JP6667124B2 - Curable composition with excellent storage stability - Google Patents

Description

  The present invention provides a curable composition containing a polymer having a hydrolyzable group bonded to a silicon atom and having a silicon group capable of being crosslinked by forming a siloxane bond (hereinafter also referred to as “crosslinkable silicon group”). And a curable composition having excellent storage stability.

  It is known that a polymer having a crosslinkable silicon group has a property of being crosslinked by the formation of a siloxane bond by the action of moisture or the like even at room temperature to obtain a cured product such as rubber. Among polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene-based polymer or an acrylate-based polymer are already industrially produced, such as sealing materials and adhesives. Widely used for applications.

  A curable composition containing a polymer having a crosslinkable silicon group is usually cured using a curing catalyst such as an organic tin compound having a carbon-tin bond represented by dibutyltin bis (acetylacetonate). . When it is necessary to cure in a short time at the time of use, a method such as increasing the amount of a curing catalyst is generally used. However, in recent years, the toxicity of organotin compounds has been pointed out, and their use requires caution from the viewpoint of environmental safety. Patent Documents 1 and 2 disclose tin carboxylate and other metal salts of carboxylic acids as curing catalysts other than the organotin compound, and Patent Document 3 discloses a catalyst system using a carboxylic acid and an amine compound in combination. . However, these catalysts are often inferior in curability to organotin-based catalysts.

  Patent Documents 4 and 5 disclose that a compound or a polymer having a silicon group having a Si—F bond (hereinafter, also referred to as a fluorosilyl group) or a polymer can be used without using an organotin-based catalyst. It is disclosed that curability is obtained.

  In the composition of the polymer having a crosslinkable silicon group, additives having a fine particle size such as calcium carbonate or fumed silica are used as a filler or a thixotropic (thixotropic) imparting agent (anti-sagging agent). Often done. However, as disclosed in Patent Document 6, it is known that when calcium carbonate is added to a curable composition using a compound having a fluorosilyl group or a polymer, curing hardly proceeds. Therefore, paragraphs 0103 to 0106 of Patent Document 6 and Examples disclose that it is preferable to use silica such as fumed silica without using calcium carbonate. However, when silica such as fumed silica is added to a curable composition using a compound or polymer having a fluorosilyl group, curing proceeds, but the viscosity of the composition increases when the composition containing silica is stored. It was found that the handleability decreased.

JP-A-55-9669 JP-A-2003-206410 JP-A-5-117519 International Publication No. 2007-123167 International Publication No. 2008-032539 JP 2009-215331 A

  The problem to be solved by the present invention is to use a compound having a fluorosilyl group as a curing catalyst for an organic polymer having a crosslinkable silicon group, a curable composition using silica as a thixotropy imparting agent, An object of the present invention is to provide a curable composition in which viscosity does not easily increase even when stored and storage stability (storage stability) is improved.

  In order to solve the above problems, the present inventors have conducted intensive studies, and as a result, obtained by adding Michael with a compound having a (meth) acryloyl group and a compound having an amino group to silica, It has been found that a curable composition having improved storage stability can be obtained when a compound having a silicon group having a bonded hydrolyzable group is used in combination.

  That is, the curable composition of the present invention comprises (A) an organic polymer having a hydrolyzable group bonded to a silicon atom and having a silicon group which can be cross-linked by forming a siloxane bond (provided that Si-F 100 parts by mass (excluding those having a bond), (B) 0.1 to 20 parts by mass of a compound having a silicon group having a Si-F bond, (C) 0.1 to 30 parts by mass of fumed silica, and (D) A) a compound obtained by Michael addition of a compound having a (meth) acryloyl group and a compound having an amino group, the compound having 0.5 to 20 parts by mass of a compound having a silicon group having a hydrolyzable group bonded to a silicon atom; It is characterized by containing.

  The main chain skeleton of the polymer (A) is preferably at least one compound selected from the group consisting of a polyoxyalkylene polymer and a (meth) acrylic polymer.

  The adhesive of the present invention is an adhesive using the curable composition of the present invention.

  The sealing material of the present invention is a sealing material using the curable composition of the present invention.

  The product of the present invention is a product produced using the curable composition of the present invention.

  According to the present invention, there is provided a curable composition using a compound having a fluorosilyl group as a curing catalyst for an organic polymer having a crosslinkable silicon group, and using silica as a thixotropy-imparting agent, with improved storage. A curable composition having stability can be provided.

  Hereinafter, embodiments of the present invention will be described. However, these are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

  The curable composition of the present invention comprises (A) an organic polymer having a crosslinkable silicon group (excluding those having a Si—F bond), (B) a silicon compound having a Si—F bond, and (C) ) Fumed silica and (D) a compound obtained by Michael addition of a compound having a (meth) acryloyl group and a compound having an amino group, the compound having a silicon group having a hydrolyzable group bonded to a silicon atom It is characterized by containing.

  The organic polymer (A) is not particularly limited as long as it has a crosslinkable silicon group and has no Si—F bond. This organic polymer has an organic polymer main chain and does not contain polysiloxane. In the case of polysiloxane, there is a problem that it contains a low molecular cyclic siloxane that causes electrical contact failure, but in the case of an organic polymer, such a problem does not occur.

  Examples of the organic polymer include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Alkylene polymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymers of butadiene with acrylonitrile and / or styrene, polybutadiene, Copolymers of isoprene or butadiene with acrylonitrile, styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid Polyester-based polymer obtained by condensation with lactone or ring-opening polymerization of lactones; (meth) acrylate-based polymer obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Copolymer; Vinyl polymer obtained by radical polymerization of monomers such as (meth) acrylate monomer, vinyl acetate, acrylonitrile, and styrene; Graft polymer obtained by polymerizing vinyl monomer in the organic polymer A polysulfide-based polymer; nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.6 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-amino Nylon 11 by condensation polymerization of undecanoic acid, ε-amino Nylon 12 by ring-opening polymerization of urolactam, polyamide-based polymer such as copolymerized nylon having two or more of the above-mentioned nylons; for example, a polycarbonate-based polymer produced by condensation polymerization from bisphenol A and carbonyl chloride; Diallyl phthalate polymers and the like.

  Among them, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers and (meth) acrylate polymers have relatively low glass transition temperatures. It is preferable because the obtained cured product has excellent cold resistance. Further, a polyoxyalkylene polymer and a (meth) acrylate polymer are particularly preferred because they have high moisture permeability and are excellent in deep curability when formed into a one-part composition.

  The crosslinkable silicon group of the organic polymer (A) used in the present invention has a hydrolyzable group bonded to a silicon atom and is a group that can be crosslinked by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (1) is preferable.

In the formula (1), R ¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or R ^1. ₃ represents a triorganosiloxy group represented by SiO— (R ¹ is the same as described above), and when two or more R ¹ are present, they may be the same or different. X represents a hydrolyzable group, and when two or more Xs are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2. Also, b in the following p general formulas (2) need not be the same. p shows the integer of 0-19. However, it is assumed that a + (sum of b) ≧ 1 is satisfied.

  The hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3, and a + (the sum of b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms forming the crosslinkable silicon group may be one, or two or more. In the case of silicon atoms linked by a siloxane bond or the like, the number may be about twenty.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (3) is preferable because it is easily available.

In the formula (3), R ¹ and X are the same as described above, and a is an integer of 1, 2, or 3. In order to obtain a curable composition having a sufficient curing speed in consideration of curability, a in Formula (3) is preferably 2 or more, and more preferably 3.

Specific examples of the R ^1, shown, for example an alkyl group such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl, and aralkyl groups such as benzyl group, with R ¹ ₃ SiO- And the like. Of these, a methyl group is preferred.

  The hydrolyzable group represented by X is not particularly limited as long as it is other than an F atom, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxyl group, an amide group and an aminooxy group are more preferred. Alkoxyl groups are particularly preferred from the viewpoint of gentle hydrolysis and easy handling. Among the alkoxyl groups, those having a smaller number of carbon atoms have higher reactivity, and the reactivity becomes lower as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. A methoxy group or an ethoxy group is usually used, although it can be selected according to the purpose and use.

Specific structures of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, and dialkoxy groups such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [—SiR ₁ (OR) ₂ ] is exemplified, and a trialkoxysilyl group [—Si (OR) ₃ ] is preferable because of high reactivity, and a trimethoxysilyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  The crosslinkable silicon groups may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain or the side chain or any of them. The number of silicon atoms forming a crosslinkable silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and has a number average molecular weight of about 500 to 100,000, more preferably 1,000 to 50,000 in terms of polyethylene glycol in GPC. 000, and particularly preferably from 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inferior in elongation properties, and if it exceeds 100,000, it tends to be disadvantageous in terms of workability due to high viscosity.

