JP6425187B2 - Moisture curable type curable composition - Google Patents

Description

  The present invention relates to a moisture curable curable composition, and more particularly to a moisture curable curable composition which does not require a metal compound as a curing catalyst.

  An organic polymer having a silicon-containing group (hereinafter, also referred to as “crosslinkable silicon group”) which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and which can be crosslinked by forming a siloxane bond is It is also known to have the property of being crosslinked by the formation of a siloxane bond accompanied by the hydrolysis reaction of the crosslinkable silicon group with moisture or the like to obtain a rubber-like cured product. Among these polymers having a crosslinkable silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a (meth) acrylate polymer are applications such as sealing materials, adhesives and paints. Widely used.

  The curable composition used for sealing materials, adhesives, paints and the like and rubber-like cured products obtained by curing have various properties such as curability, adhesion, storage stability, and mechanical properties such as modulus, strength and elongation. Many studies have been made so far on properties required and organic polymers containing a crosslinkable silicon group.

  Curable compositions containing these crosslinkable silicon group-containing organic polymers are cured using a silanol condensation catalyst, and generally, organic tin-based catalysts such as dibutyltin bis (acetylacetonate) are widely used. It is used. However, in recent years, the toxicity of organotin-based compounds is pointed out, and development of non-organotin-based catalysts is required.

  For example, Patent Documents 1 and 2 are curable compositions containing an organic polymer having a silicon group having a Si-F bond, a filler, and a polymer having one or more crosslinkable silicon groups, It is described that amine compounds such as DBU are contained as a curing catalyst. However, although the curable composition described in Patent Document 1 has quick curing, storage stability is poor, residual tack is generated, surface contamination may occur, and there is a problem in surface curability. In addition, a strong base was required to express fast curing.

  Further, Patent Document 3 is a curable composition containing a polymer obtained by subjecting a hydrogen group-containing organic polymer having a polyoxyalkylene chain and a hydroxyl group to a urethanization reaction with a compound having a reactive silicon group and an isocyanate group. The composition is further described to contain one or more selected from the group consisting of quaternary ammonium salts, amino group-containing compounds and amidine derivative salts. However, the curable composition described in Patent Document 3 has poor storage stability, and it is difficult to simultaneously achieve both adhesiveness and rapid curing, and the curing rate and adhesive strength rise slowly, and it takes time for curing, work period and so on. There was a problem that line speed became slow. In addition, residual tack may occur, surface contamination may occur, and there is a problem in surface curability.

JP, 2008-156482, A JP, 2009-215331, A JP, 2009-173856, A

  The present invention provides a moisture-curable curable composition which does not require a metal compound such as an organotin compound as a curing catalyst, and has good rapid curing, storage stability, surface curing, adhesiveness, and rise in adhesion strength. The purpose is

  MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of repeating the present inventors's earnest studies, (A) hardening | curing which contains the organic polymer containing an average 0.8 or more crosslinkable silicon group in 1 molecule In the organic composition, the metal compound is not used by using in combination a silicon compound having a Si-F bond and a compound obtained by reacting an (A) amidine with an acid as a curing catalyst. It has been found that a moisture-curable curable composition can be obtained which is compatible in adhesion and rapid curing, and excellent in storage stability, surface curability and rise of adhesive strength.

  That is, the moisture-curable curable composition of the present invention is an organic polymer containing an average of 0.8 or more crosslinkable silicon groups in one molecule (excluding those having a Si-F bond). And (B) a silicon compound having a Si-F bond, and (C) a reaction product obtained by reacting an amidine with an acid.

  The above-mentioned amidine used for the above-mentioned (C) reaction product is 1,8-diazabicyclo (5.4.0) undecen-7 and / or 5-diazabicyclo (4.3.0) nonene-5 Is preferred.

  The reaction product (C) is reacted with 0.1 to 3 moles, preferably 0.5 to 2.25 moles, more preferably 0.75 to 2.0 moles of acid per mole of amidine. Is preferably obtained.

  It is preferable that the said acid used for the said (C) reaction product is a carboxylic acid.

  The compound (B) having a Si—F bond has a number average molecular weight of 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 30,000, particularly preferably It is preferred that it is a fluorinated polymer which is 2,000 to 25,000.

  The product of the present invention is a product comprising the moisture-curable composition of the present invention as an adhesive. The building component of the present invention is a building component using the moisture-curable composition of the present invention. The automobile part of the present invention is an automobile part using the moisture-curable composition of the present invention. The electric / electronic component of the present invention is an electric / electronic component using the moisture-curable composition of the present invention.

  According to the present invention, metal compounds such as organotin compounds are not required as a curing catalyst, which is excellent in safety, and quick curing, storage stability, surface curability, adhesiveness and adhesion without using a strong base. It is possible to provide a moisture-curable curable composition having a good rise in strength. Furthermore, according to the present invention, a moisture-curable curable composition having excellent appearance and transparency can also be obtained.

  Although the embodiments of the present invention will be described below, it is needless to say that these are exemplarily shown and various modifications can be made without departing from the technical concept of the present invention.

  The moisture-curable curable composition of the present invention is an organic polymer containing an average of 0.8 or more crosslinkable silicon groups per molecule (A) (excluding those having a Si-F bond). And (B) a silicon compound having a Si-F bond, and (C) a reaction product obtained by reacting an amidine with an acid.

  The organic polymer (A) is not particularly limited as long as it has an average of 0.8 or more crosslinkable silicon groups per molecule and no Si-F bond in one molecule. However, organic polymers whose main chain is not polysiloxane and having various main chain skeletons except for polysiloxane are preferable in that they do not contain or generate low molecular weight cyclic siloxane which causes contact failure.

  Specifically, polyoxyalkylene-based weights such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Combined: ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, copolymer of isoprene or butadiene with acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene And copolymers of acrylonitrile, styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and glycols Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylate polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile and styrene; graft polymers obtained by polymerizing vinyl monomers in the above organic polymers; polysulfide systems Polymers: nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-amino laurolacta by condensation polymerization 12, a polyamide-based polymer such as copolymerized nylon having two or more components of the above nylons by ring-opening polymerization of the above-mentioned nylon; for example, a polycarbonate-based polymer produced by condensation polymerization from bisphenol A and carbonyl chloride, diallyl Examples are phthalate polymers.

  Furthermore, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylate polymers can be obtained with a relatively low glass transition temperature. The cured product is preferable because it is excellent in cold resistance. In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferable because they have high moisture permeability and are excellent in deep-part curability when made into a one-pack composition.

  The crosslinkable silicon group of the organic polymer (A) used in the present invention is a group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and which 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 above 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 SiO-(R ¹ is the same as the above) is a triorganosiloxy group, and when two or more R ¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they may be the same or different. a represents 0, 1, 2 or 3 and b represents 0, 1 or 2, respectively. Moreover, b in p following general formula (2) does not need to 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 or hydroxyl group can be bonded to one silicon atom in a range of 1 to 3 and a + (sum of b) is preferably in a range of 1 to 5. When two or more hydrolyzable groups or hydroxyl 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, but in the case of silicon atoms linked by a siloxane bond or the like, about 20 may be present.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (3) is preferable from the viewpoint of easy availability.

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

  As a hydrolysable group shown by said X, if it is except F atom, it will not be specifically limited, What is necessary is just a conventionally well-known hydrolysable group. Specific examples thereof include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoxime 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 amido group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxyl group, an amido group and an aminooxy group are more preferable. An alkoxyl group is particularly preferred from the viewpoint of mild hydrolyzability and easy handling. Among the alkoxyl groups, those having a smaller number of carbon atoms are higher in reactivity, and the reactivity becomes lower as the number of carbon atoms increases, as in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose or application, usually a methoxy group or an ethoxy group is used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups such as trimethoxysilyl group and triethoxysilyl group [-Si (OR) ₃ ], and dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. A silyl group [-SiR < ₁ > (OR) ₂ ] is mentioned and a trialkoxy silyl group [-Si (OR) ₃ ] is suitable by the thing with high reactivity, and a trimethoxy silyl group is more preferable. Here, R is an alkyl group such as a methyl group or an ethyl group.

  The crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group may be present in the main chain or side chain or in any one of them.

  The number of silicon atoms forming the crosslinkable silicon group is one or more, and in the case of silicon atoms linked by a siloxane bond or the like, it is preferably 20 or less.

  The organic polymer having a crosslinkable silicon group may be linear or branched, and the number average molecular weight thereof is about 500 to 100,000, more preferably 1,000 to 50,000 in terms of polystyrene in GPC. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the elongation characteristic of the cured product tends to be inconvenient, and if it exceeds 100,000, the viscosity tends to be inconvenient in terms of workability because of high viscosity.

  In order to obtain a rubbery cured product exhibiting high strength, high elongation and low elastic modulus, the number of crosslinkable silicon groups contained in the organic polymer is preferably 0.8 or more in average per polymer molecule. 1.0 or more, more preferably 1.1 to 5 should be present. When the number of crosslinkable silicon groups contained in the molecule is less than 0.8 on average, the curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The crosslinkable silicon group may be present at the end of the main chain or at the end of the side chain of the organic polymer molecular chain, or at both of them. In particular, when the crosslinkable silicon group is only at the end 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 long, so high strength and high elongation can be obtained. And a rubber-like cured product having a low elastic modulus can be easily obtained.

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

Specific examples of the repeating unit represented by the general formula (4) are
_{-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-
Etc. The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units.

  As a synthesis method of the polyoxyalkylene polymer, for example, an alkali catalyst polymerization method such as KOH, for example, JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-215623 A polymerization method using an organoaluminum-porphyrin complex catalyst, obtained by reacting an organoaluminum compound as shown with a porphyrin, for example, a double metal cyanide complex shown in JP-B-46-27250 and JP-B-59-15336. A polymerization method using a catalyst may, for example, be mentioned, but it is not particularly limited. According to the polymerization method by organic aluminum-porphyrin complex catalyst and the polymerization method by double metal cyanide complex catalyst, a polyoxyalkylene type having a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Polymers can be obtained.

  The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component. Examples of urethane bond components include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate, and polyoxyalkylene heavy chain having hydroxyl group It can be mentioned what is obtained from the reaction with coalescence.

