JP2012082341A - Light/moisture dual-cure system curable composition for laminating fpd - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV/moisture dual-cure system curable composition for laminating an FPD, which is a curable composition in which rapid curing is possible by light, and a part on which light is not irradiated is not left uncured, and further display unevenness of a liquid crystal part has been improved.SOLUTION: The light/moisture dual-cure system curable composition for laminating an FPD includes: a compound (A) which has at least one hydrolyzable silyl group in average in one molecule; a compound (B) which has at least an average of one polymerizable carbon-carbon double bond in one molecule; a photopolymerization initiator (C); a curing catalyst (D); and a modulus regulator (E).

Description

  The present invention relates to a compound (A) having an average of at least one hydrolyzable silyl group in one molecule, a compound (B) having an average of at least one polymerizable carbon-carbon double bond in one molecule, Light / moisture dual cure curable composition for FPD bonding containing a photopolymerization initiator (C), a curing catalyst (D), and a modulus regulator (E), and obtained by curing the curable composition The present invention relates to an FPD bonding filler and an electric / electronic device equipped with an FPD obtained by applying 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, 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. 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 the curability, when the front cover is a plastic material such as a PET film, there is a problem that the film is deformed by heating.

  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. A portion that is possible and not exposed to light does not become uncured (Patent Document 1). Therefore, a curable composition for filling between the liquid crystal module and the transparent cover board having excellent visibility, impact resistance, heat resistance, and light resistance can be obtained.

  However, when the curable composition filled between the liquid crystal module and the transparent cover board is cured, the surface protection film and the polarizing plate of the liquid crystal module are deformed due to internal stress due to curing shrinkage of the resin, and as a result, the liquid crystal display There was a problem that unevenness occurred, and a solution was necessary.

WO2008 / 041768

  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 light and that does not become uncured even in a portion that is not exposed to light, and further has an improved liquid crystal display unevenness when cured. It is an object of the present invention to provide a cured curable composition and an electric / electronic device equipped with 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 problems can be solved by using the modulus adjusting agent (E) as an additive, and the present invention has been completed.

  That is, the present invention relates to a compound (A) having an average of at least one hydrolyzable silyl group in one molecule (B), a compound having an average of at least one polymerizable carbon-carbon double bond in one molecule (B ), A photopolymerization initiator (C), a curing catalyst (D), and a modulus adjuster (E), and a light / moisture dual cure curable composition for FPD bonding.

  The modulus modifier (E) is preferably a compound that generates trimethylsilanol by hydrolysis.

  The compound that generates trimethylsilanol by hydrolysis is preferably phenoxytrimethylsilane and / or tris ((trimethylsiloxy) methyl) propane.

  The component (A) and / or the component (B) is preferably an organic polymer or oligomer.

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

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

  The organic polymer or oligomer of the component (A) and / or the organic polymer or oligomer of the component (B) is preferably an acrylic polymer.

  The organic polymer or oligomer of the component (A) and / or the organic polymer or oligomer of the component (B) is preferably an acrylate ester polymer.

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

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

  It is preferable to further contain an oligomer and / or monomer (F) having a (meth) acryloyl group and having a number average molecular weight of 3000 or less.

The hydrolyzable silyl group is preferably represented by the general formula (2).
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (2)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1).

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

  The main chain of the vinyl polymer as the component (A) and / or the vinyl polymer as the component (B) is preferably produced by a living polymerization method.

  The main chain of the vinyl polymer as the component (A) and / or the vinyl polymer as the component (B) is preferably produced by an atom transfer radical polymerization method.

  It is preferable that the hydrolyzable silyl group of the component (A) and / or the polymerizable carbon-carbon double bond of the component (B) is at the end of the molecular chain.

  The present invention relates to a cured product for FPD bonding obtained by curing a light / moisture dual cure curable composition for FPD bonding.

  The present invention relates to an electric / electronic device equipped with a flat panel display obtained by applying and curing a light / moisture dual cure curable composition for FPD bonding.

  According to the present invention, a light / moisture dual cure for FPD laminating that can be rapidly cured by light and that is not uncured even in a portion that is not exposed to light, and further has improved liquid crystal display unevenness when cured. A system curable composition can be obtained. Moreover, it aims at provision of the electrical / electronic device which mounts FPD obtained by apply | coating and hardening it.

Curable composition The curable composition of the present invention is described in detail below.
The light / moisture dual cure curable composition for FPD bonding of the present invention has a compound (A) having an average of at least one hydrolyzable silyl group in one molecule, and a polymerizable in one molecule. It contains a compound (B) having at least one carbon-carbon double bond on average, a photopolymerization initiator (C), a curing catalyst (D), and a modulus regulator (E).