  In order to obtain a high-strength, high-elongation, rubber-like cured product exhibiting a low elastic modulus, the number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more on average in one molecule of the polymer. Is preferably 1.0 or more, particularly preferably 1.1 to 5. If the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability will be insufficient and it will be difficult to exhibit good rubber elasticity behavior. The crosslinkable silicon group may be at the terminal of the main chain or the terminal of the side chain of the organic polymer molecular chain, or may be at both terminals. In particular, when the crosslinkable silicon group is only at the terminal of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product becomes longer, so that high strength and high elongation are obtained. And a rubber-like cured product having a low elastic modulus is easily obtained.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (4).
-R ² -O- ··· (4)
In the general formula (4), R ² is a linear or branched alkylene group having 1 to 14 carbon atoms, and preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. .

Specific examples of the repeating unit represented by the general formula (4) include:
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
And the like. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

  Examples of a method for synthesizing a polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, for example, JP-A Nos. 61-197631, 61-215622, 61-215623, and 61-215623. A polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting an organoaluminum compound and porphyrin as shown, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336. Examples thereof include a polymerization method using a catalyst, but are not particularly limited. According to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst, a polyoxyalkylene-based polymer having a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less and a narrow molecular weight distribution. A polymer can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bonding component. Examples of the urethane binding component include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; Those obtained from the reaction with the coalescence can be given.

  The introduction of a crosslinkable silicon group into a polyoxyalkylene polymer is carried out in a polyoxyalkylene polymer having a functional group such as an unsaturated group, a hydroxyl group, an epoxy group or an isocyanate group in the molecule. The reaction can be performed by reacting a compound having a reactive functional group and a crosslinkable silicon group (hereinafter, referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, an unsaturated group-containing polyoxyalkylene polymer is reacted with hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to hydrosilylate or mercapto to form a crosslinkable silicon group. A method for obtaining a polyoxyalkylene polymer having the following formula: The unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group having reactivity to the functional group, and Can be obtained.

  Other specific examples of the polymer reaction method include a method of reacting a polyoxyalkylene polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group, and a method of reacting a polyoxyalkylene compound having an isocyanate group at a terminal. Examples of the method include a method of reacting a polymer with a compound having an active hydrogen group such as a hydroxyl group or an amino group and a crosslinkable silicon group. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B-45-36319, JP-B-46-12154, JP-A-50-156599, JP-A-54-6096, and JP-A-55-13767. Nos. 57-164123, JP-B-3-2450, JP-A-2005-213446, JP-A-2005-306891, WO2007-040143, U.S. Patent 3,632,557, U.S. Pat. Japanese Patent Publication Nos. 4,960,844 and the like can be cited. The above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer having substantially no carbon-carbon unsaturated bond other than the aromatic ring, and the polymer constituting the skeleton thereof includes (1) ethylene, propylene, 1-butene, isobutylene and the like. (2) a diene compound such as butadiene or isoprene is homopolymerized, or the olefin compound is copolymerized with the olefin compound. After that, it can be obtained by a method such as hydrogenation.However, the isobutylene-based polymer and the hydrogenated polybutadiene-based polymer can easily introduce a functional group into a terminal, easily control a molecular weight, and have a number of terminal functional groups. Is preferred, and an isobutylene-based polymer is particularly preferred. Those whose main chain skeleton is a saturated hydrocarbon-based polymer have characteristics that are excellent in heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or a copolymer with another monomer may be used. However, from the viewpoint of rubber properties, 50 units of the repeating units derived from isobutylene are used. Those containing not less than 80% by mass are preferable, those containing not less than 80% by mass are more preferable, and those containing 90 to 99% by mass are particularly preferable.

As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have hitherto been reported. In particular, in recent years, many so-called living polymerizations have been developed. In the case of a saturated hydrocarbon polymer, in particular, an isobutylene polymer, the inifer polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843) discovered by Kennedy et al. It is known that it can be easily produced by using the compound, can be polymerized to a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups into molecular terminals.

  As a method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, JP-A-63-254149, JP-A-64-22904, These are described in, for example, Kaihei 1-197509, Japanese Patent No. 2539445, Japanese Patent No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, but are not particularly limited thereto. The above-mentioned saturated hydrocarbon polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The (meth) acrylate-based monomer constituting the main chain of the (meth) acrylate-based polymer is not particularly limited, and various types can be used. For example, (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, ( (Meth) alkyl acrylate monomers such as 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylate monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylate monomers such as ethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, and 2-aminoethyl (meth) acrylate Monomers: γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylate monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; derivatives of (meth) acrylic acid such as ethylene oxide adduct of (meth) acrylic acid; and (meth) acrylic Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylate ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate And fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylate polymer, the following vinyl monomers can be copolymerized together with the (meth) acrylate monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; and fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; Methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexyl Maleimide monomers such as maleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and cinnamon Vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

  These may be used alone or a plurality of them may be copolymerized. Among them, a polymer composed of a (meth) acrylic acid-based monomer is preferable from the viewpoint of the physical properties of the product. More preferably, it is a (meth) acrylate polymer using one or more alkyl (meth) acrylate monomers and optionally using other (meth) acrylate monomers in combination, and is a silyl. The number of silicon groups in the (meth) acrylate polymer (A) can be controlled by using a group-containing (meth) acrylate monomer in combination. Particularly preferred is a methacrylic acid ester-based polymer comprising a methacrylic acid ester monomer because of its good adhesiveness. When lowering the viscosity, imparting flexibility, or imparting tackiness, it is preferable to use an acrylate monomer as appropriate. In this specification, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylate polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112624, JP-A-2007-230947, and JP-A-2001-40037). And a synthesis method described in JP-A-2003-313397), and a radical polymerization method using a radical polymerization reaction is preferable. Examples of the radical polymerization method include a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, and introduction of a crosslinkable silicon group into a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide, or the like as a polymerization initiator has a problem that the value of the molecular weight distribution is generally as large as 2 or more, and the viscosity is increased. I have. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a high proportion of a crosslinkable functional group at a molecular chain terminal, It is preferable to use a controlled radical polymerization method.

Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and a reversible addition-fragmentation chain transfer (RAFT) polymerization method, A living radical polymerization method such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) is more preferable. Further, a reaction using a thiol compound having a crosslinkable silicon group and a reaction using a thiol compound having a crosslinkable silicon group and a metallocene compound (Japanese Patent Application Laid-Open No. 2001-40037) are also suitable. The above-mentioned (meth) acrylate polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylate polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used. Particularly, a polymer containing both a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group has advantages such as excellent weather resistance and adhesiveness. And preferred.

  A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. It has been proposed in, for example, Japanese Unexamined Patent Publication No. 63-112624, Japanese Patent Application Laid-Open No. 6-172631, and Japanese Patent Application Laid-Open No. 11-116763, but is not particularly limited thereto.

A preferred specific example is a compound having a crosslinkable silicon group and a molecular chain substantially having the following general formula (5):
_{^{-CH 2 -C (R 3) (}} COOR 4) - ··· (5)
(Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 1 to 5 carbon atoms), and a (meth) acrylate monomer unit represented by the following general formula (6):
_{^{-CH 2 -C (R 3) (}} COOR 5) - ··· (6)
(Wherein R ³ is the same as above, and R ⁵ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising a (meth) acrylate monomer unit represented by the following formula: This is a method of blending and producing a polyoxyalkylene-based polymer.

As R ^{4 in the} general formula (5), for example, a group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, preferably 1 to 4, more preferably 1 to 4 And 2 alkyl groups. The alkyl group of R ⁴ may be used alone or in combination of two or more.

Examples of ^{R 5} in the general formula (6), such as 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, carbon atoms, such as behenyl group 6 or more, usually 7-30, preferably 8-20 And a long-chain alkyl group. As in the case of R ⁴ , the alkyl group of R ⁵ may be used alone or as a mixture of two or more.

  The molecular chain of the (meth) acrylic acid ester-based copolymer substantially consists of the monomer units of the formulas (5) and (6), and “substantially” as used herein means the copolymer. It means that the total of the monomer units of the formulas (5) and (6) present therein exceeds 50% by mass. The total of the monomer units of the formulas (5) and (6) is preferably at least 70% by mass. The abundance ratio of the monomer unit of the formula (5) to the monomer unit of the formula (6) is preferably from 95: 5 to 40:60, more preferably from 90:10 to 60:40 by mass ratio.

