JP2011208072A - Curable composition having improved ordinary temperature curability, cured product and electric/electronic equipment obtained by coating and curing the curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can be rapidly curable by light and has improved curability of a part unirradiated with light.SOLUTION: The curable composition comprises an organic polymer (A) bearing at least one hydrolyzable silyl group, an organic polymer (B) bearing at least one polymerizable functional group, and a silicone compound represented by general formula (1): (R)-Si-(OR)(wherein Ris a 1-10C alkyl group; Ris a 1-10C alkyl group, a phenyl group or an alkoxy group; and a is 0, 1 or 2) and/or a partial hydrolysate condensate (C) thereof.

Description

  The present invention relates to a curable composition. More specifically, the compound (A) having at least one hydrolyzable silyl group on average, the compound (B) having at least one polymerizable carbon-carbon double bond on average, a silicon compound and / or a portion thereof A curable composition containing the hydrolysis condensate (C), and an electric / electronic device obtained by coating and curing the composition.

  For electronic and electrical equipment, room temperature, heated curable adhesives, seals and coatings were used. However, in the case of room temperature curing, it takes time for coating and post-coating curing, so that the assembly process of parts and devices is delayed. As a method for shortening the process time, there is heat curing. However, there is a problem in that the operation of precision parts due to heat, the fear of damage such as deformation of the base material, and the occurrence thereof are problematic. In recent years, a curing system using UV or LED light sources has been applied as an active energy ray with less heat generation. Curing by UV and LED leaves a problem in the curability to a dark part where light rays do not reach, on the other hand, which does not thermally damage electric parts, base materials and the like. An organic polymer having a functional group at the end of the main chain with flexibility (impact resistance) was used as a candidate technology that could improve the curability of the active energy ray non-transmitted part (hereinafter referred to as the dark part). There are examples of cured products, particularly polymers synthesized using living polymerization, but there are problems in terms of fast curability, and the use of the present invention is not intended. (Patent Documents 1 and 2). Further, as a measure for improving the curability of the dark part, various methods such as a curing reaction using active energy rays and heat curing or a combination of oxidation-reduction reactions have been proposed. However, it has been pointed out that the former is damaged by heat and the latter is difficult to be liquefied. As an effective solution to the above problem, a dual cure technique in which active energy ray curing is combined with moisture curing has been devised, and a patent application has already been filed (Patent Document 3).

  However, with regard to dark part curing by moisture curing, there are still problems such as the balance between curability and storage stability at the time of liquefaction, difficult to adjust to coating and appropriate viscosity of coating (acrylic monomer as UV curing component) There is a possibility of dilution with oligomers, but there is a concern about performance deterioration because it is uncured in the dark part.)

International Publication WO2005 / 073333, JP-A-11-130931 International Publication WO2008 / 041768

  The present invention 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. It is an object of the present invention to provide a curable composition, a cured product, and an applied electric / electronic device obtained by curing the curable composition.

  As a result of intensive studies by the present inventors in view of the above-described present situation, the compound having at least one crosslinkable silyl group on average (particularly a polymer or oligomer), and at least a polymerizable carbon-carbon bond on average. By using a curable composition characterized by containing one compound (particularly a polymer, oligomer) and a silicon compound that reacts with moisture and / or a partial hydrolysis-condensation product (C) thereof, The present inventors have found that the problem can be solved and have completed the present invention.

That is, a compound (A) characterized by having at least one hydrolyzable silyl group,
Compound (B) having at least one polymerizable carbon-carbon double bond, and silicon compound represented by general formula (1) and / or partial hydrolysis condensate thereof (C)
(R ² ) _a -Si- (OR ¹ ) _4-a (1)
(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group or an alkoxy group, and a is 0, 1 or 2)
It relates to the curable composition characterized by containing.

  (C) It is preferable that a component is a partial hydrolysis-condensation product of the silicon compound represented by General formula (1).

  In addition to the component (A), the component (B), and the component (C), the initiator (D) is preferably contained.

  In addition to the component (A), the component (B), the component (C), and the component (D), it is preferable to contain a curing catalyst (E).

  It is preferable that (A) component and (B) component are an organic polymer and an oligomer.

  The organic polymer of component (A) and component (B) is preferably at least one selected from polysiloxanes, polyethers, and vinyl polymers, and more preferably vinyl polymers.

  The main chain of the vinyl polymer is preferably a (meth) acrylic polymer, and more preferably a (meth) acrylic acid ester polymer.

  The main chain of the vinyl polymer is preferably produced by a living radical polymerization method, and more preferably produced by an atom transfer radical polymerization method.

The component (B) is represented by the general formula (2)
—OC (O) C (R ^a ) ═CH ₂ (2)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
It is preferable to have at least one (meth) acryloyl group represented by

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

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

  The initiator (D) is preferably a photopolymerization initiator and / or a thermal polymerization initiator.

  It is preferable that the initiator (D) is a redox initiator.

The hydrolyzable silyl group is preferably represented by the general formula (3).
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (3)
(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 when 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).

  It is preferable that the organic polymer of the component (A) and / or the component (B) has a molecular weight distribution of less than 1.8.

  It is preferable that the functional group of the organic polymer of (A) component and / or (B) component exists in the molecular chain terminal.

  The curable composition is preferably photocured and moisture cured.

  The curable composition is preferably heat-cured and moisture-cured.

  The present invention relates to an electric / electronic device having a cured product of the curable composition.

  The curable composition of the present invention provides a curable composition that can be rapidly cured by light and that does not become uncured even in a portion that is not exposed to light, and is excellent in the balance between curability and storage stability in one liquid. In addition, the present invention provides a curable composition, a cured product, and an electric / electronic device obtained by applying and curing the viscosity, which can be arbitrarily adjusted to an appropriate viscosity during coating and coating.

The curable composition of this invention is explained in full detail below.
<< Main skeleton of component (A) and component (B) >>
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 compound, an oligomer, and a polymer. However, in terms of a balance between flexibility, durability, and curability, the oligomer and the polymer may be used. Preferably there is.

  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.