  The introduction of the crosslinkable silicon group into the polyoxyalkylene polymer is carried out in the 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 functional group having reactivity and a crosslinkable silicon group (hereinafter referred to as a polymer reaction method).

  As a specific example of the polymer reaction method, the unsaturated group-containing polyoxyalkylene polymer is reacted with a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to hydrosilylate or mercapitize, and the crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has these can be mentioned. An unsaturated group-containing polyoxyalkylene polymer is prepared 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 that exhibit reactivity with the functional group, to obtain an unsaturated group. A polyoxyalkylene polymer containing can be obtained.

  Further, as another specific example of the polymer reaction method, a method of reacting a polyoxyalkylene polymer having a hydroxyl group at the end with a compound having an isocyanate group and a crosslinkable silicon group, or a polyoxyalkylene system having an isocyanate group at the end 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 can be mentioned. When an isocyanate compound is used, a polyoxyalkylene polymer having a crosslinkable silicon group can be easily obtained.

  As specific examples of polyoxyalkylene polymers having a crosslinkable silicon group, JP-B Nos. 45-36319 and 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767 can be mentioned. No. 57-164123, Japanese Examined Patent Application No. 3-2450, Japanese Patent Application Laid-Open Nos. 2005-213446, 2005-306891, International Publication Patent No. WO2007-040143, US Patents 3,632,557, 4,345,053, What is proposed by each gazette of the said 4,960,844 grade can be mentioned.

  The polyoxyalkylene polymer having the crosslinkable silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer substantially free of carbon-carbon unsaturated bonds other than aromatic rings, and the polymer forming the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, etc. Or an olefin-based compound having 2 to 6 carbon atoms as the main monomer, (2) homopolymerization of a diene-based compound such as butadiene, isoprene or the like, or copolymerization with the above-mentioned olefin-based compound After that, it can be obtained by a method such as hydrogenation, but the isobutylene polymer and the hydrogenated polybutadiene polymer are easy to introduce a functional group at the terminal, easy to control the molecular weight, and the number of terminal functional groups. Is preferred, and isobutylene polymers are particularly preferred.

  Those having a main chain skeleton of a saturated hydrocarbon-based polymer have excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene polymer, all of the monomer units may be formed of isobutylene units, or may be copolymers with other monomers, but from the viewpoint of rubber properties, 50 repeat units derived from isobutylene are used. Those containing at least mass% are preferable, those containing at least 80 mass% are more preferable, and those containing at from 90 to 99 mass% are particularly preferable.

  Conventionally, various polymerization methods have been reported as methods for synthesizing saturated hydrocarbon polymers, and in particular, a large number of so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, Vol. 15, p. 2843) found by Kennedy et al. It is known that it can be easily manufactured by using it, can polymerize the molecular weight distribution of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and can introduce various functional groups at the molecular terminal.

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, and the like. Although it describes in each specification etc. of the Hei 1-197509, patent gazette 2539445, patent gazette 2873395, Unexamined-Japanese-Patent No. 7-53882, etc., it is not limited in particular in these.

  The above-mentioned saturated hydrocarbon polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing 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) acrylic acid alkyl ester monomers such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; (meth) Cyclohexyl acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl ) Acrylate, dicyclopentanyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetramethyl piperidinyl (meth) acrylate, pentamethyl piperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, paraquat Mil phenoxy ethylene glycol (meth) acrylate, hydroxyethylated o-phenyl phenol (meth) acrylate, 2-hydroxy 3- phenoxy propyl (meth) acrylate, phenoxy dye Aromatic (meth) acrylic acid ester monomers such as glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate and phenylthioethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, (meth) acrylate (Meth) acrylic acid esters such as 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate Monomer; γ- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxy Silyl group-containing (meth) acrylic acid ester type monomers such as ethyl dimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adduct of (meth) acrylic acid; (meth) acrylic acid Acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2-perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl 2-perfluorobutyl ethyl, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) Acrylic acid 2-perfluorohexylethyl And fluorine-containing (meth) acrylic acid ester-based monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylic acid ester-based polymer, the following vinyl-based monomers can be copolymerized together with the (meth) acrylic acid ester-based monomer. Examples of the vinyl-based monomer include styrene-based monomers such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid and salts thereof; 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 esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohexene Maleimide-based monomers such as maleimide; nitrile-containing vinyl-based monomers such as acrylonitrile and methacrylonitrile; amide-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; and vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like.

  These may be used alone or in combination of two or more. Among them, a polymer composed of a (meth) acrylic acid-based monomer is preferable from the physical properties of the product and the like. More preferably, it is a (meth) acrylic acid ester-based polymer in which one or two or more kinds of (meth) acrylic acid alkyl ester monomers are used together with other (meth) acrylic acid monomers as needed. By using a group-containing (meth) acrylic acid ester-based monomer in combination, the number of silicon groups in the (meth) acrylic acid ester-based polymer (A) can be controlled. Particularly preferred is a methacrylic acid ester-based polymer comprising a methacrylic acid ester monomer because of good adhesion. In addition, in the case of lowering the viscosity, imparting flexibility, and imparting tackiness, it is preferable to appropriately use an acrylic acid ester monomer. In the present specification, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  In the present invention, the method for obtaining the (meth) acrylic acid ester-based polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). No., JP-A No. 2003-313397, etc. can be used, and a radical polymerization method using a radical polymerization reaction is preferred. As the radical polymerization method, radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator, or introducing a reactive silyl group at a controlled position such as an end Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a conventional free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator has a problem that the value of molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. There is. Therefore, in order to obtain a (meth) acrylic ester polymer having a narrow molecular weight distribution and a low viscosity (meth) acrylic ester polymer and having a crosslinkable functional group at the molecular chain end at a high rate, It is preferred to use a controlled radical polymerization method.

  The controlled radical polymerization includes free radical polymerization using a chain transfer agent having a specific functional group and living radical polymerization, and addition-fragmentation transfer (RAFT) polymerization, More preferred is a living radical polymerization method such as transition-metal-mediated living radical polymerization using a transition metal complex. Further, a reaction using a thiol compound having a reactive silyl group, and a reaction using a thiol compound having a reactive silyl group and a metallocene compound (JP-A-2001-40037) are also suitable.

  The (meth) acrylic acid ester-based polymer having the 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 formed by blending two or more selected from the group can also be used.

JP-A-59-122541 discloses a method of producing an organic polymer formed by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group. Japanese Patent Application Laid-Open No. 63-112642, Japanese Patent Application Laid-Open No. 6-172631, Japanese Patent Application Laid-Open No. 11-116763 and the like, but the present invention is not particularly limited thereto. A preferred embodiment has 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 is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 5 carbon atoms. A (meth) acrylic acid ester monomer unit and a compound represented by the following general formula (6):
_{^{-CH 2 -C (R 3) (}} COOR 5) - ··· (6)
(In the formula, R ³ is the same as above, R ⁵ is an alkyl group having 6 or more carbon atoms), and a crosslinkable silicon group is formed of a copolymer composed of (meth) acrylic acid ester monomer units It is the method of blending and manufacturing the polyoxyalkylene type polymer which it has.

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

The R ^{5 in the} general formula (6) has, for example, 6 or more carbon atoms such as 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group and behenyl group, usually 7 to 30, preferably 8 to 20 And long-chain alkyl groups of In addition, the alkyl group of R ⁵ may be independent or may be a mixture of two or more, as in the case of R ⁴ .

  The molecular chain of the (meth) acrylic acid ester copolymer substantially consists of monomer units of the formulas (5) and (6), and "substantially" as used herein means the copolymer It means that the sum total of the monomer unit of Formula (5) and Formula (6) which exists in more than 50 mass%. The total of the monomer units of the formulas (5) and (6) is preferably 70% by mass or more. The mass ratio of the monomer unit of the formula (5) to the monomer unit of the formula (6) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  Examples of monomer units other than the formula (5) and the formula (6) which may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. Amides such as acrylamide, methacrylamide, N-methylol acrylamide and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether and the like Monomers containing an amino group of the following; and other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

  A crosslinkable silicon group used in a method of producing an organic polymer formed by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylate polymer having a crosslinkable silicon group (meth ) As the acrylic ester polymer, for example, having a crosslinkable silicon group described in JP-A-63-112642, and having a molecular chain substantially having (1) an alkyl group having 1 to 8 carbon atoms (Meta) ) A known (meth) acrylic acid ester copolymer containing an acrylic acid alkyl ester monomer unit and a (meth) acrylic acid alkyl ester monomer unit having (2) an alkyl group having 10 or more carbon atoms (Meth) acrylic acid ester type copolymers of the following can also be used.

  600-10,000 are preferable, as for the number average molecular weight of the said (meth) acrylic acid ester type polymer, 600-5,000 are more preferable, and 1,000-4,500 are more preferable. By setting the number average molecular weight to the above range, the compatibility with the polyoxyalkylene polymer having a crosslinkable silicon group can be improved. The (meth) acrylate polymers may be used alone or in combination of two or more. The compounding ratio of the crosslinkable silicon group-containing polyoxyalkylene polymer to the crosslinkable silicon group-containing (meth) acrylic acid ester polymer is not particularly limited, but the (meth) acrylic acid ester-based polymer It is preferable that the said (meth) acrylic-ester type polymer is in the range of 10-60 mass parts with respect to a total of 100 mass parts of a polymer and the said polyoxyalkylene type polymer, More preferably, it is 20- It is in the range of 50 parts by mass, more preferably in the range of 25 to 45 parts by mass. When the amount of the (meth) acrylic acid ester-based polymer is more than 60 parts by mass, the viscosity becomes high and the workability is deteriorated.

  Organic polymers formed by blending a crosslinkable silicon group-containing saturated hydrocarbon polymer and a crosslinkable silicon group-containing (meth) acrylic acid ester copolymer are disclosed in JP-A-1-168764 and JP-A-2000- Although it is proposed by the 186176 gazette etc., it is not limited in particular in these.

  Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester copolymer having a crosslinkable silicon group, another method may be used in the presence of an organic polymer having a crosslinkable silicon group ( A method of polymerizing the (meth) acrylic acid ester type monomer can be used. This manufacturing method is specifically disclosed in JP-A-59-78223, JP-A-59-168, 14, 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 crosslinker, with respect to 100 parts by mass of the 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 hydrophobic silicon group, and it is more preferable to use 20 to 80 parts by mass.