  Monomer units other than the formulas (5) and (6) which may be contained in the copolymer include, for example, α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; acrylamide, methacrylamide An amide group such as N-methylol acrylamide and N-methylol methacrylamide; an epoxy group such as glycidyl acrylate and glycidyl methacrylate; a monomer containing an amino group such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate and aminoethyl vinyl ether; and other acrylonitrile; Examples include monomer units derived from styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  Having a crosslinkable silicon group used in a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group ) As an acrylate polymer, for example, a polymer having a crosslinkable silicon group described in JP-A-63-112842 and having a molecular chain substantially (1) having an alkyl group having 1 to 8 carbon atoms (meth) And (2) publicly known (meth) acrylic acid ester-based copolymers containing an acrylic acid alkyl ester monomer unit and (2) a (meth) acrylic acid alkyl ester monomer unit having an alkyl group having 10 or more carbon atoms. (Meth) acrylate-based copolymers can also be used.

  The number average molecular weight of the (meth) acrylate polymer is preferably from 600 to 10,000, more preferably from 600 to 5,000, even more preferably from 1,000 to 4,500. By setting the number average molecular weight in the above range, compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylate polymer may be used alone or in combination of two or more. The mixing ratio of the polyoxyalkylene polymer having a crosslinkable silicon group to the (meth) acrylate polymer having a crosslinkable silicon group is not particularly limited, but the (meth) acrylate ester is preferably It is preferable that the (meth) acrylate polymer is in the range of 10 to 60 parts by mass, more preferably 20 to 60 parts by mass, based on 100 parts by mass in total of the polymer and the polyoxyalkylene polymer. It is within the range of 50 parts by mass, and more preferably within the range of 25 to 45 parts by mass. If the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity becomes high and the workability deteriorates, which is not preferable.

  Organic polymers obtained by blending a saturated hydrocarbon polymer having a crosslinkable silicon group with a (meth) acrylate copolymer having a crosslinkable silicon group are described in JP-A-1-168774 and JP-A-2000-964. Although it is proposed in 186176 and the like, it is not particularly limited thereto.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylate copolymer having a crosslinkable silicon group, another method for producing an organic polymer in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing a (meth) acrylate monomer can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, etc. It is not limited to these.

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslinkable polymer have been added to 100 parts by mass of a polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10 to 200 parts by mass of the (meth) acrylate polymer having a functional silicon group, and it is more preferable to use 20 to 80 parts by mass.

  In the present invention, the compound (B) having a fluorosilyl group acts as a curing catalyst for the (A) crosslinkable organic polymer having a silicon group. As the compound having a fluorosilyl group (B), a known compound having a fluorosilyl group can be widely used, and there is no particular limitation. Both a low-molecular compound and a high-molecular compound can be used. An organic silicon compound having a fluorosilyl group is preferable, and an organic polymer having a fluorosilyl group is more preferable because of its high safety.

  Specific examples of the compound (B) having a fluorosilyl group include fluorosilanes represented by the following formula (7), compounds having a fluorosilyl group represented by the following formula (8), and fluorosilyl groups. Preferred examples thereof include organic polymers having the same.

R ⁶ _4-c SiF _c (7)
(In the formula (7), R ⁶ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ⁷ SiO— (R ⁷ is each independently having 1 to 20 carbon atoms. Is a substituted or unsubstituted hydrocarbon group or a fluorine atom), and c is any of 1 to 3, and c is preferably 3. R ⁶ And when there are a plurality of R ^{7 s} , they may be the same or different.)

^{_{-SiF c R 6 d Z e ···}} (8)
(In the formula (8), R ⁶ and c are the same as those in the formula (7), Z is each independently a hydroxyl group or a hydrolyzable group other than fluorine, and d is any of 0 to 2. , E is any one of 0 to 2, and c + d + e is 3. When a plurality of R ⁶ , R ⁷ and Z are present, they may be the same or different.)

  Examples of the fluorosilanes represented by the formula (7) include fluorotrimethylsilane, fluorotriethylsilane, fluorotripropylsilane, fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl ( 3-methylphenyl) silane, fluorodimethyl (4-methylphenyl) silane, fluorodimethyl (4-chlorophenyl) silane, fluorotriphenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenyl Silane, trifluoroethylsilane, trifluoropropylsilane, trifluorobutylsilane, trifluorophenylsilane, γ Methacryloxypropylfluorodimethylsilane, γ-methacryloxypropyldifluoromethylsilane, γ-methacryloxypropyltrifluorosilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1, 3-difluoro-1,1,3,3-tetramethyldisiloxane, tetrafluorosilane, octafluorotrisilane, 1,3,5,7-tetrafluoro-1,3,5,7-tetrasilatricyclo [3 3.3.1.1 (3,7)] decane, 1,1-difluoro-1-silacyclo-3-pentene, fluorotris (trimethylsiloxy) silane and the like.

  Among these, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, γ-methacryloxypropylfluorodimethylsilane, γ-methacryloxypropyldifluoro Methylsilane, γ-methacryloxypropyltrifluorosilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1,1,3,3-tetra Methyldisiloxane and the like are preferred.

  In the fluorosilyl group represented by the formula (8), examples of the hydrolyzable group represented by Z include the same groups as the hydrolyzable group represented by X in the formula (1). Examples thereof include a hydrogen atom, a halogen atom other than fluorine, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferred, and an alkoxy group is particularly preferred.

Further, as the R ^6, for example, an alkyl group such as methyl group and ethyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, aralkyl group or, R ⁷ is a methyl group such as a benzyl group, a phenyl And a triorganosiloxy group represented by R ⁷ SiO— which is a group or the like. Of these, a methyl group is particularly preferred.

  Specific examples of the fluorosilyl group represented by the formula (8) include, as a silicon group having no hydrolyzable group other than fluorine, a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, and a fluorosilyl group. A silicon group in which one fluorine is substituted on a silicon group such as a diphenylsilyl group and a fluorodibenzylsilyl group; and a silicon group such as a difluoromethylsilyl group, a difluoroethylsilyl group, a difluorophenylsilyl group and a difluorobenzylsilyl group. A silicon group in which two fluorines are substituted; a silicon group in which three fluorines are substituted on a silicon group which is a trifluorosilyl group.

  As a silicon group having both fluorine and other hydrolyzable groups, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluoromethoxyphenylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group, A fluorodipropoxysilyl group, a fluorodiphenoxysilyl group, a fluorobis (2-propenoxy) silyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, a difluorophenoxysilyl group, a fluorodichlorosilyl group, a difluorochlorosilyl group, and the like. .

A silicon group having no hydrolyzable group other than fluorine or a fluorosilyl group in which R ⁶ is a methyl group is preferred, and a trifluorosilyl group is more preferred. Further, from the ease of synthesis, fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group , A difluoromethoxysilyl group, a difluoroethoxysilyl group is more preferable, and a silicon group having no hydrolyzable group other than fluorine such as a fluorodimethylsilyl group, a difluoromethylsilyl group, and a trifluorosilyl group is more preferable from the viewpoint of stability. From the viewpoint of high curability, a silicon group in which two or three fluorines are substituted on a silicon group such as a difluoromethylsilyl group, a difluoromethoxysilyl group, a difluoroethoxysilyl group, and a trifluorosilyl group is preferable. Difluoromethylsilyl group is most preferred from the heal of.

  The compound having a fluorosilyl group represented by the formula (8) is not particularly limited, and any of a monomolecular compound and a polymer compound can be used. For example, fluorosilanes represented by the formula (7) , Fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyldifluoromethoxysilane, methyltrifluorosilane, methylfluorodiethoxysilane , Methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinylfluorodiethoxysilane, vinyldifluoroethoxysilane, phenylfur Low molecular compounds such as rhodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, phenyldifluoroethoxysilane, and fluorotrimethylsilane, and fluorination having a fluorosilyl group represented by the formula (8) at the terminal A high molecular compound such as polysiloxane is mentioned, and a polymer having a fluorosilyl group represented by the formula (8) at a terminal of a main chain or a side chain is preferable.

The fluorosilanes represented by the formula (7) and the compound having a fluorosilyl group represented by the formula (8) may be a commercially available reagent or may be synthesized from a starting compound. Although there is no particular limitation on the synthesis method, a compound having a silicon group represented by the following formula (9) and a fluorinating agent can be prepared by a known method (for example, Organometallics 1996, 15, 2,478 (Ishikawa et al.)). A compound obtained by reacting with the above is preferably used.
—SiR ⁶ _3-q Z _q (9)
(In the formula (9), R ⁶ and Z are respectively the same as the formula (8), and q is any of 1 to 3.)