  A low molecular weight compound is a compound having a structure other than an oligomer or polymer and having a structure basically free of repeating units.

  As the oligomer and polymer, polysiloxane, polyether, and vinyl polymer are preferable, and vinyl polymer is more preferable.

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

  Further, as the vinyl polymer, a (meth) acrylic polymer is preferable, and a (meth) acrylic acid ester polymer is more preferable.

  When (A) component and (B) component are organic polymers, it is preferable that molecular weight distribution is less than 1.8.

Since all oligomers and polymers can be explained in common with respect to the main chain, production method and the like, they will be explained together below.
<Polysiloxane main chain>
Known methods for hydrolyzing organochlorosilanes to produce organopolysiloxanes, No. 2599517, HYPERLINK "PNS JP 56-151731", JP 56-151731, HYPERLINK "PNS JP 59 A method of hydrolyzing an alkoxysilane described in JP-A-59-66422, HYPERLINK "PNS JP-A-59-68377" or JP-A-59-68377 in the presence of a basic catalyst or an acid catalyst. It is obtained by a known method. 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 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 a method for synthesizing an oxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, for example, a complex obtained by reacting an organoaluminum compound and a porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, for example, polymerization method using double metal cyanide complex catalyst shown in Japanese Patent Publication Nos. 46-27250 and 59-15336, polymerization method using cesium catalyst, phosphazene catalyst Examples of the polymerization method include, but are not particularly limited to. Among these, a polymerization method using a double metal cyanide complex catalyst is preferable from the viewpoint of easily obtaining a polymer having a high molecular weight and little coloring.

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

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

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

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

The polymer constituting the main chain skeleton of the hydrocarbon polymer used in the present invention is (1) carbon number 1 such as ethylene, propylene, 1,2-butadiene, 1,4-butadiene, 1-butene, isobutylene and the like. The homopolymerization or copolymerization of the olefinic compound of ˜6 as the main component, or (2) the homopolymerization or copolymerization of a diene compound such as butadiene or isoprene, or the copolymerization with the above olefinic compound Thereafter, it can be obtained by a method such as hydrogenation. Among these, an isobutylene polymer and a hydrogenated polybutadiene polymer are preferable because it is easy to introduce a functional group at a terminal, easily control the molecular weight, and increase the number of terminal functional groups. Furthermore, since the isobutylene polymer 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 has excellent weather resistance. Therefore, it is particularly preferable.
In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, or monomer units copolymerizable with isobutylene are preferably contained in the isobutylene polymer in an amount of 50% by weight or less. The content may be preferably 30% by weight or less, particularly preferably 10% by weight or less.

Examples of such monomer components include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Examples of such copolymer components include 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-methyl styrene, dimethyl styrene, monochlorostyrene, dichlorostyrene, β-pinene, indene, vinyl trichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyl Trimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane Allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyl Examples include dimethoxysilane.
In the hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers, as in the case of the isobutylene polymer, other monomer units are contained in addition to the main monomer unit. Also good.

  The number average molecular weight of the saturated hydrocarbon polymer, preferably isobutylene polymer or hydrogenated polybutadiene polymer, is preferably about 500 to 50,000, particularly 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-based monomers, aromatic vinyl-based monomers, fluorine-containing vinyl-based monomers, silicon-containing vinyl-based monomers, maleimide-based monomers such as various monomers described in JP 2005-232419 A paragraph [0018] Examples include 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 (b) 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 molecular weight distribution of vinyl polymers other than the hydrocarbon polymer in the present invention, that is, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) (Mw / Mn) is not particularly limited, but is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.6 or less, even more preferably 1.5 or less, Preferably it is 1.4 or less, Most preferably, it is 1.3 or less. If the molecular weight distribution is too large, the viscosity at the molecular weight between the same cross-linking points increases and the handling tends to be difficult. In the GPC measurement in the present invention, chloroform is used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  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, 3,000 to 100 when measured by GPC. Is more preferable, 5,000 to 80,000 is more preferable, and 8,000 to 50,000 is even more preferable. If the molecular weight is too low, the original properties of vinyl polymers other than hydrocarbon polymers tend to be difficult to express, while if 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”. 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 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 JP-A-2005-234419 The description of 2006-291073 gazette etc. can be referred to.

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

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

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

Etc.

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

  Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal, More preferably, it is 0. A transition metal complex having valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel as a central metal, particularly preferably a copper complex. Specific examples of the monovalent copper compound used to form the copper complex include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, and oxidized oxide. Cuprous, cuprous perchlorate, and the like. In the case of using a copper compound, 2,2′-bipyridyl or a derivative thereof, 1,10-phenanthroline or a derivative thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity These polyamines are added as ligands.

The polymerization reaction can be carried out without solvent, but can also be carried out in various solvents. It does not specifically limit as a kind of solvent, The solvent of Unexamined-Japanese-Patent No. 2005-232419 Paragraph [0067] is mentioned. These may be used alone or in combination of two or more. Polymerization can also be performed in an emulsion system or a system using supercritical fluid CO ₂ as a medium.

  Although superposition | polymerization temperature is not limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.

<< Method 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 (3) is preferable.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (3)
(In the formula, R ³ and R ⁴ 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 ³ or R ⁴ are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when 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 is preferably at the end of the molecular chain.

<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. Adjust to leave hydrolyzable silyl at the end. There is a method of reacting terminal chloro group-containing polysiloxane with chlorosilane containing hydrolyzable silyl.

<Introduction method to polyether>
(Α) A method of reacting a hydrosilyl compound represented by the general formula (4) after introducing an olefin group into an oxyalkylene polymer having a functional group such as a hydroxyl group.
HSiX _a R ⁴ _3-a (4) (wherein R ⁴ , 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 in which a compound represented by the general formula (5) is reacted with an oxyalkylene polymer having a functional group capable of reacting with an isocyanate compound.
(R ⁴ ) _3-a SiX _a -R ⁵ NCO (5)
(In the formula, R ⁴ , X and a are the same as above. R ⁵ 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 (6). A method of reacting a W group of a silicon compound.
(R ⁴ ) _3-a SiX _a -R ⁵ W (6)
(Wherein R ⁴ , R ⁵ , 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 (6) in which W is a mercapto group. Method.
From the viewpoint of introduction yield and simplicity of the introduction method, the methods (α) and (β) are preferred, 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 [102] to [112] 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 (2)
—OC (O) C (R ^a ) ═CH ₂ (2)
(In the formula, 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.