  In the present invention, the (B) Si-F bond-containing silicon compound acts as a curing catalyst for the (A) crosslinkable silicon group-containing organic polymer. As the silicon compound having the (B) Si-F bond, known compounds containing a silicon group having a Si-F bond (hereinafter, may be referred to as a fluorosilyl group) can be widely used, with particular limitations Although both low molecular weight compounds and high molecular weight compounds can be used, organic silicon compounds having a fluorosilyl group are preferable, and organic polymers having a fluorosilyl group are more preferable because of their high safety.

  Specific examples of the silicon compound (B) having a Si—F bond include fluorosilanes represented by the following formula (7), a compound having a fluorosilyl group represented by the following formula (8), and fluorosilyl The organic polymer etc. which have group are mentioned as a suitable example.

R ¹¹ _4-d SiF _d (7)
(In the formula (7), each R ¹¹ independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or R ¹² SiO— (R ¹² each independently has 1 to 20 carbon atoms Or a substituted or unsubstituted hydrocarbon group, or an organosiloxy group represented by fluorine atom, d is any one of 1 to 3 and d is preferably 3. R ¹¹ And when there are a plurality of R ^{12 's} , they may be the same or different.)

-SiF _d R ¹¹ _e Z _f (8)
(In the formula (8), R ¹¹ and d are respectively the same as the formula (7), Z is each independently a hydroxyl group or a hydrolyzable group other than fluorine, and e is any one of 0 to 2 And f is any of 0 to 2, and d + e + f is 3. When there are a plurality of R ¹¹ , R ¹² and Z, they may be the same or different.)

  Examples of the fluorosilanes represented by the formula (7) include known fluorosilanes represented by the formula (7), which are not particularly limited. For example, fluorotrimethylsilane, fluorotriethylsilane, fluorotripropylsilane Fluorotributylsilane, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, fluorodimethyl (3-methylphenyl) silane, fluorodimethyl (4-methylphenyl) silane, fluorodimethyl (4-chlorophenyl) silane, fluorotrimethylsilane Phenylsilane, difluorodimethylsilane, difluorodiethylsilane, difluorodibutylsilane, difluoromethylphenylsilane, difluorodiphenylsilane, trifluoroethylsilane, trifluoro Propylsilane, trifluorobutylsilane, trifluorophenylsilane, γ-methacryloxypropyl fluorodimethylsilane, γ-methacryloxypropyl difluoromethylsilane, γ-methacryloxypropyl trifluorosilane, 3-mercaptopropyl trifluorosilane, octadecyl fluorocarbon Dimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1,1,3,3-tetramethyldisiloxane, tetrafluorosilane, octafluorotrisilane, 1,3,5,7-tetra Fluoro-1,3,5,7-tetrasilatricyclo [3.3.1.1 (3,7)] decane, 1,1-difluoro-1-silacyclo-3-pentene, fluorotris (trimethylsiloxy) sila And the like.

  Among these, fluorodimethylvinylsilane, fluorodimethylphenylsilane, fluorodimethylbenzylsilane, γ-methacryloxypropylfluorodimethylsilane, and γ-methacryloxypropyl difluoro because of easy availability of raw materials and easy synthesis. Methylsilane, γ-methacryloxypropyltrifluorosilane, 3-mercaptopropyltrifluorosilane, octadecylfluorodimethylsilane, octadecyldifluoromethylsilane, octadecyltrifluorosilane, 1,3-difluoro-1,1,3,3-tetra Methyldisiloxane and the like are preferred.

  In the compound having a fluorosilyl group represented by the formula (8), as the hydrolyzable group represented by Z in the formula (8), for example, the same groups as the hydrolyzable groups represented by X in the formula (1) Specifically, hydrogen atoms, halogen atoms other than fluorine, alkoxy groups, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups Etc. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable, and an alkoxy group is preferable from the viewpoint of mild hydrolyzability. Particularly preferred.

Further, R ¹¹ in the above formula (8) is, for example, an alkyl group such as methyl group or ethyl group, a cycloalkyl group such as cyclohexyl group, an aryl group such as phenyl group, an aralkyl group such as benzyl group, R Triorganosiloxy group etc. which are shown by R < ¹² > SiO- in which ¹² is a methyl group, a phenyl group etc. are mentioned. Of these, methyl is particularly preferred.

Specific examples of the fluorosilyl group represented by the above formula (8) include a fluorodimethylsilyl group, a fluorodiethylsilyl group, a fluorodipropylsilyl group, and a fluorosilicon group as a silicon group having no hydrolyzable group other than fluorine. Silicon group in which one fluorine is substituted on silicon group such as diphenylsilyl group, fluorodibenzylsilyl group; on silicon group such as difluoromethylsilyl group, difluoroethylsilyl group, difluorophenylsilyl group, difluorobenzylsilyl group A silicon group substituted by two fluorines; a silicon group substituted by three fluorines on a silicon group which is a trifluorosilyl group; and a silicon group having both fluorine and another hydrolysable group, Methoxymethylsilyl, fluoroethoxymethylsilyl, fluoromethoxy , Fluoromethoxyphenylsilyl, fluorodimethoxysilyl, fluorodiethoxysilyl, fluorodipropoxysilyl, fluorodiphenoxysilyl, fluorobis (2-propenoxy) silyl, difluoromethoxysilyl, difluoroethoxysilyl Group, a difluorophenoxysilyl group, a fluorodichlorosilyl group, a difluorochlorosilyl group, etc., and a silicon group having no hydrolyzable group other than fluorine and a fluorosilyl group in which R ¹¹ is a methyl group are preferable, and a trifluorosilyl group is preferable. Groups are more preferred.
In addition, from the ease of synthesis, fluorodimethylsilyl group, difluoromethylsilyl group, trifluorosilyl group, fluoromethoxymethylsilyl group, fluoroethoxymethylsilyl group, fluoromethoxyethylsilyl group, fluorodimethoxysilyl group, fluorodiethoxysilyl group And difluoromethoxysilyl group and difluoroethoxysilyl group are more preferable, and from the viewpoint of stability, a silicon group having no hydrolyzable group other than fluorine such as fluorodimethylsilyl group, difluoromethylsilyl group and trifluorosilyl group is more preferable From the viewpoint of curability, preferred are silicon groups in which 2 to 3 fluorines are substituted on the silicon group, such as difluoromethylsilyl group, difluoromethoxysilyl group, difluoroethoxysilyl group, trifluorosilyl group, etc. Fluoro silyl group is most preferred.

  It does not specifically limit as a compound which has a fluoro silyl group shown by said Formula (8), Both a monomolecular compound and a high molecular compound can be used, For example, fluorosilanes shown by said Formula (7) , Fluorotrimethoxysilane, difluorodimethoxysilane, trifluoromethoxysilane, fluorotriethoxysilane, difluorodiethoxysilane, trifluoroethoxysilane, methylfluorodimethoxysilane, methyldifluoromethoxysilane, methyl trifluoromethoxysilane, methyl trifluorosilane, methyl fluorodiethoxysilane , Methyldifluoroethoxysilane, vinylfluorodimethoxysilane, vinyldifluoromethoxysilane, vinyltrifluorosilane, vinylfluorodiethoxysilane, vinyldifluoroethoxysilane, phenylfull Low molecular weight compounds such as lodimethoxysilane, phenyldifluoromethoxysilane, phenyltrifluorosilane, phenylfluorodiethoxysilane, phenyldifluoroethoxysilane, fluorotrimethylsilane, and fluorinated compounds having a fluorosilyl group represented by the formula (8) at the end Polymer compounds such as polysiloxane may be mentioned, and a polymer having a fluorosilyl group represented by the formula (8) at the end of the main chain or side chain is preferable.

The fluorosilanes represented by the formula (7) and the compound having a fluorosilyl group represented by the formula (8) may use commercially available reagents or may be synthesized from starting compounds. The synthesis method is not particularly limited, but a compound having a hydrolyzable silicon group represented by the following formula (9) and a fluorinating agent are known methods (for example, Organometallics 1996, 15, 2478 (Ishikawa et al. The compound obtained by making it react using () etc. is used suitably.
-SiR ¹¹ _3-p Z _p (9)
(In formula (9), R ¹¹ and Z are respectively the same as formula (8), and p is any of 1 to 3.)

  As a hydrolysable silicon group shown by said Formula (9), halo silyl groups, such as an alkoxy silyl group, a siloxane bond, a chloro silyl group, a hydrosilyl group, etc. are mentioned, for example.

Alkoxy Specific examples of fluorinating agents used for the fluorination of a silyl group is not particularly limited, for _{example, NH 4 F, Bu 4 NF} , HF, BF 3, Et 2 NSF 3, HSO 3 F, SbF 5 , VOF ₃ , CF ₃ CHFCF ₂ NEt _{2 and the} like.
Specific examples of fluorinating agents used for the fluorination of halosilyl group is 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, like _KF (HF) 1.5~5.
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 synthesis methods of fluorosilyl group using these fluorinating agents, the reaction is simple, the reaction efficiency is high, the safety is high, etc., and thus the fluorination method of alkoxysilane using BF ₃ Preferred is the fluorination method of chlorosilane using CuF ₂ or ZnF ₂ .

As BF ₃ , 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, BF ₃ piperidine A complex, BF ₃ phenol complex, etc. can be used, but BF ₃ ether complex, BF ₃ thioether complex, BF ₃ amine complex, BF ₃ alcohol complex, BF ₃ carboxylic acid complex, BF ₃ hydration because of easy handling etc. Are preferred. Among them, the BF ₃ ether complex, the BF ₃ alcohol complex, and the BF ₃ hydrate are preferably highly reactive, and the BF ₃ ether complex is particularly preferable.