  Examples of the hydrolyzable silicon group represented by the formula (9) include an alkoxysilyl group, a siloxane bond, a halosilyl group such as a chlorosilyl group, and a hydrosilyl group.

Specific examples of the fluorinating agent used for fluorination of the alkoxysilyl group are not particularly limited, and include, for example, NH ₄ F, Bu ₄ NF, HF, BF ₃ , Et ₂ NSF ₃ , HSO ₃ F, and SbF _5. , VOF ₃ , CF ₃ CHFCF ₂ NEt _{2 and the} like. Specific examples of the fluorinating agent used for fluorination of the halosilyl group are not particularly limited. For example, AgBF ₄ , SbF ₃ , ZnF ₂ , NaF, KF, CsF, NH ₄ F, CuF ₂ , NaSiF ₆ , NaPF ₆ , NaSbF ₆ , NaBF ₄ , Me ₃ SnF, KF (HF) _{1.5 to 5, and the} like. Specific examples of fluorinating agents used for the fluorination of hydrosilyl group is not particularly limited, for ^{_{example, AgF, PF 5, Ph 3}} CBF 4, SbF 3, NOBF 4, such as _NO 2 BF ₄ and the like. The compound having a siloxane bond is cleaved by BF ₃ or the like to obtain a fluorosilyl group.

Among the methods for synthesizing a fluorosilyl group using these fluorinating agents, a method for fluorinating an alkoxysilane using BF ₃ is preferred because the reaction is simple, the reaction efficiency is high, and the safety is high. A fluorination method of chlorosilane using CuF ₂ or ZnF ₂ is preferable.

Examples of BF ₃ include BF ₃ gas, BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ phosphate complex, BF ₃ hydrate, and BF ₃ piperidine. Complexes, BF ₃ phenol complexes and the like can be used, but BF ₃ ether complexes, BF ₃ thioether complexes, BF ₃ amine complexes, BF ₃ alcohol complexes, BF ₃ carboxylic acid complexes, BF ₃ hydrates are easy to handle. Are preferred. Among them, BF ₃ ether complex, BF ₃ alcohol complex and BF ₃ hydrate have high reactivity and are preferable, and BF ₃ ether complex is particularly preferable.

The organic polymer having a fluorosilyl group (also referred to as a fluorinated polymer in the present specification) is not particularly limited as long as it is an organic polymer having a Si—F bond. Polymers can be widely used. The position of the SiF bond in the organic polymer is not particularly limited, and the effect is exhibited at any site in the polymer molecule. If the terminal of the main chain or the side chain is -SiR ′ ₂ F, the polymer Is represented in the form of -SiR'F- or ≡SiF (R 'is independently an arbitrary group). As the organic polymer having a Si—F bond at the terminal of the main chain or the side chain, a polymer having a fluorosilyl group represented by the above formula (8) is preferable. As the fluorosilyl group in the polymer, a bifunctional fluorosilyl group in which c in the formula (8) is 2 is preferable, and a difluoromethylsilyl group is more preferable. Examples Although fluoro silyl group is incorporated in the main chain of the _{polymer, -Si (CH 3) F -} , - Si (C 6 H 5) F -, - SiF 2 -, and the like ≡SiF .

  The fluorinated polymer is a single polymer having the same type of fluorosilyl group and main chain skeleton, that is, the number of fluorosilyl groups per molecule, the bonding position thereof, and the number of F that the fluorosilyl group has, Further, the polymer may be a single polymer having the same main chain skeleton, or a mixture of a plurality of polymers in which any or all of them are different. In any case where the fluorinated polymer is a single polymer or a mixture of a plurality of polymers, the fluorinated polymer can be suitably used as a resin component of a curable composition showing rapid curability, but is high. In order to obtain a rubber-like cured product exhibiting curability, and having high strength and high elongation and exhibiting a low elastic modulus, the fluorosilyl group contained in the fluorinated polymer is at least on average per one molecule of the polymer. One, preferably 1.1 to 5, more preferably 1.2 to 3 is present. If the number of fluorosilyl groups contained in one molecule is less than one on average, curability may be insufficient, and good rubber elasticity may not be easily exhibited. When the number of fluorosilyl groups contained in one molecule is more than five on average, the rubbery cured product may have a small elongation. As described above, the fluorosilyl group may be present at the terminal of the main chain or the terminal of the side chain of the polymer molecular chain, or may be incorporated in the main chain. When present at the end of the polymer, the effective mesh length of the organic polymer component contained in the finally formed cured product increases, so that a rubber-like cured product having high strength, high elongation, and low elastic modulus is obtained. It becomes easy to be. When two or more fluorosilyl groups are present in one molecule, the respective silicon groups may be the same or different.

  Further, the fluorinated polymer contains, together with the fluorosilyl group, a substituent other than a fluorosilyl group such as a silicon group having only a hydrolyzable group other than fluorine (for example, a methyldimethoxysilyl group). May be. As such a fluorinated polymer, for example, a polymer in which one main chain terminal is a fluorosilyl group and the other main chain terminal is a silicon group having only a hydrolyzable group other than fluorine as a hydrolyzable group Can be mentioned.

  In the fluorinated polymer, any method may be used to introduce the fluorosilyl group. The introduction method (method (i)) by reacting the fluorosilyl group-containing low-molecular silicon compound with the polymer may be used. A method (method (ii)) of modifying a silicon group of a polymer containing a crosslinkable silicon group having a hydrolyzable group into a fluorosilyl group is exemplified.

The following method is a specific example of the method (i).
(A) A method in which a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule is reacted with a compound having a functional group having a reactivity to the functional group and a fluorosilyl group. For example, a method of reacting a polymer having a hydroxyl group at a terminal with isocyanatopropyldifluoromethylsilane or a method of reacting a polymer having a SiOH group at a terminal with difluorodiethoxysilane are exemplified.
(B) A method in which a hydrosilane having a fluorosilyl group is allowed to act on a polymer containing an unsaturated group in a molecule to perform hydrosilylation. For example, there is a method in which difluoromethylhydrosilane is reacted with a polymer having an allyl group at a terminal.
(C) A method in which a polymer having an unsaturated group is reacted with a compound having a mercapto group and a fluorosilyl group. For example, there is a method in which a polymer having an allyl group at a terminal is reacted with mercaptopropyldifluoromethylsilane.

  As the polymer having a crosslinkable silicon group having a hydrolyzable group other than fluorine used in the above method (ii), the above-described organic polymer (A) having a crosslinkable silicon group is suitably used.

In the method (ii), as a method for converting a crosslinkable silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group, a known method can be used. For example, the method is represented by the above-mentioned formula (9). A method of converting the crosslinkable silicon group to a fluorosilyl group with a fluorinating agent can be used. Examples of the fluorinating agent include the above-mentioned fluorinating agents. Among them, BF ₃ ether complex, BF ₃ alcohol complex and BF ₃ dihydrate have high activity, fluorination proceeds efficiently, and BF ₃ It is more preferable because no salt or the like is generated in the product and the post-treatment is easy, and a BF ₃ ether complex is particularly preferable. Further, in the fluorination by the BF ₃ ether complex, the reaction proceeds even without heating, but it is preferable to heat in order to perform the fluorination more efficiently. The heating temperature is preferably from 50 ° C to 150 ° C, more preferably from 60 ° C to 130 ° C. When the temperature is lower than 50 ° C., the reaction does not proceed efficiently and the fluorination may take time. If the temperature is higher than 150 ° C., the fluorinated polymer may be decomposed. In the fluorination with the BF ₃ complex, coloring may occur depending on the type of the raw material polymer used. However, from the viewpoint of suppressing coloring, it is preferable to use a BF ₃ alcohol complex or BF ₃ dihydrate.