<< (A) component and (B) component >>
The skeletons of the component (A) and the component (B) may be the same or different, but are preferably the same skeleton from the viewpoint of compatibility. In addition, the component (A) and the component (B) may be any of a low molecular weight compound, an oligomer, and a polymer, but are oligomers or organic in terms of a balance of flexibility, durability, and curability. A polymer is preferred, and an organic polymer is particularly preferred.

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. Furthermore, as the vinyl polymer, a (meth) acrylic polymer produced by mainly polymerizing polyisobutylene and a (meth) acrylic monomer is preferable, and a (meth) acrylic polymer is more preferable. As the (meth) acrylic polymer, an acrylic polymer is preferable, and an acrylate polymer is more preferable.

The molecular weight distribution of the organic polymer or oligomer of component (A) and / or the organic polymer or oligomer of component (B), that is, the weight average molecular weight (Mw) and number measured by gel permeation chromatography (GPC). The ratio (Mw / Mn) of the average molecular weight (Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, further preferably 1.6 or less, and further Preferably it is 1.5 or less, Especially preferably, it is 1.4 or less, Most preferably, it is 1.3 or less. When the molecular weight distribution is 1.8 or more, the viscosity increases and the handling tends to be difficult. In addition, GPC measurement in this invention uses chloroform as a mobile phase, a measurement is performed with a polystyrene gel column, and a number average molecular weight etc. can be calculated | required by polystyrene conversion.
Since any oligomer and organic polymer can be explained in common with respect to the main chain, the production method, etc., they will be explained together 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, allyl glycidyl ethers, and aryl 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 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 can also be obtained by chain extension due 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 monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, maleimides such as various monomers described in paragraph [0018] of JP-A-2005-232419 Examples thereof include vinyl monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, allyl chloride, 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, an acrylonitrile monomer, an aromatic vinyl monomer, a fluorine-containing vinyl monomer, and It is preferable that it is produced mainly by polymerizing at least one monomer selected from the group consisting of silicon-containing vinyl monomers. 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. Of these, aromatic vinyl monomers and / or (meth) acrylic acid monomers are preferred, acrylic acid ester monomers and / or methacrylic acid ester monomers are more preferred, and acrylic acid ester monomers are even more preferred from the physical properties of the product. . 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,

等が挙げられる。

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.

<< Method for Introducing Crosslinkable Silyl Group (Method for Synthesizing Component (A)) >>
The hydrolyzable silyl group as used in the field of this invention is a silicon-containing functional group which can be bridge | crosslinked by forming a siloxane bond, and the group represented by General formula (2) is preferable.
^{_{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (2)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1).

  The hydrolyzable silyl group of the component (A) may be at any molecular end in the main chain, but is preferably at the molecular end.

<Introduction method to polysiloxane>
The method for introducing a hydrolyzable silyl group is not particularly limited. For example, when a polysiloxane is synthesized using a silane compound containing a hydrolyzable silyl group as an acid and a base as a catalyst component, the hydrolysis and condensation conditions are set. There are a method of adjusting and leaving hydrolyzable silyl at the terminal, a method of reacting a terminal chloro group-containing polysiloxane with chlorosilane containing hydrolyzable silyl, and the like.

<Introduction method to polyether>
(Α) A method of reacting a hydrosilyl compound represented by the general formula (3) after introducing an olefin group into an oxyalkylene polymer having a functional group such as a hydroxyl group.
HSiX _a R ² _3-a (3)
(Wherein R ² , X and a are the same as above)

  Here, as a method for introducing an olefin group, a compound having both an unsaturated group and a functional group capable of reacting with a hydroxyl group is reacted with a hydroxyl group of an oxyalkylene polymer to form an ether bond, an ester bond, a urethane bond, and a carbonate bond. And a method of introducing an olefin group by adding and copolymerizing an olefin group-containing epoxy compound such as allyl glycidyl ether when the alkylene oxide is polymerized.

(Β) A method of reacting a compound represented by the general formula (4) with an oxyalkylene polymer having a functional group capable of reacting with an isocyanate compound.
(R ² ) _3-a SiX _a -R ³ NCO (4)
(In the formula, R ² , X and a are the same as above. R ³ is a divalent hydrocarbon group having 1 to 17 carbon atoms.)

(Γ) After an isocyanate group is introduced by reacting a polyisocyanate compound such as tolylene diisocyanate with an oxyalkylene polymer having a functional group capable of reacting with an isocyanate compound, the isocyanate group is represented by the general formula (5). A method of reacting a W group of a silicon compound.
(R ² ) _3-a SiX _a -R ³ W (5)
(Wherein R ² , R ³ , X, and a are the same as described above. W represents an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary).)