The organic polymer having a fluorosilyl group (also referred to herein as a fluorinated polymer) is not particularly limited as long as it is an organic polymer having a Si-F bond, and known organics having a Si-F bond Polymers are widely available.
The position of the SiF bond in the organic polymer is also not particularly limited, and the effect is exhibited at any site in the polymer molecule, and the end of the main chain or side chain is -SiR ' ₂ F, the polymer If it is incorporated into the main chain of the formula, it is represented in the form of -SiR'F- or ≡SiF (R's are each independently an arbitrary group).
As the organic polymer having a Si-F bond at the end of the main chain or side chain, a polymer having a fluorosilyl group represented by the above-mentioned formula (8) is 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 in which the fluorosilyl group and the main chain skeleton are the same, that is, the number of fluorosilyl group per molecule, the bonding position thereof, and the number of F which the fluorosilyl group has, And a single polymer in which the main chain skeleton is the same, or a mixture of multiple 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 exhibiting fast curing, but it is expensive. In order to obtain a rubbery cured product exhibiting curability, high strength, high elongation and low elastic modulus, the fluorosilyl group contained in the fluorinated polymer is at least on average per molecule of polymer. One, preferably 1.1 to 5, and more preferably 1.2 to 3 may be present. When the number of fluorosilyl groups contained in one molecule is less than one on average, the curability may be insufficient and it may be difficult to exhibit good rubber elastic behavior. When the number of fluorosilyl groups contained in one molecule is more than 5 on average, the elongation of the rubber-like cured product may be small. As described above, the fluorosilyl group may be present at the end of the main chain or at the end of the side chain of the polymer molecular chain, or may be incorporated into the main chain, but in particular the main chain When it is present at the end of the polymer, the effective network length of the organic polymer component contained in the finally formed cured product becomes long, so a rubbery cured product exhibiting high strength and high elongation and low elastic modulus is obtained. It becomes easy to be When two or more fluorosilyl groups exist in one molecule, each silicon group may be the same or different.

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

  In the fluorinated polymer, the introduction of the fluorosilyl group may be carried out by any method, but the introduction method (method (i)) by the reaction of the low molecular weight silicon compound having the fluorosilyl group with the polymer and the fluorine The method (method (ii)) of modifying the silicon group of a polymer containing a reactive silicon group having a hydrolyzable group (hereinafter sometimes referred to as "polymer (X)") to a fluorosilyl group It can be mentioned.

The following method is mentioned as a specific example of method (i).
(I) A method of reacting a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule with a compound having a functional group having reactivity with the functional group and a fluorosilyl group. For example, a method of reacting a polymer having a hydroxyl group at an end with isocyanate propyl difluoromethylsilane, or a method of reacting a polymer having an SiOH group at an end and difluorodiethoxysilane may be mentioned.
(Ii) A method of hydrosilylation by causing a hydrosilane having a fluorosilyl group to act on a polymer containing an unsaturated group in the molecule. For example, there is a method of reacting difluoromethyl hydrosilane with a polymer having an allyl group at the end.
(Iii) A method of reacting a compound having a mercapto group and a fluorosilyl group with a polymer containing an unsaturated group. For example, there is a method of reacting mercaptopropyl difluoromethylsilane with a polymer having an allyl group at the end.

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

Further, in the method (ii), as a method of converting a reactive silicon group having a hydrolyzable group other than fluorine into a fluorosilyl group, a known method can be used, and for example, it is shown by the above-mentioned formula (9) There is a method of converting a hydrolyzable silicon group to be a fluorosilyl group with a fluorinating agent.
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, and fluorination proceeds efficiently, and further secondary Salts and the like are not generated in the product, and post treatment is easy, which is more preferable, and BF ₃ ether complex is particularly preferable.
Furthermore, although fluorination with BF ₃ ether complex proceeds without heating, the reaction proceeds, but in order to conduct fluorination more efficiently, heating is preferable. As heating temperature, 50 degreeC or more and 150 degrees C or less are preferable, and 60 degreeC or more and 130 degreeC are more preferable. Reaction may not advance efficiently that it is 50 degrees C or less, and fluorination may take time. If the temperature is 150 ° C. or higher, the fluorinated polymer may be decomposed. In the fluorination with a BF ₃ complex, coloration may occur depending on the type of the polymer (X) to be used, but from the viewpoint of suppression of coloration, 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 if moisture is present when producing the fluorinated polymer using the method of (ii) above The silanol condensation reaction may proceed to increase the viscosity of the resulting fluorinated polymer. For this reason, it is desirable that the production of the fluorinated polymer is carried out in an environment in which the water does not exist as much as possible, and before fluorination, the polymer (X) to be fluorinated is subjected to azeotropic dehydration using toluene, hexane or the like. It is preferable to perform a dewatering operation such as feeding. However, in the case of using a BF ₃ amine complex, fluorination does not easily proceed after dehydration operation, and there is a tendency for the reactivity to be improved by adding a small amount of water, so that the increase in water viscosity is acceptable. Is preferably added. Further, from the viewpoint of the stability of the fluorinated polymer, it is preferable to remove the fluorinating agent and the by-produced fluorinating agent-derived component after fluorination by filtration, decantation, liquid separation, vacuum evaporation or the like. When producing a fluorinated polymer 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 preferred, less than 100 ppm is more preferred, and less than 50 ppm is particularly preferred. By removing BF ₃ and BF ₃ -derived components, it is possible to suppress the increase in viscosity and the like of the obtained fluorinated polymer itself and the mixture of the fluorinated polymer and the polymer (X). Taking this point into consideration, the fluorination method using BF ₃ ether complex and BF ₃ alcohol complex is preferable because the boron component can be relatively easily removed by vacuum degassing, and the method using BF ₃ ether complex is particularly preferable. .

  Here, when the polymer (X) has two or more hydrolyzable groups other than fluorine, all hydrolyzable groups may be fluorinated, or a method such as reducing the amount of fluorinating agent , And may be partially fluorinated by adjusting the conditions of fluorination. For example, in the case of producing a fluorinated polymer using the polymer (X) in the method (ii) above, the amount of the fluorinating agent used is not particularly limited, and the molar amount of fluorine atoms in the fluorinating agent The amount may be such that it is equimolar or more with respect to the molar amount of the polymer (X). When it is going to fluorinate all the hydrolysable groups which a polymer (X) contains by the method of (ii), the molar amount of the fluorine atom in a fluorinating agent contains a polymer (X) It is preferable to use an amount of fluorinating agent that is equal to or greater than the total molar amount of hydrolyzable groups in the reactive silicon group. Here, "a fluorine atom in the fluorinating agent" means a fluorine atom effective for fluorination in the fluorinating agent, specifically, a hydrolyzable group in a reactive silicon group of the polymer (X) Refers to a fluorine atom that can be substituted.

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

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

  The glass transition temperature of the fluorinated polymer is not particularly limited, but is preferably 20 ° C. or less, more preferably 0 ° C. or less, and particularly preferably −20 ° C. or less. When the glass transition temperature exceeds 20 ° C., the viscosity in winter or cold region may become high and handling may be difficult, and the flexibility of the cured product obtained when used as a curable composition is reduced, and the elongation May decrease. The glass transition temperature can be determined by DSC measurement.

  The fluorinated polymer may be linear or may have branches. The number average molecular weight of the fluorinated polymer is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, still more preferably 2,000 to 30,000, particularly preferably 2 to 100,000 in terms of polystyrene in GPC. And 25,000. If the number average molecular weight is less than 1,000, the elongation characteristic of the cured product tends to be disadvantageous, and if it exceeds 100,000, the viscosity tends to be disadvantageous because of the high viscosity.

  Although the compounding ratio of the silicon compound (B) which has the said Si-F bond does not have a restriction | limiting in particular, 0.1 mass part or more of (B) silicon compounds are preferable with respect to 100 mass parts of (A) polymers, Preferably 0. It is suitable to mix | blend 5 mass parts or more and 20 mass parts or less, preferably 10 mass parts or less.

  The amidine used in the reaction product (C) is not particularly limited as long as it is a compound having an amidine skeleton, but a cyclic diamine compound having an amidine skeleton is preferable, and 1,8-diazabicyclo (5.4.0 More preferred are undecene-7 (DBU) and 5-diazabicyclo (4.3.0) nonene-5 (DBN).

  As an acid used for the said (C) reaction product, both an organic acid and an inorganic acid can be used. Examples of the acid include carboxylic acids such as acetic acid, octylic acid, nonanoic acid, acrylic acid, benzoic acid and trifluoroacetic acid, carboxylic acids such as difluoroacetic acid, carboxylic acids such as fluoroacetic acid, and 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, etc. Carboxylic acid, carboxylic anhydride, Sulfonic acid is preferable, and carboxylic acid is more preferable from the viewpoint of low thickening rate and good stability.

  It is preferable that pKa of the said acid is -3-15, and 3-12 are more preferable.

  The reaction conditions for the above-mentioned amidine and acid are not particularly limited, but may be carried out according to the usual method of acid-base reaction, but preferably 0.1 to 3.0 moles of acid per mole of amidine, More preferably, 0.50 to 2.25 mol, further preferably 0.75 to 2.0 mol is reacted. The reaction temperature is preferably -10 ° C to 80 ° C, and more preferably -5 ° C to 50 ° C. In order to avoid contact with moisture in the air when the reaction is carried out, it is desirable to carry out the reaction in the presence of an inert gas. The inert gas may, for example, be nitrogen or helium, preferably nitrogen. Although the reaction time is not particularly limited, it is preferably set in the range of usually 0.1 to 24 hours, preferably 0.5 to 6 hours.

  The (C) reaction product may be a product of complete reaction between amidines and an acid, or may contain unreacted amidines or acids. In addition, amidines and acids may be separately added to the reaction product. The content of unreacted amidines and unreacted acid in the reaction product (C) is preferably the same as the amount of the remaining amidines and acid when they are reacted under the preferable molar ratio of the reaction conditions of the amidines and the acid described above. It is.

  Although the compounding ratio of the (C) reaction product is not particularly limited, the (C) reaction product is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, per 100 parts by mass of the (A) polymer. 20 parts by mass or less, preferably 10 parts by mass or less. By blending the reaction product (C) in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A), better adhesion can be exhibited.

  In the curable composition of the present invention, the blending ratio of (B) a silicon compound having a Si-F bond used as a curing catalyst and (C) a reaction product is (B): (C) in a mass ratio of 1 : 0.001 to 1:20 are preferable, and 1: 0.005 to 1:10 are more preferable.