The fluorinating agent used in the production of the fluorinated polymer may also act as a curing catalyst for the fluorinated polymer, and when water is present when producing the fluorinated polymer using the above method (ii). In addition, the silanol condensation reaction may proceed, and the viscosity of the obtained fluorinated polymer may increase. For this reason, it is desirable that the production of the fluorinated polymer be performed in an environment where water is not present as much as possible.Before fluorination, the fluorinated polymer is subjected to azeotropic dehydration using toluene, hexane, or the like. Preferably, a dehydration operation is performed. However, when the BF ₃ amine complex is used, fluorination hardly proceeds after the dehydration operation, and the reactivity tends to be improved by adding a small amount of water. Is preferably added. Further, from the viewpoint of the stability of the fluorinated polymer, it is preferable to remove components derived from the fluorinating agent and by-produced fluorinating agent after the fluorination by filtration, decantation, liquid separation, devolatilization under reduced pressure, or the like. When a fluorinated polymer is produced using the above-mentioned BF ₃ -based fluorinating agent, BF ₃ remaining in the produced fluorinated polymer and BF ₃ derived components produced by the reaction are less than 500 ppm in B amount. Is more preferably, less than 100 ppm, particularly preferably less than 50 ppm. By removing BF ₃ and the components derived from BF ₃ , an increase in the viscosity of the obtained fluorinated polymer itself and a mixture of the fluorinated polymer and the raw material polymer can be suppressed. Considering this point, the fluorination method using a BF ₃ ether complex or a BF ₃ alcohol complex is preferable because the boron component can be relatively easily removed by vacuum devolatilization, and the method using the BF ₃ ether complex is particularly preferable. .

  Here, when the polymer to be fluorinated has two or more hydrolyzable groups other than fluorine, all the hydrolyzable groups may be fluorinated or a method such as reducing the amount of the fluorinating agent. May be partially fluorinated by adjusting fluorination conditions. For example, in the method (ii), when a fluorinated polymer is produced using a polymer to be fluorinated, the amount of the fluorinating agent is not particularly limited, and the molar amount of fluorine atoms in the fluorinating agent is not limited. It is sufficient that the amount is equal to or greater than the molar amount of the polymer to be fluorinated. When all of the hydrolyzable groups of the polymer to be fluorinated are to be fluorinated by the method (ii), the molar amount of fluorine atoms in the fluorinating agent is determined by the amount of the crosslinking polymer contained in the starting polymer. It is preferable to use an amount of the fluorinating agent that is equal to or greater than the total molar amount of the hydrolyzable group in the silicon group. Here, the “fluorine atom in the fluorinating agent” refers to a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in a crosslinkable silicon group of a polymer to be fluorinated. Refers to a fluorine atom that can be substituted.

  The low molecular compound having a fluorosilyl group in the above method (i) can also be synthesized from a general-purpose crosslinkable silicon group-containing low molecular compound using the above fluorination method.

  In the method (i), there is a reactive group for reacting the polymer and the silicon-containing low molecular weight compound together with the fluorosilyl group. Therefore, when the reaction becomes complicated, the fluorinated polymer is obtained by the method (ii). Is preferred.

  The glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ° C or lower, more preferably 0 ° C or lower, and particularly preferably -20 ° C or lower. When the glass transition temperature is higher than 20 ° C., the viscosity in winter or in a cold region becomes high, and it may be difficult to handle. In addition, the flexibility of a cured product obtained when used as a curable composition decreases, and May decrease. The glass transition temperature can be determined by DSC measurement.

The fluorinated polymer may be linear or branched. The number average molecular weight of the fluorinated polymer is preferably from 1,000 to 100,000 in terms of polyethylene glycol in GPC, more preferably from 1,000 to 50,000, still more preferably from 2,000 to 30,000, particularly preferably. 2,000 to 25,000. If the number average molecular weight is less than 1,000, the cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the viscosity tends to be high, and the workability tends to be inconvenient.

  The compounding ratio of the silicon compound (B) having the Si-F bond is 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass of the silicon compound (B) per 100 parts by mass of the polymer (A). And more preferably 0.5 to 10 parts by mass.

  The curable composition of the present invention uses fumed silica as the component (C). Fumed silica is mainly used as a thixotropic agent (thixotropic agent, anti-sagging agent), but also acts as a reinforcing filler. Examples of the fumed silica include hydrophilic silica and hydrophobic silica, and hydrophobic silica is preferable.

Examples of the hydrophilic silica include hydrophilic fumed silica obtained by a flame hydrolysis method of silicon tetrachloride. The hydrophilic fumed silica preferably has a hydrophilic silanol group on the surface, a primary particle diameter of 5 to 20 nm, and a specific surface area (BET) of 40 to 400 m ² / g. Commercially available products of such hydrophilic fumed silica include, for example, Aerosil # 300 and # 200 (all of which are manufactured by Nippon Aerosil Co., Ltd., trade names).

The hydrophobic silica is a fumed silica obtained by chemically treating the above hydrophilic fumed silica with silane, siloxane, or the like, has a primary particle diameter of 7 to 25 nm, and has a specific surface area (BET). ) Is preferably 50 to 500 m ² / g. Commercial products of such hydrophobic fumed silica include, for example, R972, R974, RY200S (all manufactured by Nippon Aerosil Co., Ltd., trade names) and the like. The primary particle size of the hydrophilic silica and the hydrophobic silica can be measured, for example, by a dynamic light scattering method.

  The fumed silica (C) is used in an amount of 0.1 to 20 parts by mass based on 100 parts by mass of the organic polymer having a crosslinkable silicon group as the component (A). 0.5 to 10 parts by mass is preferable, and 1 to 5 parts by mass is more preferable. When the amount is less than 0.1 part by mass, the thixotropy imparting becomes insufficient, and when the amount exceeds 20 parts by mass, the viscosity of the composition tends to increase.

  The curable composition of the present invention is a compound obtained by Michael addition of a compound having a (meth) acryloyl group and a compound having an amino group as the component (D), and has a hydrolyzable group bonded to a silicon atom. A compound having a silicon group is used. Hereinafter, a silicon group having a hydrolyzable group bonded to a silicon atom is also referred to as a hydrolyzable silicon group. Examples of the method for producing the component (D) include the following.

(A) A compound having a hydrolyzable silicon group and a (meth) acryloyl group is reacted with a compound having no hydrolyzable silicon group and having an amino group.
(Ii) A compound having no (meth) acryloyl group having no hydrolyzable silicon group is reacted with a compound having a hydrolyzable silicon group and an amino group.
(C) A compound having a hydrolyzable silicon group and a (meth) acryloyl group is reacted with a compound having a hydrolyzable silicon group and an amino group.
Among them, the method (c) is preferable. Hereinafter, a compound having a hydrolyzable silicon group and a (meth) acryloyl group is also referred to as (meth) acryloylsilane, and a compound having a hydrolyzable silicon group and an amino group is also referred to as aminosilane.

  Examples of (meth) acryloylsilane include (meth) acryloxysilane compounds such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropylmethyldimethoxysilane. These may be used alone or in combination of two or more.

  Examples of the compound having an amino group without a hydrolyzable silicon group include ethylamine, allylamine, isopropylamine, 2-ethylhexylamine, 2-ethylhexyloxylpropylamine, 3-ethoxypropylamine, t-butylamine, and sec-butylamine. , Propylamine, 3-methoxypropylamine, stearylamine, mono-primary amine compounds such as 2-phenylethylamine, diisopropylamine, diethylamine, diisobutylamine, di (2-ethylhexyl) amine, 2-pyrrolidone, various imidazole compounds, pyrrolidine , Piperidine, secondary amine compounds such as 1-benzylpiperazine, and primary and secondary compounds such as 3-diethylaminopropylamine, dibutylaminopropylamine and 3- (dimethylamino) propylamine. Compounds having an amino group is preferably used. Of these, compounds having a primary amino group are preferred. These may be used alone or in combination of two or more.

  Examples of the aminosilane include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane And other special aminosilanes manufactured by Shin-Etsu Chemical Co., Ltd., trade names: KBM6063, X-12-896, KBM576, X-12-565, X-12-580, X-12-806, X-12-666, X-12-5263, KBM6123, X-12-577, X-1 -575, X-12-563B, aminosilane compounds such as X-12-562 and the like. Of these, compounds having a primary amino group are preferred. These may be used alone or in combination of two or more.

  Examples of the compound having no (meth) acryloyl group without a hydrolyzable silicon group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl. (Meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2- (Meth) acrylates such as ethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, n-stearyl (meth) acrylate, ethyl 2-cyanoacrylate, hydroxyethyl acrylate, hydroxypropyl Hydroxy group-containing (meth) acrylates such as pill acrylate, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, trade names manufactured by Toagosei Co., Ltd .: Aronix (registered trademark) M-101, M- Monofunctional special acrylates such as 102, M-110, M-111, M-113, M-117, M-120, M-156, M-5300, M-5400, M-5600, M-5700, Daicel Chemical Suitable examples include trade name: PLACCEL (registered trademark) FA-2D manufactured by Kogyo Co., Ltd. These may be used alone or in combination of two or more.

