmed, and liquid crystal display unevenness on the liquid crystal display surface was not visually confirmed after 7 days at 65 ° C. and a relative humidity of 90%, and each was improved. Therefore, this hardened | cured material is considered to be suitable as a filler for FPD bonding.

According to the present invention, it is a curable composition that can be rapidly cured by light and can transmit the scattered light even to a black coating portion that is not exposed to light, and can secure the curability. Even below, it is possible to provide a UV curable composition in which unevenness in liquid crystal display due to moisture absorption of the resin is improved, and an electric / electronic device equipped with an FPD obtained by coating and curing the composition.

Claims (14)

The compound (A) having at least one polymerizable carbon-carbon double bond on average in one molecule, the photopolymerization initiator (B), and the surface were treated with a silane coupling agent having a (meth) acryloyl group. An active energy ray-curable composition for FPD bonding, comprising silica particles (C). The active energy ray-curable composition for FPD bonding according to claim 1, wherein the component (A) is an organic polymer or an oligomer. The active energy ray for FPD bonding according to claim 2, wherein the organic polymer or oligomer of the component (A) is at least one selected from polysiloxane, polyether, and vinyl polymer. Curable composition. The active energy ray-curable composition for FPD bonding according to claim 2 or 3, wherein the organic polymer or oligomer of the component (A) is a (meth) acrylic polymer. 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 composition for FPD bonding according to any one of claims 1 to 4, wherein The number average molecular weight of (A) component is more than 3000, The active energy ray curable composition for FPD bonding in any one of Claims 2-5 characterized by the above-mentioned. The active energy ray-curable composition for FPD bonding according to claim 6, further comprising an oligomer having a (meth) acryloyl group polymerizable group and a number average molecular weight of 3000 or less, and / or a monomer (D). object. The active energy ray-curable composition for FPD bonding according to any one of claims 2 to 7, wherein the molecular weight distribution of the organic polymer or oligomer of the component (A) is less than 1.8. The active energy ray-curable composition for FPD bonding according to any one of claims 3 to 8, wherein the main chain of the vinyl polymer of component (A) is produced by a living radical polymerization method. object. The active energy ray curability for FPD bonding according to any one of claims 3 to 9, wherein the main chain of the vinyl polymer (A) is produced by an atom transfer radical polymerization method. Composition. The active energy ray-curable composition for FPD bonding according to any one of claims 1 to 10, wherein the polymerizable carbon-carbon double bond of the component (A) is at the molecular chain end. Silica particles (C) in which the addition amount of the photopolymerization initiator (B) is 0.001 to 10 parts by weight with respect to 100 parts by weight of the component (A) and the surface is treated with a silane coupling agent having a (meth) acryloyl group The active energy ray-curable composition for FPD bonding according to any one of claims 1 to 11, wherein the amount of addition of A) is 5 to 100 parts by weight per 100 parts by weight of the total amount of component (A) . FPD obtained by apply | coating and hardening the active energy ray curable composition for FPD bonding in any one of Claims 1-12. Applying the active energy ray-curable composition for FPD bonding according to any one of claims 1 to 12 to a substrate having a portion where the active energy rays do not reach directly, and irradiating the active energy rays. The method of hardening | curing the curable composition of the part which an active energy ray does not reach directly.