  The curable composition of the present invention uses the silicon compound having the (B) Si-F bond and the (C) reaction product as a curing catalyst, but other curing catalysts may be used to such an extent that the effects of the present invention are not reduced. It can also be used in combination. Examples of the other curing catalyst include organic metal compounds and amines, and in particular, a silanol condensation catalyst is preferably used. Examples of the silanol condensation catalyst include stannas octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dibutyltin bistriethoxy silicate, dibutyltin distearate Organotin compounds such as dioctyltin dilaurate, dioctyltin diversatate, tin octylate and tin naphthenate; dialkyltin oxides such as dimethyltin oxide, dibutyltin oxide and dioctyltin oxide; reaction products of dibutyltin oxide and phthalate ester Titanates such as tetrabutyl titanate, tetrapropyl titanate, etc .; aluminum tris acetylacetonate, aluminum tris ethoxide Organoaluminum compounds such as acetoacetate and diisopropoxyaluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; organic acid lead such as lead octylate and lead naphthenate; bismuth octylate And bismuth of an organic acid such as bismuth neodecanoate and bismuth rosin acid; and other acidic catalysts and basic catalysts which are known as silanol condensation catalysts. However, depending on the addition amount, the toxicity of the curable composition obtained may become strong depending on the addition amount.

The curable composition of the present invention preferably further contains (D) a filler. The cured product can be reinforced by blending the (D) filler.
As the (D) filler, known fillers can be widely used, and there is no particular limitation. For example, calcium carbonate, magnesium carbonate, diatomaceous earth hydrous silicic acid, hydrous silicic acid, silicic acid anhydride, silicic acid silicate, calcium silicate Fine powder silica, titanium dioxide, clay, talc, carbon black, slate powder, mica, kaolin, zeolite, polymer powder and the like, calcium carbonate, fine powder silica and polymer powder are preferable, and surface-treated carbonated One or more selected from the group consisting of calcium, amorphous silica having a particle size of 0.01 to 300 μm, and polymer powder having a particle size of 0.01 to 300 μm is more preferable. In addition, glass beads, silica beads, alumina beads, carbon beads, styrene beads, phenol beads, acrylic beads, porous silica, shirasu balloon, glass balloon, silica balloon, saran balloon, acrylic balloon, etc. can also be used. Among them, an acrylic balloon is more preferable in that the decrease in elongation after curing of the composition is small.

As the calcium carbonate, any of heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, ground calcium carbonate and the like can be used, but colloidal calcium carbonate is more preferable. These calcium carbonates may be used alone or in combination of two or more.
The primary particle diameter of the calcium carbonate is preferably 0.5 μm or less, and more preferably 0.01 to 0.1 μm. Thixotropy can be imparted to the curable composition by using such finely divided calcium carbonate having a small particle size.

  Further, among calcium carbonates, surface-treated calcium carbonate is preferable from the viewpoint of imparting thixotropy and a reinforcing effect on a cured product (hardened film), and finely ground calcium carbonate which has been surface-treated is more preferable. In addition, other calcium carbonate, for example, calcium carbonate which is not surface-treated and has a large particle size, calcium carbonate, calcium carbonate having a large particle size, and the like may be used in combination with the surface-treated fine powdered calcium carbonate. May be When the surface-treated finely ground calcium carbonate and other calcium carbonate are used in combination, the ratio (mass ratio) of the surface-treated finely ground calcium carbonate to the other calcium carbonate is preferably 1: 9 to 9: 1, and 3: 7 ~ 7: 3 is more preferred.

  In the surface-treated calcium carbonate, the surface treatment agent to be used is not particularly limited, and known surface treatment agents can be widely used. Examples of the surface treatment agent include higher fatty acid compounds, resin acid compounds, aromatic carboxylic acid esters, anionic surfactants, cationic surfactants, nonionic surfactants, paraffin, titanate couplings. Agents and silane coupling agents, with higher fatty acid compounds and paraffin being more preferred. These surface treatment agents may be used alone or in combination of two or more.

Examples of the higher fatty acid compounds include higher fatty acid alkali metal salts having 10 or more carbon atoms such as sodium stearate.
Examples of the resin acid compound include abietic acid, neoabietic acid, d-pimaric acid, id-pimaric acid, bodocarp acid, benzoic acid, cinnamic acid and the like.
Examples of the aromatic carboxylic acid ester include esters of phthalic acid with octyl alcohol, butyl alcohol, isobutyl alcohol, etc., lower alcohol esters of naphthoic acid, lower alcohol esters of rosin acid, and maleic acid of aromatic dicarboxylic acid or rosin acid There may be mentioned partial esterified products of aromatic polycarboxylic acids such as acid adducts or esterified products of different alcohols.
As the anionic surfactant, for example, a sulfate ester type such as sodium dodecyl sulfate, or a sulfonic acid type anionic surfactant such as sodium dodecyl benzene sulfonate, sodium lauryl sulfonate, and dodecyl benzene sulfonic acid Can be mentioned.

  As the surface-treated calcium carbonate, known surface-treated calcium carbonate can be widely used, and there is no particular limitation. For example, Vigot 15 (manufactured by Shiroishi Calcium Co., Ltd., light carbonate surface-treated with a fatty acid) Surface treated light calcium carbonate such as calcium, primary particle size 0.15 μm); Vigot 10 (manufactured by Shiroishi Calcium Co., Ltd., colloidal calcium carbonate surface treated with fatty acid, primary particle size 0.10 μm), white matting DD (white mineral calcium) Co., Ltd., colloidal calcium carbonate surface-treated with resin acid, primary particle diameter 0.05 μm, Carlex 300 (manufactured by Maruo Calcium Co., Ltd.), colloidal calcium carbonate surface-treated with fatty acid, primary particle diameter 0. 05 μm), Neolite SS (manufactured by Takehara Chemical Industries, Ltd., surface-treated with fatty acid) Dar calcium carbonate, average particle size 0.04 μm, Neolite GP-20 (Takehara Chemical Industries, Ltd., colloidal calcium carbonate surface-treated with resin acid, average particle size 0.03 μm), Calcyth P (Kamishima Chemical Co., Ltd.) Co., Ltd., surface-treated colloidal calcium carbonate such as colloidal calcium carbonate surface-treated with fatty acid, average particle size 0.15 μm), MC coated P1 (manufactured by Maruo Calcium Co., Ltd., heavy carbonated surface-treated with paraffin) Calcium, primary particle diameter 3.3 μm, AFF-95 (manufactured by Fimatech Co., Ltd., ground calcium carbonate surfaced with cationic polymer, primary particle diameter 0.9 μm), AFF-Z (manufactured by Fimatech Co., Ltd.) , Heavy calcium carbonate surfaced with cationic polymer and antistatic agent, primary particle diameter 1.0 μm), etc. Calcium and the like.

  It is preferable to mix | blend 0-500 mass parts with respect to 100 mass parts of said (A) organic polymers, it is more preferable to mix | blend 10-300 mass parts, and, as for the said surface-treated calcium carbonate, 15-100 mass parts combination It is further preferable to do. The surface-treated calcium carbonate may be used alone or in combination of two or more. In addition, surface-treated calcium carbonate may be used in combination with calcium carbonate which has not been subjected to surface treatment.

Amorphous silica known in the art can be widely used as the amorphous silica, and there is no particular limitation, but the particle size is preferably 0.01 to 300 μm, and more preferably 0.1 to 100 μm. And 1 to 30 μm are more preferable.
By using amorphous silica in which the difference between the refractive index of the (A) organic polymer and the refractive index of the amorphous silica is 0.1 or less, the transparency can be further improved. The difference between the refractive index of the organic polymer (A) and the refractive index of the amorphous silica is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.03 or less.

  It is preferable to mix | blend 0-500 mass parts with respect to 100 mass parts of said (A) organic polymers, it is more preferable to mix | blend 1-200 mass parts, and the said amorphous silica is 5-50 mass parts combination. It is further preferable to do. The said amorphous silica may be used by 1 type, and may be used in combination of 2 or more types. Further, together with amorphous silica having a particle size of 0.01 to 300 μm, amorphous silica or crystalline silica having a particle size range different from the above may be used in combination.

  A wide variety of known polymer powders can be used as the polymer powder, and there is no particular limitation, but the particle size is preferably 0.01 to 300 μm, and more preferably 0.1 to 100 μm. And 1 to 30 μm are more preferable.

  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 Preferably, a polymer powder obtained by polymerizing a copolymer obtained by copolymerizing with a polymer is used, an acrylic polymer powder and a vinyl polymer powder are more preferable, and an acrylic polymer powder is further preferable. preferable.

In order to further improve the transparency of the curable composition of the present invention, the difference between the refractive index of the liquid phase component mainly composed of the (A) organic polymer and the refractive index of the polymer powder is set to 0.1. It is preferable to set it as the following, 0.05 or less is more preferable, and 0.03 or less is more preferable.
There is no particular limitation on the method of setting the difference between the refractive index of the liquid phase component mainly composed of the organic polymer (A) and the refractive index of the polymer powder to 0.1 or less. (A) A method of matching the refractive index of a liquid phase component containing an organic polymer as a main component to the refractive index of molecular powder, and (2) the refractive index of a polymer powder to the refractive index of (A) organic polymer And the like.

  As a method of the above (1), for example, a method of adjusting the refractive index of the liquid phase component by blending a necessary amount of a refractive index modifier compatible with the liquid phase component containing the (A) organic polymer as the main component Can be mentioned. Specifically, in an embodiment in which the refractive index of the (A) organic polymer is about 1.46 to 1.48 and the refractive index of the polymer powder is higher, it is higher than the (A) organic polymer. Refractive index modifiers having a refractive index {eg, epoxy resin (eg, Epicoat 828 (bisphenol A, manufactured by Yuka Shell Epoxy Co., Ltd., refractive index 1.57)), petroleum resin (eg, FTR 6100 (C5 and C9) Copolymer, Mitsui Petrochemicals Co., Ltd. product, refractive index 1.56)], terpene phenol resin [Example: Polystar T145 (Yashara Chemical Co., Ltd. product, refractive index 1.59)]}, (A) organic weight The method of heat-melting to uniting is mentioned.

  As a method of said (2), the method of changing suitably the monomer combination of polymer powder, for example is mentioned. Specifically, in the embodiment in which the refractive index of the (A) organic polymer is about 1.46 to 1.48 and the acrylic polymer powder is used as the polymer powder, the refractive index of the polymer powder is As a method of increasing the amount, for example, a monomer such as vinyl chloride [refractive index 1.53 (polymer)], arylonitrile [refractive index 1.52 (polymer)], etc. The method of copolymerizing to the body is mentioned. In the embodiment, as a method for lowering the refractive index of the polymer powder (E4), for example, lauryl methacrylate [refractive index 1.44 (monomer)], allyl methacrylate [refractive index 1.44 (single And copolymers of monomers such as 2) (2-ethoxyethoxy) ethyl acrylate [refractive index 1.43 (monomers)] and the like to a meta) acrylic ester monomer.