  The polymerizable carbon-carbon double bond 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, hydrolyzable silyl, and a terminal silanol-terminated polysiloxane described in HYPERLINK "PNE Patent No. 3193866" Patent No. Examples thereof include a method of subjecting a group-containing (meth) acryloyl compound to a 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). Method. <2> A method of reacting a compound of the general formula (1) containing an isocyanate group with a polyoxyalkylene having a hydroxyl group end <3> A polyfunctional isocyanate and a hydroxyl group are contained in a polyoxyalkylene having a hydroxyl group end Method of reacting vinyl monomer <4> Hydrosilylation capable double bond terminal (for example, allyl group terminal) polyoxyalkylene is reacted with polyfunctional type hydrosilyl compound and further hydrosilylation compound such as allyl (meth) acrylate There is a method of reacting. 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, but the following method is preferable.

(Introduction method 1)
It is preferable to be produced by replacing the terminal halogen group of the vinyl polymer of the general formula (7) with a compound having a polymerizable carbon-carbon double bond of the general formula (8).
-CR ⁶ R ⁷ X (7)
(In the formula, R ⁶ and R ⁷ are groups bonded to the ethylenically unsaturated group of the vinyl monomer. X represents chlorine, bromine or iodine.)
M ⁺ -OC (O) C (R) = CH ₂ (8)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal or a quaternary ammonium ion.)

  The vinyl polymer having a terminal structure represented by the general formula (2) is a method of polymerizing a vinyl monomer using the above-described organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or Although it is produced by a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, the former is preferred.

Formula is not particularly restricted but includes compounds represented by (3), specific examples of R, for _{example, -H, -CH 3, -CH 2} CH 3, - (CH 2) n CH 3 (n is It represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and is preferably -H, -CH _3.

M ⁺ is a counter cation of an oxyanion, and examples of M ⁺ include alkali metal ions, specifically lithium ions, sodium ions, potassium ions, and quaternary ammonium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion, preferably sodium ion and potassium ion. The usage-amount of the oxyanion of General formula (8) becomes like this. Preferably it is 1-5 equivalent with respect to the halogen group of General formula (7), 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 (9) with a vinyl polymer having a hydroxyl group at a terminal.
XC (O) C (R) = CH ₂ (9)
(In the formula, R 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 (10).
HO-R'- OC (O) C (R) = CH ₂ (10)
(In the formula, R represents hydrogen or an organic group having 1 to 20 carbon atoms. R ′ represents a divalent organic group having 2 to 20 carbon atoms.)
Among these methods, (Introduction method 1) is most preferable because it is easy to control.

<< Silicone Compound or Partially Hydrolyzed Condensate (C) >>
The curable composition of the present invention has the general formula (1)
(R ² ) _a -Si- (OR ¹ ) _4-a (1)
(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group or an alkoxy group, and a is 0, 1 or 2)
Is included, and a partial hydrolysis condensate of the silicon compound is preferable.

In the general formula (1), R ¹ has 1 to 10 carbon atoms, preferably 1 carbon atom such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, or an i-butyl group. An alkyl group having 4 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an araryl group having 7 to 10 carbon atoms, preferably an aryl group having 6 to 9 carbon atoms such as a phenyl group, and a 7 to 9 carbon atom such as a benzyl group. It is a monovalent hydrocarbon group selected from aralkyl groups. When the alkyl group has more than 10 carbon atoms, the reactivity of the partially hydrolyzed condensate (C) component of the silicon compound is lowered. Further, when R ¹ is other than the alkyl group, aryl group or aralkyl group, the reactivity is lowered.

In the general formula (1), R ² is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an araryl group having 7 to 10 carbon atoms, preferably ¹ carbon atom similar to R 1. It is a monovalent hydrocarbon selected from ˜4 aralkyl groups, C 6-9 aryl groups, and C 7-9 aralkyl groups.

In the general formula (1), (R ¹ O) _4-a is selected so that 4-a is 3 or more, that is, a is 0 to 1, but is formed from the composition of the present invention. A is preferably 0 from the viewpoint of improving the curability of the coating film.

When there are a plurality of (R ¹ O) _4-a present in the general formula (1), they may be the same or different.

  Specific examples of the silicon compound as the component (C) include tetraalkyl such as tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra i-propyl silicate, tetra n-butyl silicate and tetra i-butyl silicate. Silicates: methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltrisec-octyloxysilane, methyltriphenoxysilane, methyl Examples include triisopropoxysilane and methyltributoxysilane.

  Specific examples of the partially hydrolyzed condensate of the silicon compound as component (C) include those obtained by condensing water by adding water to the tetraalkylsilicate or trialkoxysilane by a conventional method. For example, MSI51, MSI53A, ESI40, ESI48, HAS-1, HAS-10 (above, made by Colcoat Co.), MS51, MS56, MS56S (above, made by Mitsubishi Chemical Corporation), M silicate 51, FR-3 , Silicate 40, silicate 45, silicate 48, ES-48 (above, manufactured by Tama Chemical Co., Ltd.), etc., partially hydrolyzed condensates of tetraalkoxysilane, such as AFP-1 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. And a partially hydrolyzed condensate of trialkoxysilane. Among the partially hydrolyzed condensates of the silicon compound of the component (C), the compatibility with the resin (A) component and the curability of the resulting composition of the present invention are good, and the composition is formed using the composition. MSI51, MSI53A, MS51, MS56, MS56S (tetrahydrosilane partial hydrolysis condensate), ESI48, HAS-1 (tetraethoxy) from the viewpoint of controlling the adhesion of pollutants rather than being excellent in hardness of the coating film. It is preferable to use a partial hydrolysis condensate of tetraalkoxysilane, such as MS56S and ESI48 having a weight average molecular weight of more than 1000, because the compounding amount can be reduced. Further preferred. The hydrolysis condensate (C) component of the silicon compound may be used alone or in combination of two or more.