(Δ) An olefin group is introduced into an oxyalkylene polymer having a functional group into which an olefin group can be introduced, and the olefin group is reacted with a silicon compound represented by the general formula (5) in which W is a mercapto group. Method.
Of these, the methods (α) and (β) are preferred from the introduction yield and the simplicity of the introduction method, and the method (α) is more preferred from the viewpoint of resin physical properties such as viscosity.

<Introduction method to vinyl polymer>
1) Hydrocarbon polymer There is no particular limitation, but introduction by the method (α) is preferable in terms of introduction yield and ease of reaction.
2) Vinyl-based polymers other than hydrocarbon-based methods The methods described in paragraphs [0102] to [0112] of JP-A-2004-210858 can be mentioned. Among these methods, it is produced by a method in which the alkenyl group of a polymer having a terminal alkenyl group is converted to a crosslinkable silyl group by a hydrosilylation reaction with a hydrosilane compound having a crosslinkable silyl group because it is easier to control. It is preferable that
<< Polymerizable carbon-carbon double bond introduction method (method for synthesizing component (B)) >>
The polymerizable carbon-carbon double bond of the component (B) is not particularly limited, but the general formula (1)
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The (meth) acryloyl group represented by these is preferable.
In addition, the polymerizable carbon-carbon double bond of the component (B) 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. 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 in which the terminal halogen group of the vinyl polymer of the general formula (6) is substituted with a compound having a polymerizable carbon-carbon double bond of the general formula (7).
-CR ⁴ R ⁵ X (6)
(In the formula, R ⁴ and R ⁵ are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R ^a ) ═CH ₂ (7)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

  The vinyl polymer having a terminal structure represented by the general formula (6) 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.

As the compound represented by the general formula (7) is not particularly limited, specific examples of ^{R a} are, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (7) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (6), 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 (8) with a vinyl polymer having a hydroxyl group at the terminal. XC (O) C (R ^a ) = CH ₂ (8)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group.)

(Introduction method 3)
A method 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 (9).
HO-R ^b- OC (O) C (R ^a ) ═CH ₂ (9)
(In the formula, R ^a represents hydrogen or an organic group having 1 to 20 carbon atoms. R ^b represents a divalent organic group having 2 to 20 carbon atoms.)
Among these methods, (Introduction method 1) is most preferable because it is easy to control.

<< Photoinitiator (C) >>
In the curable composition of the present invention, a photopolymerization initiator (C) is used in order to cure quickly or to 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 (C) does not have a restriction | limiting in particular, 0.001-10 weight part is preferable with respect to 100 weight part of (B) component from the point of sclerosis | hardenability and storage stability.

<< Curing Catalyst (D) >>
Although it does not specifically limit to the curable composition of this invention, It is preferable to use a curing catalyst (D). The compound (A) having an average of at least one hydrolyzable silyl group used in the present invention is present in the presence of various conventionally known condensation catalysts (also referred to as curing catalysts or “curing agents”), or non- Crosslink and cure by forming siloxane bonds in the presence. As the properties of the cured product, a wide range from rubbery to resinous can be prepared depending on the molecular weight and main chain skeleton of the polymer.

  In the curable composition of the present invention, various conventionally known condensation catalysts used for polymers having a crosslinkable silyl group may be used.

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

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

<Amine compound>
In the curable composition of the present invention, an amine compound may be added to further increase the activity of the condensation catalyst.

Examples of the amine compound include amine-based amines such as aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, aliphatic unsaturated amines, and aromatic amines as described above. Compounds, polyamine compounds and the like can be mentioned, but are not limited to the exemplified substances. These amine compounds may be used alone or in combination of two or more.
The amount of these amine compounds added is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 100 parts by weight of the compound (A) having at least one hydrolyzable silyl group on average. More preferable is 20 parts by weight. If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 50 parts by weight, the pot life may become too short, which is not preferable from the viewpoint of workability.

  When this amine compound is added, it may be mixed and reacted with the curing catalyst in advance, or may be mixed later. If they are mixed and reacted in advance, the catalytic activity becomes higher and fast curability may be realized.

  Further, in the curable composition of the present invention, in order to further enhance the activity of the condensation catalyst, it is also possible to use the above-mentioned silane coupling agent having an amino group as a cocatalyst in the same manner as the amine compound. . The amino group-containing silane coupling agent is a compound having a silicon atom to which a hydrolyzable group is bonded (hereinafter referred to as a hydrolyzable silyl group) and an amino group, and the groups already exemplified as the hydrolyzable group. A methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more.