  It is preferable to mix | blend 0-500 mass parts with respect to 100 mass parts of said (A) organic polymers, it is more preferable to mix | blend 0.5-100 mass parts, and, as for the said polymer powder, 1-50 mass parts is preferable. It is more preferable to mix | blend. The polymer powder may be used alone or in combination of two or more.

Moreover, in the curable composition of the present invention, it is preferable to further contain a conductive filler. By using a conductive filler, it is possible to impart conductivity to the cured product. The conductive filler may be surface-treated with a surface treatment agent.
As the conductive filler, known conductive fillers can be used. For example, silver, copper, nickel, iron, silver-coated copper, silver-coated glass, silver-coated nickel, zinc oxide, silver oxide, tin oxide, Indium tin oxide, carbon fillers, carbon nanofibers and the like can be mentioned. The conductive fillers may be used alone or in combination of two or more.

  In the curable composition of the present invention, the compounding ratio of the (D) filler is not particularly limited, but 0 to 500 mass of the (D) filler with respect to 100 parts by mass of the (A) organic polymer. It is preferable to mix in parts, more preferably 2 to 250 parts by mass, and even more preferably 5 to 125 parts by mass. The (D) filler may be used alone or in combination of two or more.

The curable composition of the present invention preferably further contains (E) a diluent. Physical properties such as viscosity can be adjusted by blending the (E) diluent.
(E) As the diluent, known diluents can be widely used, and there is no particular limitation. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, linearene dimer (trade name of Idemitsu Kosan Co., Ltd.) Α-olefin derivatives represented by the following formula (I) such as: aromatic hydrocarbon solvents such as toluene and xylene; alcohols such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol and diacetone alcohol Solvents, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate, acetyl triethyl citrate, acetyl tributyl citrate, citric acid ester solvents such as triethyl citrate, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone And various solvents such as .
R ⁵¹ -Z-R ⁵² (I)
(In the above formula (I), R ⁵¹ and R ⁵² each independently represent a linear alkyl group having 2 to 20 carbon atoms, and Z is a group represented by any one of the following formulas (Ia) to (Ic) Represents a valence group)

(In formula (Ib), R ⁵³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 40 carbon atoms.)

The flash point of the (E) diluent is not particularly limited, but in view of the safety of the resulting curable composition, it is desirable that the flash point of the curable composition be as high as possible, and the volatile substances from the curable composition Is preferred.
Therefore, the flash point of the (E) diluent is preferably 60 ° C. or more, and more preferably 70 ° C. or more. When mixing and using 2 or more (E) diluents, it is preferable that the flash point of the mixed diluent is 70 degreeC or more. However, since a diluent having a high flash point generally tends to have a low dilution effect on the curable composition, the flash point is preferably 250 ° C. or less.

  In consideration of both the safety and the dilution effect of the curable composition of the present invention, a saturated hydrocarbon solvent is suitable as the (E) diluent, and normal paraffin and isoparaffin are more preferable. The carbon number of normal paraffins and isoparaffins is preferably 10 to 16. 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.), IP solvent 2028 (Isoparaffin, manufactured by Idemitsu Kosan Co., Ltd., carbon number 10 to 16, flash point 86 ° C.), and the like.

  The blending ratio of the (E) diluent is not particularly limited, but it is preferable to blend 0 to 50 parts by mass of the (E) diluent with respect to 100 parts by mass of the (A) organic polymer. It is more preferable to mix | blend 1-30 mass parts, and it is further more preferable to mix | blend 0.1-15 mass parts. The (E) diluent may be used alone or in combination of two or more.

The curable composition of the present invention preferably further contains a metal hydroxide. By blending the metal hydroxide, the flame retardancy can be imparted, the workability can be improved, and the cured product can be reinforced. Furthermore, metal hydroxides also exhibit the effect of being highly safer than other flame retardants such as halogen-based flame retardants. In particular, by combining the metal hydroxide and the surface-treated calcium carbonate, the workability (thixotropy) can be further improved, and the flame retardancy can be imparted. The metal hydroxide may be a metal hydroxide surface-treated with a surface treatment agent.
Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide, and aluminum hydroxide is more preferable.

  Although the compounding ratio of the said metal hydroxide does not have a restriction | limiting in particular, It is preferable to mix | blend 0-500 mass parts of said metal hydroxides with respect to 100 mass parts of said (A) organic polymers, and 2-250 mass It is more preferable to mix a part, and it is further preferable to mix 5 to 125 parts by mass. The metal hydroxides may be used alone or in combination of two or more. In addition, other known flame retardants may be used in combination.

  The curable composition of the present invention may, in addition to the above-mentioned components, if necessary, an ultraviolet light absorber, an antioxidant, an antiaging agent, an adhesion imparting agent, a physical property modifier, a plasticizer, a thixotropic agent, and dehydration. Substances such as preservatives (storage stability modifiers), flame retardants, tackifiers, anti-sagging agents, coloring agents, radical polymerization initiators may be blended, and even if other polymers compatible are blended. Good.

  The said antioxidant is used in order to prevent the oxidation of a curable composition and to improve a weather resistance and heat resistance, for example, the antioxidant etc. of a hindered amine type and a hindered phenol type etc. are mentioned. Be Examples of hindered amine antioxidants include N, N ′, N ′ ′, N ′ ′-tetrakis- (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-) 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine · 1,3,5-triazine · N, N′-bis- (2,2,6 , 6-Tetramethyl-4-piperidyl-1,6-hexamethylenediamine · N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1 1,3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-Tetramethyl-4- Peridyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, [bis (2,2,6,6-tetramethyl-decanedioate) 1 (Octyloxy) -4-piperidyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide with octane (70%)]-polypropylene (30%), bis (1,2,2,6,6-) Pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl seba Kate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9- Examples thereof include, but are not limited to, tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, etc. Examples of hindered phenolic antioxidants include, for example, Erythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene-bis [3- (3,5-di-ter) t-Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropioamide), benzenepropanoic acid 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4 -Dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ', 3 ", 5, 5 ', 5 "-hexane-tert-butyl-4-a, a', a"-(mesitylene-2,4,6-tolyl) tri-p-cresol, calci Methyldiethylbis [[[3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthiomethyl) -o-cresol, ethylene bis (oxyethylene) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3 5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, N-phenylbenzenamine Of 2,6-tri-methylpentene and 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5 Triazin-2-ylamino) phenol and the like, but not limited thereto. The antioxidants may be used alone or in combination of two or more.

  The said ultraviolet absorber is used in order to prevent the photodegradation of a curable composition and to improve a weather resistance, For example, ultraviolet absorption of a benzotriazole type, a triazine type, a benzophenone series, a benzoate type etc. Agents and the like. Examples of the UV absorber include 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol and 2- (2H-benzotriazol-2-yl) -4,6- Di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H-benzotriazole-2) -Yl) -5-tert-Butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300 reaction product, 2- (2H-benzotriazol-2-yl) -6- (linear and branched dodecyl) -4 -Benzotriazole ultraviolet absorbers such as methylphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[( Triazine series UV absorbers such as (sil) oxy] -phenol, benzophenone series UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate etc. Although a benzoate series ultraviolet absorber etc. are mentioned, it is not limited to these. The UV absorbers may be used alone or in combination of two or more.

  The antiaging agent is used to prevent heat deterioration of the curable composition to improve the heat resistance. For example, antiaging agent such as amine-ketone system, aromatic secondary amine system Antiaging agents, benzimidazole antiaging agents, thiourea antiaging agents, phosphorous acid antiaging agents, etc. may be mentioned.

  As an anti-aging agent such as the amine-ketone type, for example, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline And amine-ketones such as a reaction product of diphenylamine and acetone, but not limited thereto.

  Examples of the aromatic secondary amine-based anti-aging agent include N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (P-toluenesulfonylamide) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine And aromatic aromatic compounds such as N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine and N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine Although secondary amine type etc. are mentioned, it is not limited to these.

  Examples of the benzimidazole-based anti-aging agent include benzimidazole-based compounds such as 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, zinc salt of 2-mercaptobenzimidazole, and the like, but are limited thereto is not.

  Examples of the thiourea-based antioxidant include, but not limited to, thiourea-based agents such as 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea.

  Examples of the phosphorous acid-based anti-aging agent include, but are not limited to, phosphorous acid-based compounds such as tris (nonylphenyl) phosphite and the like.

  The amount of the antiaging agent used is not particularly limited, but preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the (A) organic polymer. It is preferable to use in the range of 0.2 to 5 parts by mass, more preferably.

  The physical property modifier is added for the purpose of improving the physical properties of the curable composition such as tensile physical properties. As an example of the physical property modifier, for example, a silicon compound having one silanol group in one molecule and having a primary amino group is suitably used. Examples of the silicon compound include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol and the like.

  The plasticizer is added for the purpose of enhancing the elongation property after curing and enabling the reduction of the modulus. The type of the plasticizer is not particularly limited. For example, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, diisoundecyl phthalate and the like; dioctyl adipate, isodecyl succinate, sebacine Aliphatic dibasic acid esters such as dioctyl acid and dibutyl adipate; glycol esters such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate and pentaerythritol ester; and aliphatics such as butyl oleate and methyl acetyl ricinoleate Esters; Phosphate esters such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributyl phosphate, tricresyl phosphate etc .; Epoxy plasticizers such as hydrogenated soybean oil, epoxidized linseed oil, epoxy benzyl stearate and the like; 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, diethylene glycol diethyl ether, etc. with 2 repetitions, triethylene glycol diethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether etc. with 3 repetitions, tetra ethylene glycol Diethyl ether, tetraethylene glycol ethyl methyl ether, tetra ethylene glycol diethyl ether, etc. have 4 repetitions , Polyoxyethylene alkyl ethers such as polyoxyethylene dimethyl ether having more repetition; poly-α-methyl styrene, polystyrenes such as polystyrene; polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, water Hydrocarbon oligomers such as hydrogenated polybutadiene, hydrogenated polyisoprene, and process oil; Chlorinated paraffins; Acrylics such as UP-1080 (manufactured by Toagosei Co., Ltd.) and UP-1061 (produced by Toagosei Co., Ltd.) Hydroxyl group-containing acrylic plasticizers such as UP-2000 (made by Toagosei Co., Ltd.), UHE-2012 (made by Tohosei Co., Ltd.), etc .; UC-3510 (made by Tohosei Co., Ltd.) Carboxyl group-containing acrylic polymers such as; UG-4 Epoxy group-containing acrylic polymers such as 00 (manufactured by Toagosei Co., Ltd.); less than 0.8 such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.) And preferably less than 0.4 silyl group-containing acrylic polymers and the like.

  Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica and asbestos powder, organic bentonites, organic polyesters such as modified polyester polyol and fatty acid amide, hydrogenated castor oil derivative, fatty acid amide wax, aluminum stearylate And barium stearylate.

  The dehydrating agent is added for the purpose of removing water during storage. Examples of the dehydrating agent include zeolite, calcium oxide, magnesium oxide, zinc oxide and the like.

  Examples of the flame retardant include phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; bromine-based flame retardants; and chlorine-based flame retardants.

  The curable composition of the present invention can be made into a one-component type or a two-component type as needed, but it can be suitably used particularly as a one-component type. The curable composition of the present invention can be cured at room temperature by the moisture in the air, and is suitably used as a room temperature moisture curing type curable composition, but if necessary, curing is appropriately accelerated by heating. You may

The method for producing the curable composition of the present invention is not particularly limited. For example, the components (A), (B) and (C) are compounded in predetermined amounts, and other compounded substances are compounded as necessary. It can be manufactured by degassing and stirring.
There is no restriction | limiting in particular in the compounding order of component (A)-(C), and another compounding substance, What is necessary is just to determine suitably.

  The curable composition of the present invention can be used as an adhesive, sealing material, adhesive material, coating material, potting material, paint, putty material, primer and the like. The curable composition of the present invention is particularly preferably used as an adhesive because it is excellent in adhesiveness, storage stability and curability. However, it is preferably used for various other constructions, for automobiles, civil engineering, electricity and electronics. It can be used for the field etc.

The product of the present invention is a product using the moisture-curable composition of the present invention as an adhesive, and more specifically, an adherend by the adhesive using the moisture-curable composition of the present invention Glued, manufactured product.
The building component of the present invention is a building component using the moisture-curable curable composition of the present invention, and more specifically, is a building component manufactured using the moisture-curable curable composition of the present invention .
The automobile part of the present invention is an automobile part using the moisture-curable curable composition of the present invention, and more specifically, the automobile part manufactured using the moisture-curable curable composition of the present invention .
The electric / electronic component of the present invention is an electric / electronic component comprising the moisture-curable curable composition of the present invention, and more specifically, produced using the moisture-curable curable composition of the present invention Electrical and electronic components.

  EXAMPLES The present invention will be more specifically described below with reference to examples, but it is needless to say that these examples are exemplarily shown and should not be construed as limiting.

Analysis and measurement in the synthesis examples, examples and comparative examples were carried out according to the following methods.
1) Measurement of Number Average Molecular Weight Measurement was performed by gel permeation chromatography (GPC) under the following conditions. In the present invention, the molecular weight of the maximum frequency measured by GPC under the measurement conditions and converted to standard polyethylene glycol is referred to as number average molecular weight.
THF solvent measuring device / analyzer: Alliance (manufactured by Waters), 2410 differential refractive detector (manufactured by Waters), type 996 multi-wavelength detector (manufactured by Waters), Milleniam data processing device (manufactured by Waters)
Column: Plgel GUARD + 5 μm Mixed-C x 3 (50 x 7.5 mm, 300 x 7.5 mm: manufactured by PolymerLab)
Flow rate: 1 mL / min Converted polymer: polyethylene glycol Measuring temperature: 40 ° C.
FT-NMR measuring apparatus: JNM-ECA 500 (500 MHz) manufactured by JEOL Ltd.
FT-IR measuring apparatus: FT-IR 460 Plus manufactured by JASCO Corporation

2) Storage Stability Test and Curability (TFT) Test The viscosity and curing time immediately after blending of the curable composition were measured. The conditions were referred to as the initial state, and the measured viscosity and curing time were respectively defined as the initial viscosity and the initial TFT.

The viscosity is measured by a BS type rotational viscometer (rotor No. 7-10 rpm) when the viscosity of the curable composition is 160 Pa · s or more, and when the viscosity of the curable composition is less than 160 Pa · s, BH type It measured by the rotational viscometer (rotor No. 7-20 rpm) (measurement temperature 23 degreeC).
As for the curing time, in accordance with the JIS A 1439 5.19 tack free test, the touch-to-touch time (TFT) was measured under an environment of 23 ° C. RH 50%.

Next, the curable composition in the sealed glass container was allowed to stand under a 50 ° C. atmosphere for 1 week, and the viscosity and the curing time were measured. The measured viscosity and curing time were respectively used as the viscosity after storage and the TFT after storage.
The thickening rate was calculated by dividing the viscosity after storage by the initial viscosity. Moreover, the thickening rate after 1 week storage was evaluated by the following evaluation criteria.
○: 0.90 or more and 1.35 or less, x: 1.36 or more or 0.89 or less.
Also, the change rate was calculated by dividing the TFT after storage by the initial TFT. Moreover, the change rate after 1 week storage was evaluated by the following evaluation criteria.
○: 0.90 or more and 1.20 or less, x: 0.89 or less or 1.21 or more.

3) Surface Curability Test A cured product of a curable composition having a size of 100 mm × 100 mm × 3 mm was prepared by standing for 7 days under an environment of 23 ° C. RH 50%, and judged by finger touch. Evaluation criteria are as follows.
○: not sticky, ×: sticky.

4) Confirmation of Transparency The cured product of the curable composition having a size of 100 mm × 100 mm × 3 mm was prepared by leaving it for 7 days under an environment of 23 ° C. and 50% RH, and the transparency was confirmed. Evaluation criteria are as follows.
:: very clear and transparent, ○: transparent, △: somewhat cloudy, ×: cloudy

5) Adhesiveness test 0.2 g of the curable composition was uniformly applied on the adherend, and they were immediately bonded together in an area of 25 mm × 25 mm. After bonding, the adhesive strength was measured according to the test method for tensile shear adhesive strength of JIS K 6850 rigid adherend immediately after pressing with a small eyeball clip for 60 minutes or 7 days under an atmosphere of 23 ° C. RH 50%. . Plywood was used as the adherend for the adhesive strength test after 60 minutes, and hard polyvinyl chloride (PVC), polycarbonate (PC) and alumite aluminum (Al) were used as the adherend for the adhesive strength test after 7 days .

Synthesis Example 1
A hydroxyl value obtained by reacting propylene oxide with ethylene glycol as an initiator and in the presence of a zinc hexacyanocobaltate-glyme complex catalyst in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser A polyoxypropylene diol having a converted molecular weight of 24,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, and methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene diol into a sodium alkoxide to obtain a polyoxyalkylene polymer M1. The

Next, at a compounding ratio shown in Table 1, allyl chloride is reacted with polyoxyalkylene polymer M1 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at the end. I got a union. A trimethoxysilane which is a silicon hydride compound is reacted with a polyoxyalkylene polymer having an allyl group at this end by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A1 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A1 having a trimethoxysilyl group at the end by GPC, the peak top molecular weight was 25,000, and the molecular weight distribution was 1.3. The terminal trimethoxysilyl group was 1.7 per molecule according to H ¹ -NMR measurement.

(Composition example 2)
A hydroxyl value obtained by reacting propylene oxide with ethylene glycol as an initiator and in the presence of a zinc hexacyanocobaltate-glyme complex catalyst in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser A polyoxypropylene diol having a converted molecular weight of 11,000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, and methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene diol to a sodium alkoxide to obtain a polyoxyalkylene polymer M2. The

Next, at a compounding ratio shown in Table 1, allyl chloride is reacted with polyoxyalkylene polymer M2 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at the end. I got a union. A trimethoxysilane which is a silicon hydride compound is reacted with a polyoxyalkylene polymer having an allyl group at this end by adding 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt%, and trimethoxysilyl at the end. A polyoxyalkylene polymer A2 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A2 having a trimethoxysilyl group at the end by GPC, the peak top molecular weight was 12000, and the molecular weight distribution was 1.3. The terminal trimethoxysilyl group was 1.7 per molecule according to H ¹ -NMR measurement.

(Composition example 3)
Glycerol was used as an initiator in a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer, and reflux condenser, and the hydroxyl value conversion was obtained by reacting propylene oxide in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. A polyoxypropylenetriol having a molecular weight of 14000 and a molecular weight distribution of 1.3 was obtained. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene triol, and the methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylene triol into a sodium alkoxide to obtain a polyoxyalkylene polymer M3. The

Next, at a compounding ratio shown in Table 1, allyl chloride is reacted with polyoxyalkylene polymer M3 to remove unreacted allyl chloride, and purification is carried out to obtain a polyoxyalkylene polymer having an allyl group at the end. I got a union. As a polyoxyalkylene polymer having an allyl group at this end, 3-mercaptopropyltrimethoxysilane (trade name: KBM 803, manufactured by Shin-Etsu Chemical Co., Ltd.) which is a silyl compound is a polymerization initiator 2, The reaction was carried out using 2'-azobis-2-methylbutyronitrile (AIBN, manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a polyoxyalkylene polymer A3 having a trimethoxysilyl group at its terminal.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A3 having a trimethoxysilyl group at the end by GPC, the peak top molecular weight was 15,000, and the molecular weight distribution was 1.3. The terminal trimethoxysilyl group was 2.2 per molecule according to H ¹ -NMR measurement.

(Composition example 4)
In a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser, a polyoxypropylene diol having a number average molecular weight of Mn = 3000 (trade name: Diol 3000, manufactured by Mitsui Chemicals, Inc.) is placed, and sodium methoxide The methanol solution was added thereto, and methanol was distilled off under heating and reduced pressure to convert the terminal hydroxyl group of polyoxypropylenetriol to a sodium alkoxide to obtain a polyoxyalkylene polymer M4.