  The partially hydrolyzed condensate of the silicon compound (C) can also be obtained by hydrolyzing the silicon compound and / or the partially hydrolyzed condensate of the silicon compound in an alcohol solvent under acidic conditions.

  Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, and isobutyl alcohol.

  These may be used alone or in combination of two or more. Of these, methanol, ethanol, and isopropanol are preferable from the viewpoint of improving stability. The acidic condition refers to a condition in which <1> an acidic substance is added and <2> is treated with a cation exchange resin.

  <1> Acidic substances are inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and sulfurous acid; phosphate esters such as monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, dioctyl phosphate, and didecyl phosphate; Carboxylic acid compounds such as formic acid, acetic acid, maleic acid, adipic acid, oxalic acid, and succinic acid; sulfonic acid compounds such as dodecylbenzenesulfonic acid, paratoluenesulfonic acid, 1-naphthalenesulfonic acid, and 2-naphthalenesulfonic acid Can be mentioned.

  Among these, hydrochloric acid, nitric acid, sulfurous acid, and formic acid having a relatively low boiling point are preferable because the acid can be easily removed after the acid treatment.

Examples of the <2> cation exchange resin include Amberlyst 15 (Rohm and Haas), Duolite C-433 (Sumitomo Chemical Co., Ltd.), and the like. After the treatment with the cation exchange resin and water, it is preferable to remove the cation exchange resin by filtration or decantation. It is preferable to add methyl orthoacetate as a dehydrating agent to the partially hydrolyzed condensate (C) component of these silicon compounds in advance from the viewpoint of storage stability after blending with the component (A). The amount of component (C) used is 0 to 200 parts by weight, preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of component (A). When the amount of component (B) used exceeds 200 parts, the cured product layer becomes cloudy or cracks are generated. In order to improve the compatibility between the component (A) and the component (C), the component (C) is added with the component (C) during the polymerization of the component (A). The ingredients can be hot blended.
(C) Component mixed with resin (A) component becomes a composition having room temperature curing property and heat curing property, and the coating film formed using the composition has excellent stain resistance, The reason why the coating film has excellent stain resistance has not yet been clarified. Probably, the improvement in surface hardness and hydrophilicity is considered to have an influence from the point of good balance between the difference in relative curing speed and compatibility between the resin (A) component and the (C) component.

<< Initiator (D) >>
Although it does not specifically limit to the curable composition of this invention, In order to make it harden | cure quickly or to obtain the hardened | cured material of sufficient property, it is preferable to use an initiator (D).

  The initiator (D) is not particularly limited, and examples thereof include a photopolymerization initiator, a thermal polymerization initiator, and a redox initiator.

  The photopolymerization initiator, the thermal polymerization initiator, and the redox initiator may be used alone or as a mixture of two or more. When used as a mixture, various initiators are used. It is preferable that the usage-amount of an agent exists in each below-mentioned range.

  As a photoinitiator, a photoradical initiator, a photoanion initiator, a near-infrared photoinitiator, etc. are mentioned, A photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable.

  Examples of the photo radical initiator include acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4 -Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoin, benzoy Methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzylmethoxy ketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl- Phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl 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.

  When using a photoinitiator, the addition amount does not have a restriction | limiting in particular, However, 0.001-10 weight part is preferable with respect to 100 weight part of (B) component from the point of sclerosis | hardenability and storage stability.

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

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

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

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

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

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

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

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

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

  Preferred redox initiators are a combination of organic peroxide and tertiary amine, a combination of organic peroxide and transition metal, and more preferably a combination of cumene hydroperoxide and anilines, cumene hydroperoxide. And cobalt naphthate.

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

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

  Considering that the curable composition for filling between the liquid crystal module / transparent cover board is temporarily fixed with light such as UV, it is preferable to mainly use a photopolymerization initiator among the above initiators. .

<< Curing catalyst (E) >>
The compound (A) having at least one hydrolyzable silyl group used in the present invention is present in the presence or absence of various conventionally known condensation catalysts (also referred to as curing catalysts or “curing agents”). Crosslink and cure by forming siloxane bonds. 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 hydrolyzable silyl groups 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 Acetylacetonate bis (chelates such as ethyl acetoacetate and titanium tetraacetylacetonate; methylamine, ethylamine, propylamine, isopropylamine, butyl 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; Aliphatic amines such as triallylamine and oleylamine Japanese amines; aromatic amines such as lauryl aniline, stearyl aniline, triphenyl amine; 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 and 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), or these amine compounds Salts of carboxylic acids, etc .; reaction products and mixtures of amine compounds and organotin compounds such as laurylamine and tin octylate reaction products or mixtures; low molecular weight polyamides obtained from excess polyamines and polybasic acids Resin; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-amino Propylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminopropyltriethoxysilane, N- (Β-aminoethyl) aminopropylmethyldi Toxisilane, 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.

As the organic acidic phosphoric acid ester compound of the acidic catalyst, (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) (- OH) 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, etc. The substance is not limited to the exemplified substances.

  The combined system of these organic acids and amines is more preferable from the viewpoint of reducing the amount of use because the catalytic activity is increased. Among organic acid and amine combined systems, acidic phosphate ester and amine, organic carboxylic acid and amine, especially organic acidic phosphate ester and amine, and aliphatic carboxylic acid and amine combined system have higher catalytic activity and faster speed. It is preferable from the viewpoint of curability. Details are shown below.

  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 amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine, etc. Aliphatic primary amines: dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methylstearyl Aliphatic secondary amines such as amine, ethylstearylamine, butylstearylamine; triamylamine, trihexylamine Aliphatic tertiary amines such as trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatic amines such as laurylaniline, stearylaniline and triphenylamine; and other amines, Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4, 6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabi Amine compounds such as black (5,4,0) undecene-7 (DBU), polyamine compounds, 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) aminopropylmethyldiethoxysilane, N- (β-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ -Aminopropyltrimethoxy Orchid, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, and the like. Moreover, amino groups such as silane coupling agents having amino groups such as amino-modified silyl polymer, silylated amino polymer, unsaturated aminosilane complex, phenylamino long chain alkylsilane, aminosilylated silicone, etc. Examples thereof include, but are not limited to the exemplified substances.