  The compounding amount of these amino group-containing silane coupling agents is preferably about 0.05 to 10 times by weight with respect to the curing catalyst, and more preferably 0.1 to 3 parts by weight. If the compounding amount of the amino group-containing silane coupling agent is too small or too large, the curing rate may be slow, the curing reaction may not proceed sufficiently, or the pot life may be too short. It is not preferable from the viewpoint of workability. These amino group-containing silane coupling agents may be used alone or in combination of two or more.

  These amine compounds are more preferable from the viewpoint of reducing the amount of use because they have high catalytic activity when used in combination with the above organic acids. Among organic acid and amine combined systems, there are acidic phosphoric acid esters and amines, carboxylic acid and amine combinations, among others, organic acidic phosphoric acid esters and amines, and organic carboxylic acid and amine combined systems are catalytically active. Is preferable from the viewpoint of fast curability, and further, a combined system of an organic carboxylic acid and an amine, particularly a combined system of an aliphatic carboxylic acid and an amine is preferable.

  Furthermore, a silicon compound having no amino group or silanol group may be added as a promoter. These silicon compounds are not limited, but phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like are preferable. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are most preferable because of low cost and easy availability.

  The compounding amount of the silicon compound is preferably about 0.01 to 20 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the compound (A) having at least one hydrolyzable silyl group on average. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

  The type and amount of the curing catalyst / curing agent can control the curability and mechanical properties of the present invention according to the purpose and application. Also, the type and amount of the curing catalyst / curing agent can be changed depending on the reactivity of the silyl group of the polymer having a crosslinkable silyl group, and the amount of the curing catalyst (D) added is the hydrolyzable silyl group. 0.01 to 10 parts is preferable with respect to 100 parts of compound (A) having at least one compound on average, but when the reactivity is high, it can be sufficiently cured in a small range of 0.01 to 1 part. is there.

  The type and amount of the curing catalyst / curing agent include, for example, the hydrolyzable silyl group of the compound (A) having an average of at least one hydrolyzable silyl group of the present invention, and the type of Y in the general formula (2). And a can be selected depending on the number of a and a, and the curability and mechanical properties of the present invention can be controlled according to the purpose and application. When Y is an alkoxy group, the smaller the number of carbons, the higher the reactivity, and the larger a the higher the reactivity, so that it can be sufficiently cured in a small amount.

<< Modulus Modifier (E) >>
A modulus regulator (E) is used for the curable composition of this invention. The modulus modifier (E) is a compound capable of producing a compound having one silanol group in the molecule or a compound having one silanol group in the molecule. The hydrolyzable silyl of component (A) By reacting with the group, the crosslinked structure of the component (A) can be changed, and the cured product can have a lower modulus.

  Examples of the compound having one silanol group in the molecule include trimethylsilanol, triethylsilanol, and triphenylsilanol. Examples of compounds that can produce a compound having one silanol group in the molecule include N-trimethylsilylacetamide, hexamethyldisilazane, methoxytrimethylsilane, ethoxytrimethylsilane, isopropyloxytrimethylsilane, butoxytrimethylsilane, and hexyloxytrimethylsilane. 2-ethylhexyloxysilane, n-octyloxysilane, 2-chloropropyloxytrimethylsilane, phenoxytrimethylsilane, 2-methylphenoxytrimethylsilane, 2-chlorophenoxytrimethylsilane, methoxydimethylphenylsilane, methoxymethyldiphenylsilane, phenoxy Examples include dimethylphenylsilane, phenoxytrimethylsilane, and tris ((trimethylsiloxy) methyl) propane. Also, ethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol A compound in which a hydroxyl group of a polyvalent hydroxy compound such as trimethylsilyl ether is used can also be used.

Among them, compounds that generate trimethylsilanol by hydrolysis are preferable, and phenoxytrimethylsilane and tris ((trimethylsiloxy) methyl) propane are particularly preferable. These may be used alone or in combination of two or more.
The amount of the modulus adjusting agent (E) is not particularly limited, but is preferably 0.1 to 20 parts by weight per 100 parts by weight of the compound (A) having an average of at least one hydrolyzable silyl group in one molecule. When the modulus adjusting agent (E) is 0.1 parts by weight or less, the effect of reducing the modulus of the cured product by the modulus adjusting agent may be insufficient, and when it is 20 parts by weight or more, the progress of curing due to moisture. May be inhibited.

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

<Oligomer and / or monomer (F) having a polymerizable group and a number average molecular weight of 3000 or less>
When the number average molecular weight of the component (B) 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 (F) 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 group such as (meth) acryl group, styrene group, acrylonitrile group, vinyl ester group, N-vinylpyrrolidone group, acrylamide group, conjugated diene group, vinyl ketone group, and chloride. A vinyl group etc. are mentioned. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.