  The reaction conditions of the compound having a (meth) acryloyl group and the amine compound are not particularly limited, but it is preferable to carry out a mixed reaction at -20 ° C to 120 ° C for about 0.5 to 1000 hours. Both reactions may be carried out at room temperature to 120 ° C., but may be cooled if necessary. The reaction may be carried out in the presence of a medium such as an organic solvent, or may be carried out for more than 1000 hours without any problem. The compounding ratio of the amine and the (meth) acryloyl compound at the time of the reaction was such that the number of active hydrogens in one mole of the amine was γ and the number of functional groups reacting with the amino group in one mole of the (meth) acryloyl compound was δ. In this case, it is preferable that (meth) acryloylsilane be in a range of 1 / δ to γ mol per 1 mol of aminosilane.

  The compounding amount of the component (D) is 0.5 to 20 parts by mass based on 100 parts by mass of the organic polymer having a crosslinkable silicon group of the component (A). 0.5 to 10 parts by mass is preferable, and 1 to 5 parts by mass is more preferable. When the amount is less than 0.5 part by mass, the effect is insufficient, and when the amount exceeds 20 parts by mass, there is a tendency to be uneconomical.

  The curable composition of the present invention further comprises a curing catalyst (silanol condensation catalyst) other than the component (B), a filler other than the component (C), a plasticizer, an adhesion promoter, and a thixotropy other than the component (C). Granting agents, dehydrating agents, antioxidants, ultraviolet absorbers, diluents, pigments, lubricants, and the like can be added as necessary.

  The compound having a fluorosilyl group of the component (B) of the present invention acts as a curing catalyst (silanol condensation catalyst), but a curing catalyst other than the component (B) may be added to the curable composition of the present invention. .

  Examples of such curing catalysts include titanates such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic acid leads such as lead octylate and lead naphthenate; organic acid bismuth such as bismuth octylate, bismuth neodecanoate and bismuth rosinate; silanol condensation catalyst And other known basic catalysts such as organic amines, acidic catalysts such as organic carboxylic acids, and salts of acidic catalysts and basic catalysts.

  Among these, a basic catalyst such as an organic amine, an acidic catalyst such as an organic carboxylic acid, or a salt of an acidic catalyst and a basic catalyst is preferable, and a salt of an acidic catalyst and a basic catalyst is particularly preferable. As the basic catalyst, organic amines are preferable, amidines are more preferable, cyclic diamine compounds having an amidine skeleton are more preferable, and 1,8-diazabicyclo (5.4.0) undecene-7 (DBU) and 5-diazabicyclo ( 4.3.0) Nonene-5 (DBN) and the like are particularly preferred.

  As the acidic catalyst constituting the salt, any of an organic acid and an inorganic acid can be used. Examples of the acid include acetic acid, octylic acid, nonanoic acid, acrylic acid, benzoic acid, carboxylic acids such as trifluoroacetic acid, carboxylic acids such as difluoroacetic acid, carboxylic acids such as fluoroacetic acid, carboxylic acids such as trichloroacetic acid, Carboxylic acids such as dichloroacetic acid; carboxylic acids such as chloroacetic acid; phenols such as phenol and o-cresol; sulfonic acids such as benzenesulfonic acid; and acid anhydrides thereof; Sulfonic acid is preferred, and carboxylic acid is more preferred from the viewpoint of good stability.

  It is preferable to use a salt of an acidic catalyst and a basic catalyst (a reaction product of an acidic catalyst and a basic catalyst), and it is particularly preferable to use a reaction product of an amidine and an acid. Such a reaction product may be a product in which an amidine and an acid have completely reacted, or may contain an unreacted amidine or an acid. Further, an amidine or an acid may be separately added to the reaction product.

  When a curing catalyst other than the component (B) is used, 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 100 parts by mass per 100 parts by mass of the polymer of the component (A). It is preferable to mix 10 to 10 parts by mass.

  The curable composition of the present invention can further use a filler other than the component (C) as long as the object of the present invention is achieved. Examples of such fillers include calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, anhydrous silicic acid, calcium silicate, silica other than the component (C), titanium dioxide, clay, talc, and slate powder. , Mica, kaolin, zeolite, carbon black, polymer powder, and the like. Calcium carbonate, silica other than the component (C), carbon black, and polymer powder are preferable. At least one selected from the group consisting of amorphous silica other than the component (C) having a particle size of from 300 to 300 μm and polymer powder having a particle size of from 0.01 to 300 μm is more preferable. Further, glass beads, silica beads other than the component (C), alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica other than the component (C), shirasu balloons, glass balloons, silica balloons, Saran balloons And acrylic balloons can be used. Among them, acrylic balloons are more preferable from the viewpoint of less decrease in elongation after curing of the composition.

  As the amorphous silica other than the component (C), known amorphous silica can be widely used, and there is no particular limitation, but the particle diameter is preferably 0.01 to 300 μm. 1-100 micrometers is more preferable, and 1-30 micrometers is still more preferable.

  Carbon black also acts as a thixotropic agent (anti-sagging agent) and a pigment. Examples of carbon black include acetylene black, oil furnace black, thermal black, and channel black. Among these, acetylene black and oil furnace black are preferable, acetylene black and ketjen black which is oil furnace black are preferable, and ketjen black which is oil furnace black is most preferable. These carbon blacks can be used alone or in combination of two or more.

  The DBP oil absorption of carbon black is usually in the range of 30 to 800 ml / 100 g, preferably 200 to 700 ml / 100 g, and more preferably 300 to 700 ml / 100 g. Two or more carbon blacks having different DBP oil absorptions may be used in combination.

The DBP oil absorption is the number of ml of oil contained per 100 g of carbon black, and can be measured by a conventional method using a dibutyl phthalate absorption meter. More specifically, the DBP oil absorption can be measured according to the method specified in JIS K6217. Carbon black is put into a chamber of a measuring device (Absorptometer), and DBP (n-dibutyl phthalate) is added into the chamber at a constant rate. As the DBP is absorbed, the viscosity of the carbon black increases, but the DBP oil absorption is calculated based on the amount of DBP absorbed by the time the viscosity reaches a certain level. The viscosity is detected by a torque sensor.

The content of volatile components of carbon black is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. Volatiles are desorbed gases heated at 950 ° C. The nitrogen specific surface area of carbon black is usually 50 to 2000 m ² / g.

  When using carbon black, the compounding amount of carbon black is 0.01 to 10 parts by mass, more preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the organic polymer having a crosslinkable silicon group as the component (A). Parts, particularly preferably 0.1 to 5 parts by mass.

  As the polymer powder, known polymer powders can be widely used and are not particularly limited, but the particle size is preferably from 0.01 to 300 μm, more preferably from 0.1 to 100 μm. , 1 to 30 μm are more preferred.

  As the polymer powder, for example, a monomer selected from the group consisting of (meth) acrylic acid ester, vinyl acetate, ethylene and vinyl chloride is polymerized alone, or the monomer and one or more vinyl monomers Polymer powder obtained from a polymer obtained by copolymerizing the polymer is preferably used, acrylic polymer powder or vinyl polymer powder is more preferable, and acrylic polymer powder is more preferable. preferable.

  When a filler other than the component (C) is used, it is preferable to mix 0.1 to 500 parts by weight, preferably 2 to 250 parts by weight, based on 100 parts by weight of the organic polymer of the component (A). And more preferably 5 to 125 parts by mass. The polymer powder may be used alone or in combination of two or more.

  The plasticizer is added for the purpose of enhancing elongation properties after curing and enabling reduction in modulus. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate and diisoundecyl phthalate; dioctyl adipate, isodecyl succinate, dioctyl sebacate, dibutyl adipate and the like. Aliphatic dibasic acid esters; glycol esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetyl ricinoleate; tricresyl phosphate and phosphoric acid Phosphates such as trioctyl, octyl diphenyl phosphate, tributyl phosphate, tricresyl phosphate; epoxidized soybean oil, epoxidized linseed oil, epoxy Epoxy plasticizers such as benzyl stearate; polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; polyethers such as polypropylene glycol and polyethylene glycol derivatives; diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether; Those having a repeat of 2, such as diethylene glycol diethyl ether, those having a repeat of 3, such as triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, and triethylene glycol diethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol ethyl methyl ether, Polyoxyethylene having a repetition of 4, such as tetraethylene glycol diethyl ether, and a repetition of 4 or more Polyoxyethylene alkyl ethers such as dimethyl ether; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutadiene, hydrogenated polyisoprene, Hydrocarbon oligomers such as process oils; chlorinated paraffins; acrylic plasticizers such as UP-1080 (manufactured by Toagosei Co., Ltd.) and UP-1061 (manufactured by Toagosei Co., Ltd.); UP-2000 Hydroxyl-containing acrylic plasticizers such as (Toagosei Co., Ltd.) and UHE-2012 (Toagosei Co., Ltd.); and carboxyl group-containing acrylic polymers such as UC-3510 (Toagosei Co., Ltd.) Such as UG-4000 (manufactured by Toagosei Co., Ltd.) Xyl group-containing acrylic polymers such as US-6110 (Toagosei Co., Ltd.) and US-6120 (Toagosei Co., Ltd.) containing less than 0.8, preferably less than 0.4 silyl groups Acrylic polymers are exemplified.