  Of the aminosilane compounds, 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.

  These amine compounds may be used alone or in combination of two or more.

  When these amine compounds are added, the blending amount is preferably about 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the compound (A) having at least one hydrolyzable silyl group. Part is more preferred. 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 30 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 amine compounds 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 amount of the amine compound is too small or too large, the curing rate may be slow, the curing reaction may not proceed sufficiently, and the pot life may be too short. Is not preferable.

  These amine compounds 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 organic acids. Among organic acid and amine combination systems, there are combinations of acidic phosphoric acid esters and amines, carboxylic acids and amines, etc. Among them, the combination system of carboxylic acid and amine has a higher catalytic activity and a quick curing viewpoint. Further, a combined system with an organic carboxylic acid, 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. 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. If the reactivity is high, a small amount of 0.01 to 1 part It is possible to sufficiently cure within the range.

  The type and amount of the curing catalyst / curing agent include, for example, the hydrolyzable silyl group of the compound (A) having at least one hydrolyzable silyl group of the present invention, the type of Y in the general formula (101), and a The number can be selected depending on the number, 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 carbon atoms, the higher the reactivity, and the higher the number a, the higher the reactivity, so that it can be sufficiently cured in a small amount.

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

<< Polymerizable monomer and / or oligomer (F) >>
When the number average molecular weight of the component (B) exceeds 3000, the curable composition of the present invention has a (meth) acryloyl group within a range not impairing the effects of the present invention, and the number average molecular weight is 3000 or less. Oligomers and / or monomers can be added.

  Specific examples of the monomer include those described in paragraphs [0124] to [0129] and [0131] of JP-A-2006-265488.

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

  Further, the number average molecular weight of the monomer and / or oligomer having a (meth) acryloyl group is preferably 3000 or less. However, in order to improve surface curability and reduce viscosity for improving workability, the monomer Is more preferably 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 thereof 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 Japanese Patent Application Laid-Open No. 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 it is more preferable to use a micro hollow body having a true specific gravity of 0.5 g / cm ³ or less.

  As the inorganic balloon and the organic balloon, balloons described in paragraphs [0168] to [0170] of JP-A-2005-232419 can be used.

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

  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.

<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.

  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, and specifically, for example, Tinuvin P, Tinuvin 234, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinuvin 329, Tinuvin 213 (all above) Examples thereof include benzotriazole compounds such as Ciba Geigy (Japan), triazine compounds such as Tinuvin 1577, benzophenone compounds such as CHIMASSORB 81, and benzoate compounds such as Tinuvin 120 (Ciba Geigy Japan).

  Further, hindered amine compounds are also preferable, and specific examples of such compounds include, but are not limited to, those described in JP 2006-274084 A. 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 it is less than 0.1 parts by weight, the effect of improving the weather resistance is small, and if it exceeds 10 parts by weight, there is no great difference in the effect, which is economically disadvantageous.

<Adhesive agent>
An adhesiveness-imparting agent can be added to the curable composition of the present invention for the purpose of further improving the substrate adhesion. Examples of the adhesiveness-imparting agent include a crosslinkable silyl group-containing compound and a vinyl group having a polar group. A monomer is preferable, and a silane coupling agent and an acid-containing vinyl monomer are more preferable.

  Specific examples thereof include the adhesion-imparting agent described in paragraph [0184] of JP-A-2005-232419.

  An organic group having an atom other than a carbon atom and a hydrogen atom, such as an epoxy group, an isocyanate group, an isocyanurate group, a carbamate group, an amino group, a mercapto group, a carboxyl group, a halogen group, and a (meth) acryl group in the molecule; A silane coupling agent having a crosslinkable silyl group can be used.

  Specific examples thereof include a silane coupling agent having both a crosslinkable silyl group and an organic group having an atom other than a carbon atom and a hydrogen atom described in paragraph [0185] of JP 2005-232419 A.

  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 are described in, for example, the specifications of JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, and JP-A-64-22904. Yes.

<< Method for producing cured product >>
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 >>
The cured product of the present invention is obtained by curing the curable composition. The method for curing the curable composition is not particularly limited, but it is preferable to perform photocuring and moisture curing, heat curing and moisture curing.

  When a thermal radical initiator is used as component (D), the curing temperature varies depending on the type of thermal radical initiator used, component (A), component (B), other compounds added, etc., but usually 50 C. to 250.degree. C. is preferable, and 70.degree. C. to 250.degree. C. is more preferable.

  (D) When using a photoinitiator as a component, it can be hardened by irradiating light or an electron beam with an active energy ray source.

  Although there is no limitation in particular as an active energy ray source, According to the property of the photoinitiator to be used, a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation apparatus, a halogen lamp, a light emitting diode, a semiconductor laser, a metal halide etc. are mentioned, for example.

  (D) When using a photoinitiator as a component, 0 to 150 degreeC is preferable, and 5 to 120 degreeC is more preferable.

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

<< Molding method >>
The coating method of the curable composition of the present invention is not particularly limited, and various commonly used coating methods can be used. For example, there are a method using a dispenser, a method using a coater, a method using a spray, and the like.

<< Usage >>
Elastic sealants for buildings, sealants for siding boards, sealants for double-glazed glass, self-cleaning glass and self-cleaning polycarbonate, sealing agents for self-cleaning tiles, sealing agents for vehicles, and other building and industrial sealing agents, Electrical / electronic component materials such as solar cell backside sealants, permanent resist applications, solder resist applications, dry film resist applications, electrodeposition resist applications, etc., electrical insulation materials such as electric wire / cable insulation coatings, adhesives Agents, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, paints, powder paints, coating materials, foams, sealing materials such as can lids, heat dissipation sheets, electric and electronic Potting agent, film, gasket, marine deck caulking, casting material, various molding materials, artificial marble, and mesh Anti-rust / waterproof sealing material for glass and laminated glass end faces (cutting parts), anti-vibration / vibration / soundproof / isolation materials used in automobiles, ships, home appliances, etc., automotive parts, electrical parts, various machines It can be used for various applications such as liquid sealants and waterproofing agents used in parts.