Examples of the anionic polymerizable group include a (meth) acryloyl group such as a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, and a vinyl ketone group. Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention are preferable.
Specific examples of the monomer include those described in paragraphs [0123] to [0131] of JP-A-2006-265488.
Examples of the oligomer include those described in paragraph [0132] of JP-A-2006-265488.

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

  The amount of the polymerizable monomer and / or oligomer used is 100 parts by weight (hereinafter simply referred to as “component (A)” and “component (B)”) from the viewpoints of improving surface curability, imparting toughness, and workability due to viscosity reduction. To 200 parts, and more preferably 5 to 100 parts.

<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. In the case of using a filler, it is preferable to use the filler in the range of 5 to 1000 parts by weight with respect to the total of 100 parts by weight of the component (A) and the component (B), and 20 to 500 parts by weight. More preferably, it is used in a 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.

  The addition amount of the balloon is not particularly limited, but is preferably in the range of 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). Can be used in 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 and (B) component total, More preferably, it is 0.5-5 weight part Can be used in a range of

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

  Although the number average molecular weight of the said polymeric plasticizer was described as 500-15000, Preferably it is 800-10000, More preferably, it is 1000-8000. If the molecular weight is too low, the plasticizer may flow out 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 and (B) component total, 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 amount of the reactive diluent added is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and still more preferably 1 with respect to 100 parts by weight of the total of the components (A) and (B). ~ 50 parts by weight.

<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. 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 the range of 0.1-10 weight part with respect to 100 weight part of (A) component and (B) component total. If the amount 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, the effect is not very different, 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 with respect to 100 parts by weight as a total of the components (A) and (B). 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.

Cured product for FPD bonding The cured product for FPD bonding of the present invention is obtained by curing the curable composition.
<< Curing method >>
The method for curing the curable composition is not particularly limited.
By using the photopolymerization initiator (C), the curable composition can be cured by irradiation with light or an electron beam from an active energy ray source. Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example. The curing temperature is preferably 0 ° C to 150 ° C, more preferably 5 ° C to 120 ° C.

The curable composition of the present invention can be further cured by moisture curing. The relative humidity during moisture curing is preferably 5 to 95%, and more preferably 10 to 80%.
Moreover, since the curable composition of this invention can be hardened | cured by photocuring with moisture hardening, while being hardened rapidly by light, it does not become uncured also about the part which does not receive light. (C) When using 2 or more types of mixtures as a component, according to the kind of initiator, hardening conditions can be combined suitably.

<< Molding method >>
When using the curable composition of this invention as a filler for FPD bonding, it is not specifically limited, Various application methods generally used 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.

<< Hardening shrinkage >>
The curing shrinkage when the curable composition of the present invention is cured with light / moisture is preferably 2% or less. If the curing shrinkage rate exceeds 2%, the surface protection film or polarizing plate of the liquid crystal module may be deformed due to internal stress due to the curing shrinkage of the resin, and as a result, display unevenness of the liquid crystal may occur.

<< Usage >>
There are no particular restrictions on the site where the FPD bonding filler is used, but there are no particular limitations on the touch panel, mobile phone liquid crystal, organic EL or organic TFT screen, computer liquid crystal, organic EL or organic TFT screen, car navigation liquid crystal, organic EL or organic TFT screen, liquid crystal, organic EL or organic TFT TV display, etc.
The present invention includes an electric / electronic device on which a flat panel display obtained by applying and curing the curable composition for FPD bonding is mounted.

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

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

The liquid crystal display unevenness was confirmed by laminating the compound between the liquid crystal module and a glass plate having a UV non-transmitting part in the periphery so that the film thickness was 100 μm, and a UV irradiation device (Light Hammer 6; Fusion UV system Japan). The product was irradiated with an integrated light amount of 3000 mJ / cm ² and further cured for 7 days at room temperature (23 ° C.) and a relative humidity of 55%.

<Production of hydrolyzable silyl group-containing (meth) acrylic polymer>
(Production Example 1)
(1) Polymerization step Acrylic acid ester (in the case of copolymerization, a predetermined amount of acrylic acid ester mixed in advance) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1) and diethyl-2,5-dibromoadipate as an initiator were added and mixed, and pentamethyldiethylenetriamine (hereinafter referred to as triamine) was mixed at a temperature of about 80 ° C. (Omitted) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during polymerization is shown in Table 1 as polymerization triamine. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, volatile components were removed by devolatilization under reduced pressure to obtain a polymer concentrate.