  Examples of the adhesion-imparting agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- Amino group-containing silanes such as (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 1,3-diaminoisopropyltrimethoxysilane; γ Epoxy-containing silanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane; Mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; vinyl-type unsaturated groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-acryloyloxypropylmethyldimethoxysilane Silanes; chlorine atom-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanate-containing silanes such as γ-isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; methyldimethoxysilane, trimethoxysilane, methyldisilane Specific examples include hydrosilanes such as ethoxysilane, but are not limited thereto.

  In the case of using an adhesion-imparting agent, if too much is added, the modulus of the cured product increases, and if it is too small, the adhesiveness decreases, so that 0.1 to 0.1 part by mass of the organic polymer (A) is used. Preferably, it is added in an amount of from 15 to 15 parts by mass, more preferably from 0.5 to 10 parts by mass.

  The curable composition of the present invention may further use a thixotropic agent other than the component (C) as long as the object of the present invention is achieved. Examples of the thixotropic agent other than the component (C) include inorganic thixotropic agents such as asbestos powder, organic bentonites, modified polyester polyols, organic thixotropic agents such as fatty acid amides, hydrogenated castor oil derivatives, fatty acid amide waxes, Examples include aluminum stearylate and barium stearylate.

  The dehydrating agent is added for the purpose of removing water during storage. Examples of dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethydimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane, zeolites, calcium oxide, and oxidants. Examples include magnesium and zinc oxide. When a dehydrating agent is used, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A).

  Examples of the antioxidant include hindered phenols, monophenols, bisphenols, polyphenols, and hindered amines. Hindered phenols and hindered amines are particularly preferred. When an antioxidant is used, it is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A).

  An ultraviolet absorber can be added to the curable composition of the present invention. When an ultraviolet absorber is used, the surface weather resistance of the cured product can be increased. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferred. When an ultraviolet absorber is used, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the component (A).

  A diluent can be added to the curable composition of the present invention. By adding a diluent, physical properties such as viscosity can be adjusted. As the diluent, known diluents can be widely used and are not particularly limited. Examples thereof include saturated hydrocarbon solvents such as normal paraffin and isoparaffin, and α such as linearene dimer (trade name of Idemitsu Kosan Co., Ltd.). -Olefin derivatives, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, and diacetone alcohol; ethyl acetate, butyl acetate, amyl acetate, and acetic acid. Various solvents such as ester solvents such as cellosolve, citrate esters such as acetyltriethyl citrate, acetyltributyl citrate, and triethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

  The flash point of the diluent is not particularly limited, but considering the safety of the obtained curable composition, it is desirable that the flash point of the curable composition be high, and that the volatile matter from the curable composition be small. preferable. Therefore, the flash point of the diluent is preferably at least 60 ° C, more preferably at least 70 ° C. When two or more diluents are used in combination, the flash point of the mixed diluent is preferably 70 ° C. or higher. However, in general, a diluent having a high flash point tends to have a low diluting effect on the curable composition. Therefore, the flash point is preferably 250 ° C. or lower.

  In consideration of both the safety and the diluting effect of the curable composition of the present invention, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. Normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Co., Ltd., carbon number 11, flash point 68 ° C.), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Co., Ltd., carbon number 12, flash point 85 ° C.) and IP Solvent 2028 (isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., having 10 to 16 carbon atoms, flash point 86 ° C.).

  The mixing ratio of the diluent is not particularly limited, but is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the organic polymer having a crosslinkable silicon group as the component (A). 0.1 to 30 parts by mass, more preferably 0.1 to 15 parts by mass. The diluent may be used alone or in combination of two or more.

  The curable composition of the present invention can be of a one-pack type or a two-pack type, if necessary, but can be suitably used particularly as a one-pack type. The curable composition of the present invention can be cured at room temperature by moisture in the air, and is suitably used as a room temperature moisture-curable curable composition. May be.

  The method for producing the curable composition of the present invention is not particularly limited. For example, the components (A), (B), (C) and (D) are mixed in a predetermined amount, and if necessary, other components may be mixed. It can be produced by blending substances and stirring with degassing. The order of blending the components (A) to (D) and other blending substances is not particularly limited, and may be determined as appropriate.

  The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive, a coating material, a potting material, a paint, a putty material, a primer, and the like. In particular, it can be suitably used for an adhesive or a sealing material. The curable composition of the present invention is excellent in thixotropy, adhesiveness, storage stability, and curability, and is particularly preferably used for an adhesive, for various types of buildings, automobiles, civil engineering, electricity, It can be used for electronic fields.

  The product of the present invention is a product produced using the curable composition of the present invention, and can be suitably used for various products such as electronic circuits, electronic components, building materials, civil engineering products, and automobiles.

The analysis and measurement in Synthesis Examples, Examples and Comparative Examples were performed according to the following methods.
1) Measurement of number average molecular weight It was measured by gel permeation chromatography (GPC) under the following conditions. In the present invention, the molecular weight of the highest frequency measured by GPC under the above measurement conditions and converted with standard polyethylene glycol is referred to as a number average molecular weight.
-Analyzer: Alliance (manufactured by Waters), 2410 type differential refraction detector (manufactured by Waters), 996 type multi-wavelength detector (manufactured by Waters), Millennium data processor (manufactured by Waters)
・ Column: Plgel GUARD + 5 μm Mixed-C × 3 (50 × 7.5 mm, 300 × 7.5 mm: manufactured by PolymerLab)
-Solvent: THF
-Flow rate: 1 mL / min-Converted polymer: polyethylene glycol-Measurement temperature: 40 ° C

2) Measurement of the number of crosslinkable silicon groups per polymer molecule It was measured using an FT-NMR measurement device (JNM-ECA500 (500 MHz) manufactured by JEOL Ltd.).

3) Viscosity When the viscosity of the curable composition is less than 200 Pa · s, it is measured with a BH-type rotational viscometer (rotor No. 7-20 rpm). When the viscosity of the curable composition is 200 Pa · s or more, it is BS type. It was measured with a rotational viscometer (rotor No. 7-10 rpm) (measuring temperature 23 ° C.).

4) Thixotropic property The thixotropy was evaluated by measuring the SVI value. That is, when the viscosity of the curable composition is less than 200 Pa · s, the viscosity of the curable composition is calculated by dividing the viscosity at 2 rpm by the viscosity at 20 rpm using a BH-type rotational viscometer (Rotor No. 7). When the viscosity was 200 Pa · s or more, the viscosity was calculated by dividing the viscosity at 1 rpm by the viscosity at 10 rpm using a BS-type rotational viscometer (Rotor No. 7) (measuring temperature 23 ° C.). The SVI value obtained above was used as an index indicating thixotropy.

5) Curing time In accordance with JIS A14395.19 tack-free test, the dry time to touch (TFT) was measured in an environment of 23 ° C. and 50% RH.

6) Viscosity and thixotropy after storing the composition The curable composition was left in a sealed glass container under an atmosphere of 50 ° C for 4 weeks, and the viscosity, curing time and SVI value were measured. The measured viscosity, curing time, and SVI value were defined as the viscosity after storage, the TFT after storage, and the SVI value after storage, respectively. The thickening rate was calculated by dividing the viscosity after storage by the initial viscosity.

(Synthesis example 1)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, a hydroxyl value obtained by reacting propylene oxide with ethylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. A polyoxypropylene diol having a reduced molecular weight of 24,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene diol to sodium alkoxide, thereby obtaining a polyoxyalkylene polymer. .

Next, 100 parts by mass of the polyoxyalkylene polymer was reacted with 0.74 parts by mass of allyl chloride to remove unreacted allyl chloride, purified, and purified with a polyoxyalkylene having a terminal allyl group. A polymer was obtained. To the polyoxyalkylene polymer having an allyl group at the terminal, 150 ppm of a platinum vinyl siloxane complex isopropanol solution containing 3% by weight of platinum was added using 1.17 parts by mass of trimethoxysilane as a catalyst, and reacted. A polyoxyalkylene polymer A1 having a silyl group was obtained. As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 25,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis example 2)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, a hydroxyl value obtained by reacting propylene oxide with ethylene glycol as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Polyoxypropylene diol having a reduced molecular weight of 11,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene diol to sodium alkoxide, thereby obtaining a polyoxyalkylene polymer. .