  Furthermore, the molded product showing rubber elasticity obtained from the curable composition of the present invention can be widely used mainly for gaskets and packings. For example, in the automobile field, it can be used as a body part as a sealing material for maintaining airtightness, an anti-vibration material for glass, an anti-vibration material for vehicle body parts, particularly a wind seal gasket and a door glass gasket. As chassis parts, it can be used for vibration-proof and sound-proof engines and suspension rubbers, especially engine mount rubbers. As engine parts, they can be used for hoses for cooling, fuel supply, exhaust control, etc., sealing materials for engine oil, and the like. It can also be used for exhaust gas cleaning device parts and brake parts. In the home appliance field, it can be used for packing, O-rings, belts and the like. Specifically, decorations for lighting fixtures, waterproof packings, anti-vibration rubbers, insect-proof packings, anti-vibration / sound absorption and air sealing materials for cleaners, drip-proof covers for electric water heaters, waterproof packings, heater parts Packing, electrode packing, safety valve diaphragm, hose for sake cans, waterproof packing, solenoid valve, waterproof packing for steam microwave oven and jar rice cooker, water tank packing, water absorption valve, water receiving packing, connection hose, belt, heat insulation Oil packing for combustion equipment such as heater packing, steam outlet seal, O-ring, drain packing, pressure tube, blower tube, feed / intake packing, anti-vibration rubber, oil filler packing, oil meter packing, oil feed tube, Speaker gaskets, speaker edges, turntables for acoustic equipment such as diaphragm valves and air pipes Seat, belts, pulleys, and the like. In the construction field, it can be used for structural gaskets (zipper gaskets), air membrane roof materials, waterproof materials, fixed sealing materials, vibration-proof materials, sound-proof materials, setting blocks, sliding materials, and the like. In the sports field, it can be used for all-weather pavement materials, gymnasium floors, etc. as sports floors, shoe sole materials, midsole materials, etc. as sports shoes, golf balls etc. as ball for ball games. In the field of anti-vibration rubber, it can be used as anti-vibration rubber for automobiles, anti-vibration rubber for railway vehicles, anti-vibration rubber for aircraft, anti-vibration materials, and the like. In the marine and civil engineering fields, structural materials include rubber expansion joints, bearings, waterstops, waterproof sheets, rubber dams, elastic pavements, anti-vibration pads, protective bodies, etc., rubber molds, rubber packers, rubber skirts as construction secondary materials , Sponge mats, mortar hoses, mortar strainers, etc., rubber sheets, air hoses, etc. as construction auxiliary materials, rubber buoys, wave-absorbing materials, etc. as safety measures products, oil fences, silt fences, antifouling materials, marine hoses, etc. Can be used for draging hoses, oil skimmers, etc. In addition, it can be used for sheet rubber, mats, foam boards and the like.

  Among these, the curable composition of the present invention is particularly useful as a sealing material and an adhesive, and is also particularly useful for applications requiring weather resistance and heat resistance and for applications requiring transparency. Moreover, since the curable composition of this invention is excellent in a weather resistance and adhesiveness, it can be used for the construction method of an outer wall tile adhesion | attachment without joint filling. In addition, the use of elastic adhesives for the adhesion of materials with different linear expansion coefficients, the adhesion of members that are repeatedly displaced by heat cycles, and the application of coating agents in applications where the ground can be seen utilizing transparency It is also useful for adhesives used for laminating transparent materials such as glass, polycarbonate and methacrylic resin. In addition, making use of its good heat resistance and oil resistance, it is suitable for use in liquid sealing materials used in on-site molded gaskets, applications called FIPG (Formed In Place Gasket), so-called automobile parts, electrical parts, various machine parts, etc. Is also possible.

  Among the above uses, it is particularly useful for adhesives, sealing materials, and coating materials for electric and electronic devices.

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

In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804 and K-802.5; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
In the following examples, “average terminal hydrolyzable silyl group or (meth) acryloyl group number” is “number of crosslinkable silyl groups introduced per polymer molecule, (meth) acryloyl group number”, and ¹ H-NMR. It calculated from the number average molecular weight calculated | required by analysis and GPC.
(However, ¹ H-NMR was measured at 23 ° C. using Bruker ASX-400 and deuterated chloroform as a solvent.)
In the examples and comparative examples below, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

<Production of hydrolyzable silyl group-containing oxyalkylene polymer>
(Production Example 1)
GPC measurement (polystyrene conversion) number average molecular weight 10800 by polymerizing propylene oxide using Actocol P-23 (manufactured by Mitsui Takeda Co., Ltd., polyoxypropylene glycol) as an initiator and a zinc hexacyanocobaltate glyme complex. Polyoxypropylene glycol having Mw / Mn of 1.2 was produced, and then the terminal hydroxyl group was metaloxylated. Further, allyl chloride is reacted to introduce unsaturated groups at all ends, and then methyldimethoxysilane is reacted to 0.75 equivalents with respect to the unsaturated groups to obtain a polymer [P1] having a methyldimethoxysilyl group at the ends. It was. The viscosity of [P1] (23 ° C .: B-type viscometer) was 5.9 Pa · s.

<Production of hydrolyzable silyl group-containing (meth) acrylic polymer>
(Production Example 2)
Table 1 shows the amount of each raw material used.
(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. At the stage where the temperature of the mixture was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter abbreviated as triamine). ) Was added to initiate the polymerization reaction. The remaining 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 the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C. 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, and a filter aid, an adsorbent (KYOWARD 700SEN: manufactured by Kyowa Chemical), hydrotalcite (KYOWARD 500SH: manufactured by Kyowa Chemical)) are added, and 80 to After stirring at about 100 ° C., 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 [P2] 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 Example 3)
Polymerization, diene reaction, purification, high-temperature heat treatment / adsorption purification step, silylation are carried out in the same manner as in Production Example 2 using the amounts of each raw material shown in Production Example 3 of Table 1. Polymer [P3] Obtained. 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.