(2) Diene reaction step 1,7-octadiene (hereinafter abbreviated as diene or octadiene) and acetonitrile (described in Table 1 as acetonitrile for diene reaction) are added to the concentrate, and a triamine (in Table 1, triamine for diene reaction) Added). While adjusting the internal temperature to about 80 ° C. to about 90 ° C., the mixture was heated and stirred for several hours to react the octadiene with the polymer terminal. Acetonitrile and unreacted octadiene were removed by devolatilization under reduced pressure to obtain a concentrate containing a polymer having an alkenyl group at the terminal.

(3) Rough purification step The above concentrate is diluted with toluene, filter aid, adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical Industry Co., Ltd.) ) Was added and the mixture was heated and stirred at about 80 to 100 ° C., and then the solid component was filtered off. The filtrate was concentrated to obtain a crude polymer product.

(4) High-temperature heat treatment / adsorption purification process Crude polymer product, heat stabilizer (Sumilyzer GS: manufactured by Sumitomo Chemical Co., Ltd.), adsorbent (KYOWARD 700SEN, KYOWARD 500SH) are added, and devolatilization under reduced pressure. The temperature was raised while heating and stirring, and heating and stirring and vacuum devolatilization were performed for about several hours at a high temperature of about 170 ° C to about 200 ° C. Adsorbents (Kyoward 700SEN, Kyoward 500SH) were added, about 10 parts by weight of toluene was added to the polymer, and the mixture was further heated and stirred at a high temperature of about 170 ° C. to about 200 ° C. for several hours. The treatment liquid was further diluted with toluene, and the adsorbent was filtered off. The filtrate was concentrated to obtain a polymer having alkenyl groups at both ends.

(5) Silylation step Polymer obtained by the above method, methyldimethoxysilane (DMS), methyl orthoformate (MOF), platinum catalyst [bis (1,3-divinyl-1,1,3,3-tetramethyl A predetermined amount of (disiloxane) platinum complex catalyst in isopropanol solution: hereinafter referred to as platinum catalyst] was mixed and heated to about 100 ° C. with stirring. After heating and stirring for about 1 hour, volatile components such as unreacted DMS were distilled off under reduced pressure to obtain a polymer [P1] having methoxysilyl groups at both ends. The number of silyl groups introduced per molecule of the obtained polymer, the molecular weight, and the molecular weight distribution are shown together in Table 1.

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Example 2)
Table 2 shows the amount of each raw material used.
(1) Polymerization process The acrylic ester (premixed acrylic ester) was deoxygenated. The inside of the stainless steel reaction vessel equipped with a stirrer was deoxygenated, and cuprous bromide and a part of the total acrylic ester (described as the initial charge monomer in Table 2) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 2) and diethyl-2,5-dibromoadipate (DBAE) as an initiator were added and mixed, and pentamethyldiethylenetriamine (hereinafter referred to as “the temperature of the mixture” was adjusted to about 80 ° C.) , Abbreviated as triamine), and the polymerization reaction was started. The remaining acrylic ester (described as an additional monomer in Table 2) was sequentially added to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during polymerization is shown in Table 2 as polymerization triamine. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.

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

(3) First crude purification Butyl acetate was used as a diluent solvent for the polymer. The concentrate of (2) is diluted with about 100 to 150 kg of butyl acetate with respect to 100 kg of the polymer, and a filter aid (Radiolite R900, manufactured by Showa Chemical Industry Co., Ltd.) and / or an adsorbent (KYOWARD 700SEN, Kyoward 500SH) 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. A polymer [P2] having was obtained. Table 2 shows the number of acryloyl groups introduced per molecule of the obtained polymer, the number average molecular weight, and the molecular weight distribution.

Example 1
(A) 50 parts of the polymer [P1] obtained in Production Example 1 as the component, (B) 50 parts of the polymer [P2] obtained in Production Example 2 as the component, and (C) the component DAROCUR1173 (2- 0.4 parts of hydroxy-2-methyl-1-phenyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) and IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine) 0.1 parts of oxide (manufactured by Ciba Specialty Chemicals), 2.4 parts of neodecanoic acid (trade name Versatic 10, product of Japan Epoxy Resin) as component (D), 1,8-diazabicyclo (5, 4,0) Undecene-7 (DBU) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.55 parts, (E) component as tris ((trimethylsiloxy) methyl) pro (Trade name AZ-6170, manufactured by Toray Dow Corning) 3 parts, trimethylsilyl phenyl ether (trade name TMSP, manufactured by Toray Dow Corning) 3 parts, and isoboronyl acrylate (trade name IBXA, Osaka Organics) 15 parts of Synthetic Industry Co., Ltd., 15 parts of dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.), vinyltrimethoxysilane (trade name SILQUEST A171, Momentive Performance Materials) 1.2 parts, γ-glycidoxypropyltrimethoxysilane (trade name SILQUEST A187, manufactured by Momentive Performance Materials Japan), 3-acryloxypropyltrimethoxysilane (trade name) KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 It was adjusted sufficiently mixed by stirring with the curable composition.
When this compound was checked for the display unevenness state of the liquid crystal, no display unevenness was observed.