Next, 0.53 parts by mass of allyl chloride is reacted with 100 parts by mass of this polyoxyalkylene-based polymer to remove unreacted allyl chloride, and purified to obtain a polyoxyalkylene-based terminal having an allyl group at the terminal. A polymer was obtained. To the polyoxyalkylene polymer having an allyl group at the terminal, 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% was added using 2.44 parts by mass of trimethoxysilane as a catalyst and reacted. A polyoxyalkylene polymer A2 having a silyl group was obtained. The molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal was measured by GPC. As a result, the peak top molecular weight was 12,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal trimethoxysilyl groups was 1.7 per molecule.

(Synthesis example 3)
In a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, polyoxypropylene diol having a molecular weight of about 2,000 was used as an initiator, and propylene oxide was added in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. A polyoxypropylene diol having a hydroxyl value-converted molecular weight of 14,500 and a molecular weight distribution of 1.3 obtained by the reaction was obtained. A methanol solution of sodium methoxide was added to the obtained polyoxypropylene diol, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene diol to sodium alkoxide, thereby obtaining a polyoxyalkylene polymer. .

Next, 1.6 parts by mass of allyl chloride is reacted with 100 parts by mass of this polyoxyalkylene-based polymer to remove unreacted allyl chloride, purified, and purified with a polyoxyalkylene-based polymer having an allyl group at the terminal. A coalescence was obtained. The polyoxyalkylene polymer having an allyl group at its terminal was reacted by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% with 1.8 mass parts of methyldimethoxysilane as a silicon hydride compound as a catalyst. As a result, a polyoxyalkylene polymer A3 having a methyldimethoxysilyl group at a terminal was obtained. As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A3 having a methyldimethoxysilyl group at the terminal by GPC, the peak top molecular weight was 15,000 and the molecular weight distribution was 1.3. According to H ¹ -NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

(Synthesis example 4)
400 g of the polyoxyalkylene polymer A1 having a trimethoxysilyl group at the terminal obtained in Synthesis Example 1 was placed in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, and Synthesis Example 2 200 g of the polyoxyalkylene polymer A2 having a trimethoxysilyl group at the terminal obtained in the above was added, and the mixture was heated to 80 ° C. In another container, 247 g of methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Co., Ltd.), 23 g of n-butyl acrylate, 49 g of stearyl methacrylate (trade name: Light Ester S, manufactured by Kyoeisha Co., Ltd.), 3-methacryloxy 45 g of propyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 23.77 g of 3-mercaptopropyltrimethoxysilane, and 10.56 g of AIBN were mixed, stirred, filled in a dropping device, and taken for 3 hours. It was dropped. After the completion of the dropwise addition, the mixture was further reacted for 3 hours, and an organic polymer A4 having a trimethoxysilyl group, which was a mixture of a polyoxyalkylene polymer and a vinyl polymer (molecular weight measured by GPC, about 5000, molecular weight distribution 1.6). I got The mixing weight ratio between the polyoxyalkylene polymer and the vinyl polymer is 61:39.

(Synthesis example 5)
600 g of the polyoxyalkylene polymer A3 having a methyldimethoxysilyl group at the end obtained in Synthesis Example 3 was added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser. Was heated. In another container, 247 g of methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Co., Ltd.), 23 g of n-butyl acrylate, 49 g of stearyl methacrylate (trade name: Light Ester S, manufactured by Kyoeisha Co., Ltd.), 3-methacryloxy 45 g of propyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 23.77 g of 3-mercaptopropyltrimethoxysilane, and 10.56 g of AIBN were mixed, stirred, filled in a dropping device, and taken for 3 hours. It was dropped. After the completion of the dropwise addition, the mixture was further reacted for 3 hours to obtain an organic polymer A5 which was a mixture of a polyoxyalkylene polymer and a vinyl polymer (molecular weight measured by GPC: about 5000, molecular weight distribution 1.6). The mixing weight ratio between the polyoxyalkylene polymer and the vinyl polymer is 61:39.

(Synthesis example 6)
A flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was degassed under reduced pressure, replaced with nitrogen gas, and 2.4 g of a BF ₃ diethyl ether complex was added under a nitrogen gas stream, and heated to 50 ° C. Warmed. Subsequently, a mixture of 1.6 g of dehydrated methanol was slowly dropped and mixed. In a new flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 100 g of the polymer A3 obtained in Synthesis Example 3 and 5 g of toluene were placed. After stirring at 23 ° C for 30 minutes, the mixture was heated to 110 ° C and stirred under reduced pressure for 2 hours to remove toluene. 4.0 g of the mixture obtained above was slowly added dropwise to the container under a nitrogen stream, and after the completion of the addition, the reaction temperature was raised to 120 ° C., and the mixture was reacted for 30 minutes. After completion of the reaction, degassing was performed under reduced pressure to remove unreacted substances. A polyoxyalkylene polymer B1 having a difluoromethylsilyl group at a terminal was obtained. When the 1H-NMR spectrum of the obtained polymer B1 (measured in a CDCl ₃ solvent using NMR400 manufactured by Shimazu) was measured, it was found that the silylmethylene (—CH ₂ —Si) of the polymer A3 as a raw material was obtained. The corresponding peak (m, 0.63 ppm) disappeared, and a broad peak appeared on the low magnetic field side (from 0.7 ppm).

(Synthesis example 7)
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM603, Shin-Etsu Chemical Co., Ltd.) is added to 1 mol of 3-methacryloxypropyltrimethoxysilane (KBM503, Shin-Etsu Chemical Co., Ltd.) per mole. The compound D1 was obtained by Michael addition reaction by adding a mol and heating at 80 degreeC for 3 days.

(Examples 1 and 2)
To a 300 mL flask equipped with a stirrer, thermometer, nitrogen inlet, monomer charging tube and water-cooled condenser, add each component shown in Table 1 in an amount shown in Table 1 (unit: g), and degas at 25 ° C. The mixture was stirred to obtain a curable composition. The viscosity, thixotropy (SVI value), and curability (tack free time, TFT) of the curable composition were measured at the initial stage and after storage. The results are shown in Table 2.

(Comparative Examples 1 and 2)
Curable compositions were prepared in the same manner as in Examples 1 and 2, except that the compound D1 of Synthesis Example 7 was not used, using the components and amounts shown in Table 1, and the properties were evaluated. The results are shown in Table 2.

(Comparative Example 3)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that acryloylsilane and aminosilane were used without previously reacting using the components and amounts shown in Table 1. The results are shown in Table 2.

* 1 Aerosil R972: manufactured by Nippon Aerosil Co., Ltd. * 2 KBM503: manufactured by Shin-Etsu Chemical Co., Ltd. * 3 Reaction of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) with octylic acid Product, U-CAT SA102: manufactured by San Apro Co., Ltd. * 4 EC600JD: manufactured by Lion Co., Ltd. * 5 Zefiac F320: manufactured by Zeon Kasei Co., Ltd. * 6 ARUFON UP-1110: manufactured by Toagosei Co., Ltd. * 7 KBM603: Shin-Etsu * 8 KBM1003 manufactured by Chemical Industry Co., Ltd. * 9 N-11 manufactured by Shin-Etsu Chemical Co., Ltd. manufactured by JX Nippon Oil & Energy Corporation

  As is clear from Table 2, the comparative examples 1 and 2 did not use the acryloylsilane and aminosilane reactants, and the comparative example 3 used the acryloylsilane and aminosilane without prior reaction. When the reactants 1 and 2 of acryloylsilane and aminosilane were used, the thickening was suppressed even after the storage stability test.

Claims (4)

(A) 100 parts by mass of an organic polymer having a silicon group which has a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond (however, excluding those having a Si-F bond);
(B) 0.1 to 20 parts by mass of a compound having a silicon group having a Si-F bond,
(C) 0.1 to 30 parts by mass of fumed silica, and (D) a compound obtained by Michael addition of a compound having a (meth) acryloyl group and a compound having an amino group, the hydrolysis being bonded to a silicon atom Containing 0.5 to 20 parts by mass of a compound having a silicon group having a functional group ,
A curable composition, wherein the main chain skeleton of the polymer (A) is at least one compound selected from the group consisting of a polyoxyalkylene polymer and a (meth) acrylic polymer .   An adhesive comprising the curable composition according to claim 1.   A sealing material comprising the curable composition according to claim 1.   A product manufactured using the curable composition according to claim 1.