<Manufacture of oxyalkylene polymer having (meth) acryloyloxy group at terminal>
(Production Example 4)
Polyoxypropylene having a GPC measurement (polystyrene conversion) number average molecular weight of 10800 and Mw / Mn of 1.2 by polymerizing propylene oxide using Actocol P-23 as an initiator and a zinc hexacyanocobaltate glyme complex Glycol was produced and 1.1 equivalents of 2-acryloyloxyethyl isocyanate were reacted with the hydroxyl group to obtain a polymer [P4] having a radical-reactive double bond at the terminal. The viscosity of [P4] (23 ° C .: B-type viscometer) was 10 Pa · s.

<Production of (meth) acrylic polymer having (meth) acryloyloxy group at terminal>
(Production Examples 5 and 6)
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 1) were charged and stirred with heating. Acetonitrile (described as “Acetonitrile for polymerization” in Table 1), diethyl 2,5-dibromoadipate (DBAE) or ethyl 2-bromobutyrate as an initiator were added and mixed, and the temperature of the mixture was adjusted to about 80 ° C. Pentamethyldiethylenetriamine (hereinafter abbreviated as triamine) was added to initiate the polymerization reaction. The remaining acrylic ester (described as an additional monomer in Table 1) was added sequentially to proceed the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization is shown in Table 1 as a triamine for polymerization. As the polymerization proceeds, the internal temperature rises due to the heat of polymerization, so the polymerization was allowed to proceed while adjusting the internal temperature to about 80 ° C to about 90 ° C.

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

(3) First crude purification Butyl acetate was used as a diluent solvent for the polymer. 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 (Kyoword 700 SEN, Kyoward 500 SH ) Was added. After introducing an oxygen-nitrogen mixed gas into the gas phase part of the reaction vessel, the mixture was heated and stirred at about 80 ° C. for several hours. Insoluble catalyst components were removed by filtration. The filtrate was colored and slightly turbid due to the polymerization catalyst residue.

(4) Second crude purification The filtrate was charged into a stainless steel reaction vessel equipped with a stirrer, and adsorbents (Kyoward 700SEN, Kyoward 500SH) were added. After introducing an oxygen-nitrogen mixed gas into the gas phase and heating and stirring at about 100 ° C. for several hours, insoluble components such as an adsorbent were removed by filtration. The filtrate was almost clear and clear. The filtrate was concentrated to obtain an almost colorless and transparent polymer.

(5) (Meth) acryloyl group introduction step 100 kg of polymer is dissolved in about 100 kg of N, N-dimethylacetamide (DMAC), potassium acrylate (about 2 molar equivalents relative to terminal Br group), thermal stabilizer (H -TEMPO: 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl) and an adsorbent (Kyoward 700SEN) were added, and the mixture was heated and stirred at about 70 ° C for several hours. DMAC was distilled off under reduced pressure, the polymer concentrate was diluted with about 100 kg of toluene with respect to 100 kg of the polymer, a filter aid was added, the solid content was filtered off, the filtrate was concentrated, and an acryloyl group was added to the end. Polymers [P5] and [P6] having 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
50 parts of the polymer [P1] obtained in Production Example 1 as the component (A), 50 parts of the polymer [P4] obtained in Production Example 4 as the component (B), and MSI53A (tetramethoxy) as the component (C) 10 parts of silane partially hydrolyzed condensate (manufactured by Colcoat) and DAROCUR1173 (2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, manufactured by Ciba Specialty Chemicals) as component (D) 0 4 parts, IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by Ciba Specialty Chemicals) 0.1 part, IBXA (isoboronyl acrylate, Osaka Organic Chemical Industry) as a monomer component 10 parts), FA-513M (dicyclopentanyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.), 20 parts, , 1 part of SILUQUEST-A171 (vinyltrimethoxysilane, manufactured by Momentive Japan) as a dehydrating agent, 2 parts of SILUQUEST-A187 (3-glycidoxypropyltrimethoxysilane, manufactured by Momentive Japan) as a silane coupling agent, KBM- 5103 (3-acryloyloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), 2.4 parts of Versatic 10 (neodecanoic acid, manufactured by Shell Chemical) as a curing catalyst for [P1], SILUQUEST-A1100 (3-aminopropyltri A curable composition is prepared by thoroughly stirring and mixing 0.4 parts of ethoxysilane (Momentive Japan), applied to a glass plate to a thickness of 500 μm, and UV irradiation device (Light Hammer 6: Fusion UV system Japan). Made) A cured product was obtained by irradiating with an integrated light amount of 3000 mJ / cm ² . Further, the curing time (gel time) was 3 hours under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

(Example 2)
The amount of MSI53A added was changed from 10 parts to 5 parts to 50 parts of polymer [P5] instead of polymer [P4] instead of [P1] in Example 1 to 10 parts of IBXA. Adjustment of the curable composition and evaluation of curability were performed in the same manner as in Example 1 except that the addition amount was 20 parts and the addition amount of FA-513M was 10 parts.
Furthermore, when the UV irradiation unit was used to irradiate an integrated light amount of 3000 mJ / cm ² , the UV irradiation unit was irradiated for about 15 seconds, but a slight remaining strong tack was observed, but the shape of the cured product was retained. And hardened well without flowing. In addition to obtaining a cured product by UV irradiation, the curing time (gel time) was 4 hours under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

(Example 3)
Example 1 [P1] instead of polymer [P2] 50 parts, polymer [P4] instead of polymer [P5] 30 parts, [P6] 20 parts, IBXA 15 parts, FA-513M Adjustment of the curable composition and evaluation of curability were carried out in the same manner as in Example 1 except that 15 parts and 4 parts of A187 were changed.