(Example 2)
As the component (A), 40 parts of the polymer [P1] obtained in Production Example 1, as the component (B), 60 parts of the polymer [P2] obtained in Production Example 2, and as the component (C) DAROCUR1173 (2- 0.4 parts of hydroxy-2-methyl-1-phenyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) and IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine) 0.1 parts of oxide (manufactured by Ciba Specialty Chemicals), 1 part of 2-ethylhexyl acid phosphate (trade name AP-8, manufactured by Daihachi Chemical Industry) as component (D), 1,8-diazabicyclo ( 5,4,0) Undecene-7 (DBU) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3 part, Tris ((trimethylsiloxy) methyl) pro as component (E) (Trade name AZ-6170, manufactured by Toray Dow Corning) 0.8 part, trimethylsilylphenyl ether (trade name TMSP, manufactured by Toray Dow Corning) 0.8 part, and methoxypolyethylene glycol acrylate (trade name) Light acrylate 130A, manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts, dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 10 parts, vinyltrimethoxysilane (trade name SILQUEST A171, Momentive Performance・ Materials Japan Co., Ltd.) 1.2 parts, γ-glycidoxypropyltrimethoxysilane (trade name SILQUEST A187, Momentive Performance Materials Japan Co., Ltd.) 4 parts, 3-acryloxypropyltrimethoxy Silane (product name BM-5103, was adjusted by Shin-Etsu Chemical Co., Ltd.) 2 parts, and sufficiently stirred and mixed with the curable composition.
With respect to this blend, when the liquid crystal display uneven state was confirmed, slight display unevenness was observed.

(Comparative Example 1)
(A) 50 parts of the polymer [P1] obtained in Production Example 1 as the component, (B) 50 parts of the polymer [P2] obtained in Production Example 2 as the component, and (C) the component DAROCUR1173 (2- 0.4 parts of hydroxy-2-methyl-1-phenyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) and IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine) 0.1 parts of oxide (manufactured by Ciba Specialty Chemicals), 2.4 parts of neodecanoic acid (trade name Versatic 10, product of Japan Epoxy Resin) as component (D), 1,8-diazabicyclo (5, 4,0) Undecene-7 (DBU) (manufactured by Wako Pure Chemical Industries, Ltd.) 1.1 parts, and isoboronyl acrylate (trade name IBXA, Osaka Organic Synthesis) 15 parts, dicyclopentanyl methacrylate (trade name FA-513M, manufactured by Hitachi Chemical Co., Ltd.), 15 parts vinyltrimethoxysilane (trade name SILQUEST A171, Momentive Performance Materials Japan) 1.2 parts, γ-glycidoxypropyltrimethoxysilane (trade name SILQUEST A187, made by Momentive Performance Materials Japan), 3-acryloxypropyltrimethoxysilane (trade name KBM) -5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was sufficiently stirred and mixed to prepare a curable composition.
When this compound was checked for the display unevenness state of the liquid crystal, strong display unevenness was observed.

(Comparative Example 2)
As the component (A), 40 parts of the polymer [P1] obtained in Production Example 1, as the component (B), 60 parts of the polymer [P2] obtained in Production Example 2, and as the component (C) DAROCUR1173 (2- 0.4 parts of hydroxy-2-methyl-1-phenyl-1-propan-1-one (manufactured by Ciba Specialty Chemicals) and IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine) 0.1 parts of oxide (manufactured by Ciba Specialty Chemicals), 1 part of 2-ethylhexyl acid phosphate (trade name AP-8, manufactured by Daihachi Chemical Industry) as component (D), 1,8-diazabicyclo ( 5,4,0) Undecene-7 (DBU) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.3 part, and methoxypolyethylene glycol acrylate (trade name LA 130 parts of triacrylate 130A, manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of dicyclopentenyloxyethyl methacrylate (trade name FA-512M, manufactured by Hitachi Chemical Co., Ltd.), vinyltrimethoxysilane (trade name SILQUEST A171, Momentive Performance Materials Japan Co., Ltd.) 1.2 parts, γ-glycidoxypropyltrimethoxysilane (trade name SILQUEST A187, Momentive Performance Materials Japan Co., Ltd.) 4 parts, 3-acryloxypropyltri A curable composition was prepared by sufficiently stirring and mixing 2 parts of methoxysilane (trade name KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.).
When this compound was checked for the display unevenness state of the liquid crystal, strong display unevenness was observed. Table 3 shows the compositions and evaluation results of the cured products of Examples and Comparative Examples.