Furthermore, when the UV irradiation unit was used to irradiate an integrated light amount of 3000 mJ / cm ² , the UV irradiation unit was irradiated for about 15 seconds, but a slight remaining strong tack was observed, but the shape of the cured product was retained. And hardened well without flowing. In addition to obtaining a cured product by UV irradiation, the curing time (gel time) was 3 hours under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

Example 4
The amount of addition of MSI53A was changed from 10 parts to 5 parts to 50 parts of the polymer [P3] instead of [P1] in Example 1, except that IBXA was 15 parts, FA-513M was 15 parts, and A187 was 4 parts. Adjustment of the curable composition and evaluation of curability were carried out in the same manner as in Example 1.

Furthermore, when the UV irradiation unit was used to irradiate an integrated light amount of 3000 mJ / cm ² , the UV irradiation unit was irradiated for about 15 seconds, but a slight remaining strong tack was observed, but the shape of the cured product was retained. And hardened well without flowing. In addition to obtaining a cured product by UV irradiation, the curing time (gel time) was 4 hours under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

(Comparative Example 1)
Except not adding MSI53A of Example 1, adjustment of the curable composition and sclerosis | hardenability evaluation were implemented by the method similar to Example 1. FIG.
Furthermore, when the UV irradiation unit was used to irradiate an integrated light amount of 3000 mJ / cm ² , the UV irradiation unit was irradiated for about 15 seconds, but a slight remaining strong tack was observed, but the shape of the cured product was retained. And hardened well without flowing. In addition to obtaining a cured product by UV irradiation, the curing time (gel time) was 12 hours or longer under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

(Comparative Example 2)
Except not adding MSI53A of Example 2, adjustment of the curable composition and sclerosis | hardenability evaluation were implemented by the method similar to Example 1. FIG.
Furthermore, when the UV irradiation unit was used to irradiate an integrated light amount of 3000 mJ / cm ² , the UV irradiation unit was irradiated for about 15 seconds, but a slight remaining strong tack was observed, but the shape of the cured product was retained. And hardened well without flowing. In addition to obtaining a cured product by UV irradiation, the curing time (gel time) was 12 hours or longer under the condition of 23 ° C. × 55% of the UV non-irradiated part (film thickness 500 μm).

  From the comparison between Examples 1 to 4 and Comparative Examples 1 and 2, it was found that the crosslinkable silyl group-containing organic polymer (A) component, the polymerizable functional group-containing organic polymer (B) component and the silico compound were partially hydrolyzed. The curable composition containing the decomposition condensate (C) is excellent in UV curing, and the curability under light shielding is fast, whereas the curable composition not containing the component (C) is curable upon UV irradiation. However, it is slow to cure under light shielding. The curable composition of the present invention is expected to contribute to shortening the production process by quickly eliminating the uncured state of the UV unexposed portion in the coating, bonding, sealing and the like of electronic components.

  Contains an organic polymer (A) characterized by having at least one hydrolyzable silyl group, an organic polymer (B) having at least one polymerizable functional group, and a partial hydrolysis condensate (C) of a silico compound The present invention provides a coating material, a sealing material, an adhesive, and the like excellent in UV and moisture curing.

Claims (22)

Compound (A) characterized by having at least one hydrolyzable silyl group,
Compound (B) having at least one polymerizable carbon-carbon double bond, silicon compound represented by general formula (1), and / or partially hydrolyzed condensate thereof (C)
(R ² ) _a -Si- (OR ¹ ) _4-a (1)
(Wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 1 to 10 carbon atoms, a phenyl group or an alkoxy group, and a is 0, 1 or 2)
A curable composition comprising:   The curable composition according to claim 1, wherein the component (C) is a partial hydrolysis-condensation product of a silicon compound represented by the general formula (1).   The curable composition according to claim 1, further comprising an initiator (D) in addition to the component (A), the component (B), and the component (C).   The curable composition according to claim 1, further comprising a curing catalyst (E) in addition to the component (A), the component (B), the component (C), and the component (D).   (A) component and (B) component are organic polymer and oligomer, The curable composition in any one of Claims 1-4 characterized by the above-mentioned.   6. The curable composition according to claim 5, wherein the organic polymer of the component (A) and the component (B) is selected from at least one of polysiloxane, polyether, and vinyl polymer.   The curable composition according to any one of claims 5 to 6, wherein the organic polymer of the component (A) and the component (B) is a vinyl polymer.   The curable composition according to claim 7, wherein the main chain of the vinyl polymer is a (meth) acrylic polymer.   The curable composition according to claim 7, wherein the main chain of the vinyl polymer is a (meth) acrylic acid ester polymer.   The curable composition according to claim 7, wherein the main chain of the vinyl polymer is produced by a living radical polymerization method.   The curable composition according to claim 7, wherein the main chain of the vinyl polymer is produced by an atom transfer radical polymerization method. The component (B) is represented by the general formula (2)
—OC (O) C (R ^a ) ═CH ₂ (2)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
The curable composition according to claim 1, which has an average of at least one (meth) acryloyl group represented by the formula:   The number average molecular weight of (B) component is more than 3000, The curable composition in any one of Claims 5-12 characterized by the above-mentioned.   The curable composition according to claim 13, further comprising an oligomer having a (meth) acryloyl group and a number average molecular weight of 3000 or less, and / or a monomer (F).   The curable composition according to any one of claims 1 to 14, wherein the initiator (D) is a photopolymerization initiator and / or a thermal polymerization initiator.   The curable composition according to any one of claims 1 to 14, wherein the initiator (D) is a redox initiator. The curable composition according to claim 1, wherein the hydrolyzable silyl group is represented by the general formula (3).
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (3)
(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 when 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 curable composition according to any one of claims 5 to 17, wherein the organic polymer of the component (A) and / or the component (B) has a molecular weight distribution of less than 1.8.   The curable composition according to any one of claims 1 to 18, wherein the functional group of the organic polymer of the component (A) and / or the component (B) is at the end of the molecular chain.   A cured product obtained by photocuring and moisture curing the curable composition according to claim 1.   Hardened | cured material obtained by heat-hardening and moisture-hardening the curable composition in any one of Claims 1-19.   An electric / electronic device comprising the cured product according to claim 20.