  From the comparison between Examples 1 and 2 and Comparative Examples 1 and 2, the display unevenness of the liquid crystal is improved by using the modulus adjusting agent (E). This cured product is considered to be suitable as a filler for FPD bonding.

  According to the present invention, it is a curable composition that can be quickly cured by light and does not become uncured even in a portion that is not exposed to light, and further UV unevenness in liquid crystal display when cured is improved. / Moisture dual cure curable composition and electric / electronic equipment equipped with FPD obtained by coating and curing the composition can be provided.

Claims (18)

Compound (A) having an average of at least one hydrolyzable silyl group in one molecule, Compound (B) having an average of at least one polymerizable carbon-carbon double bond in one molecule, Photopolymerization initiator A light / moisture dual cure curable composition for FPD bonding, comprising (C), a curing catalyst (D), and a modulus modifier (E). The light / moisture dual cure curable composition for FPD bonding according to claim 1, wherein the modulus modifier (E) is a compound that generates trimethylsilanol by hydrolysis. The light / moisture dual cure system for FPD bonding according to claim 2, wherein the compound that generates trimethylsilanol by hydrolysis is phenoxytrimethylsilane and / or tris ((trimethylsiloxy) methyl) propane. Curable composition. The light / moisture dual cure curable composition for FPD bonding according to any one of claims 1 to 3, wherein the component (A) and / or the component (B) is an organic polymer or oligomer. object. The organic polymer or oligomer of the component (A) and / or the organic polymer or oligomer of the component (B) is at least one selected from polysiloxane, polyether, and vinyl polymer. The light / moisture dual cure curable composition for FPD bonding according to claim 4. 6. The organic polymer or oligomer as the component (A) and / or the organic polymer or oligomer as the component (B) is a (meth) acrylic polymer. A light / moisture dual cure curable composition for FPD bonding. 6. The FPD pasting according to claim 4, wherein the organic polymer or oligomer of the component (A) and / or the organic polymer or oligomer of the component (B) is an acrylic polymer. Light / moisture dual cure curable composition for combination. 6. The organic polymer or oligomer as the component (A) and / or the organic polymer or oligomer as the component (B) is an acrylate ester polymer. Light / moisture dual cure curable composition for FPD bonding. The polymerizable carbon-carbon double bond of the component (B) is represented by the general formula (1).
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The light / moisture dual cure curable composition for FPD bonding according to any one of claims 1 to 8, wherein the curable composition is a group represented by the following formula. (B) The number average molecular weight of a component is over 3000, The light / moisture dual cure curable composition for FPD bonding in any one of Claims 4-9 characterized by the above-mentioned. The light / humidity dual cure for FPD bonding according to claim 10, 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 (F). System curable composition. The hydrolyzable silyl group is represented by the general formula (2), The light / moisture dual cure curable composition for FPD bonding according to any one of claims 1 to 11.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (2)
(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO. (In the formula, R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. The plurality of R ′ may be the same or different. When two or more R ¹ or R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and two or more Y are present. , They may be the same or different, a represents 0, 1, 2, or 3. b represents 0, 1, or 2. m represents an integer of 0 to 19. A + mb ≧ 1). The molecular weight distribution of the organic polymer or oligomer of the component (A) and / or the organic polymer or oligomer of the component (B) is less than 1.8. A light / moisture dual cure curable composition for FPD bonding. The main chain of the vinyl polymer of the component (A) and / or the vinyl polymer of the component (B) is produced by a living polymerization method. A light / moisture dual cure curable composition for FPD bonding. The main chain of the vinyl polymer as the component (A) and / or the vinyl polymer as the component (B) is produced by an atom transfer radical polymerization method. The light / moisture dual cure curable composition for FPD bonding according to 1. 16. The FPD according to claim 1, wherein the hydrolyzable silyl group of component (A) and / or the polymerizable carbon-carbon double bond of component (B) is at the end of the molecular chain. Light / moisture dual cure curable composition for bonding. The hardened | cured material for FPD bonding obtained by hardening the light / moisture dual cure type curable composition for FPD bonding in any one of Claims 1-16. An electric / electronic device equipped with a flat panel display obtained by applying and curing the light / moisture dual cure curable composition for FPD bonding according to claim 1.