Next, at a compounding ratio shown in Table 1, allyl chloride is reacted with polyoxyalkylene polymer M4 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at an end. I got a union. The polyoxyalkylene polymer having an allyl group at this end is reacted with 3-mercaptopropyltrimethoxysilane which is a silyl compound using AIBN which is a polymerization initiator, and a poly having a trimethoxysilyl group at an end. An oxyalkylene polymer A4 was obtained.
The molecular weight of the obtained polyoxyalkylene polymer A4 having a trimethoxysilyl group at the end was measured by GPC, and as a result, the peak top molecular weight was 3,500 and the molecular weight distribution was 1.2. The terminal trimethoxysilyl group was 1.7 per molecule according to H ¹ -NMR measurement.

(Composition example 5)
In a new flask equipped with a stirrer, nitrogen gas inlet, thermometer and reflux condenser, polyoxypropylene diol of about 2,000 molecular weight is used as initiator and propylene oxide in the presence of zinc hexacyanocobaltate-glyme complex catalyst. The reaction product was reacted to obtain a polyoxypropylene diol having a hydroxyl value reduced molecular weight of 14500 and a molecular weight distribution of 1.3. A methanol solution of sodium methoxide is added to the obtained polyoxypropylene diol, and the methanol is distilled off under heating and reduced pressure to convert the terminal hydroxyl group of the polyoxypropylene diol to a sodium alkoxide to obtain a polyoxyalkylene polymer M5. The

Next, at a compounding ratio shown in Table 1, allyl chloride is reacted with polyoxyalkylene polymer M5 to remove unreacted allyl chloride, and purification is performed to obtain a polyoxyalkylene polymer having an allyl group at the end. I got a union. Methyldimethoxysilane, which is a silicon hydride compound, is reacted with 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3% by weight with a polyoxyalkylene polymer having an allyl group at the end to cause methyldimethoxysilyl terminal A polyoxyalkylene polymer A5 having a group was obtained.
As a result of measuring the molecular weight of the obtained polyoxyalkylene polymer A5 having a trimethoxysilyl group at an end by GPC, the peak top molecular weight was 15,000, and the molecular weight distribution was 1.3. As a result of H ¹ -NMR measurement, the number of terminal methyldimethoxysilyl groups was 1.7 per molecule.

  In Table 1, the compounding amount of each compounding substance is shown by g. The polyoxyalkylene polymers M1 to M5 are polyoxyalkylene polymers M1 to M5 obtained in Synthesis Examples 1 to 5, respectively.

Synthesis Example 6
As shown in Table 2, a polyoxyalkylene polymer having a trimethoxysilyl group at the end obtained in Synthesis Example 1 in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser 400 g of A1 and 200 g of polyoxyalkylene polymer A2 having a trimethoxysilyl group at an end obtained in Synthesis Example 2 were added, and the mixture was heated to 80 ° C. In a separate container, methyl methacrylate (trade name: Light Ester M, manufactured by Kyoeisha Co., Ltd.) 247 g, n-butyl acrylate 23 g, stearyl methacrylate (trade name: Light Ester S, Kyoeisha Co., Ltd.) 49 g, 3-methacryloxy Propyltrimethoxysilane (trade name: KBM 503, Shin-Etsu Chemical Co., Ltd. product) 45g, 3- mercaptopropyltrimethoxysilane 23.77g, AIBN 10.56g are mixed, after stirring, the dropping device is filled and taken over 3 hours It dripped. After completion of the dropwise addition, the reaction was further carried out for 3 hours to obtain an organic polymer A6 having a trimethoxysilyl group which is a mixture of a polyoxyalkylene polymer and a vinyl polymer.
As a result of measuring the molecular weight of the obtained organic polymer A6 having a trimethoxysilyl group by GPC, the peak top molecular weight was 4000, and the molecular weight distribution was 1.6. The terminal trimethoxysilyl group was 2.35 per molecule according to H ¹ -NMR measurement.

Synthesis Example 7
As shown in Table 2, 152.8 g of ethyl acetate was charged into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, and heated to 70 ° C. In another container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate, 13.1 g of 3-acryloxypropyltrimethoxysilane, 12.60 g of 3-mercaptopropyltrimethoxysilane and 4.68 g of AIBN are mixed and stirred. The solution was charged into a dropping device and dropped over 3 hours. After completion of the dropwise addition, the reaction was further carried out for 3 hours to obtain a vinyl polymer A7 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A7 by GPC, the peak top molecular weight was 6000, and the molecular weight distribution was 1.6. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 2.11 per molecule.

Synthesis Example 8
As shown in Table 2, 166 g of ethyl acetate was introduced into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. In a separate container, 247 g of methyl methacrylate, 23 g of n-butyl acrylate, 56 g of lauryl methacrylate, 33.7 g of 3-acryloxypropyltrimethoxysilane, 4.31 g of 3-methacryloxypropyltrimethoxysilane, 16 of 3-mercaptopropyltrimethoxysilane .91 g and 11.13 g of Perocta O (manufactured by NOF Corporation, organic peroxide, polymerization initiator) were mixed, stirred, filled in a dropping device, and dropped over 3 hours. After completion of the dropwise addition, reaction was further carried out for 3 hours to obtain a vinyl polymer A8 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A8 by GPC, the peak top molecular weight was 4200 and the molecular weight distribution was 1.6. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 3.03 per molecule.

  In Table 2, the compounding quantity of each compounding substance is shown by g. The polyoxyalkylene polymers A1 and A2 are the polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively.

Synthesis Example 9
As shown in Table 3, 10 g of propylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) in a flask equipped with a stirrer, a nitrogen gas inlet pipe, a thermometer and a reflux condenser. 30 g, n-butyl acrylate 100 g, lauryl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) 49 g, 3-acryloxypropyltrimethoxysilane 11.62 g, 3- (trimethoxysilyl) propyl-2-bromopropiol synthesized 5.21 g of ammonium nitrate and 4.74 g of CuBr as a transition metal catalyst, and N, N, N ', N'',N''-pentamethylenediethylene triamine (trade name: KAOLYZER No. 3, manufactured by Kao Corporation) as a ligand ) 2.86 g Preparation The contents of the flask are 80 while introducing nitrogen gas into the flask.
Heated to ° C. After the reaction for 12 hours, the temperature of the reaction product is returned to room temperature, the atmosphere is turned on to stop the polymerization, and the reaction product is purified by precipitation with dehydrated methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), vinyl having a trimethoxysilyl group Based polymer A9 was obtained.
The number average molecular weight of the obtained vinyl polymer A9 was 10000, and Mw / Mn = 1.1. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 2.0 pieces per molecule.

Synthesis Example 10
As shown in Table 3, 100 g of ethyl acetate, 60 g of methyl methacrylate, 10 g of n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. Prepare 10 g of lauryl methacrylate, 14.05 g of 3-methacryloxypropyl trimethoxysilane, 5 g of the synthesized 2-cyanoprop-2-yl dithiobenzoate, 1.86 g of AIBN, introduce nitrogen gas into the flask and introduce the contents of the flask to 80 ° C. Heated to Heating and cooling were carried out for 8 hours so that the temperature of the contents in the flask under stirring could be maintained at 80 ° C. After the reaction, the temperature of the reaction product was returned to room temperature to obtain a vinyl polymer A10 having a trimethoxysilyl group.
The number average molecular weight of the obtained vinyl polymer A10 was 4000, and Mw / Mn = 1.1. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 2.0 pieces per molecule.

Synthesis Example 11
As shown in Table 3, 188 g of ethyl acetate was put into a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device and a reflux condenser, and heated to 70 ° C. In a separate container, 264 g of methyl methacrylate, 24 g of n-butyl acrylate, 48 g of lauryl methacrylate, 40 g of 2-ethylhexyl methacrylate, 25.17 g of acryloxymethyltrimethoxysilane, 10.68 g of methacryloxymethyltrimethoxysilane (Gelest), mercapto 15.48 g of methyltrimethoxysilane (Gelest) and 6.71 g of AIBN were mixed, and after stirring, the resultant was charged in a dropping device and dropped over 3 hours. After completion of the dropwise addition, reaction was further performed for 3 hours to obtain a vinyl polymer A11 having a trimethoxysilyl group.
As a result of measuring the molecular weight of the obtained vinyl polymer A11 by GPC, the peak top molecular weight was 4500, and the molecular weight distribution was 1.6. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 3.21 per molecule.

Synthesis Example 12
As shown in Table 3, 40.00 g of ethyl acetate, 70.00 g of methyl methacrylate, 2-ethylhexyl methacrylate (Tokyo Chemical Industry Co., Ltd.) in a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. 3) 3 g of 3-acryloxypropyl trimethoxysilane and 0.10 g of titanocene diclide as a metal catalyst, and the contents of the flask were heated to 80 ° C. while introducing nitrogen gas into the flask. . Then, 4.30 g of mercaptomethyltrimethoxysilane fully purged with nitrogen gas was added at once in the flask under stirring. After 4.30 g of mercaptomethyltrimethoxysilane was added, heating and cooling were performed for 4 hours so that the temperature of the contents in the flask under stirring could be maintained at 80.degree. Furthermore, 4.30 g of fully nitrogen gas substituted mercaptomethyltrimethoxysilane was additionally added to the flask with stirring over 5 minutes. After the addition of 4.30 g of the total amount of mercaptomethyltrimethoxysilane, the reaction was carried out for 4 hours while further cooling and heating so that the temperature of the contents in the flask under stirring could be maintained at 90 ° C. After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product is returned to room temperature, and 20.00 g of a benzoquinone solution (95% THF solution) is added to the reaction product to terminate the polymerization, and vinyl system having trimethoxysilyl group Polymer A12 was obtained. The peak top molecular weight was 4000, and the molecular weight distribution was 2.4. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 2.00 per molecule.

Synthesis Example 13
As shown in Table 3, 100.00 g of n-butyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and zirconocene dichloride as a metal catalyst were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser. The contents of the flask were heated to 80 ° C. while introducing 0.10 g and introducing nitrogen gas into the flask. Then, 6.90 g of sufficiently nitrogen gas-substituted mercaptomethyltrimethoxysilane was added in one go into the flask while stirring. After the addition of 6.90 g of mercaptomethyltrimethoxysilane, heating and cooling were carried out for 4 hours so that the temperature of the contents in the flask under stirring could be maintained at 80.degree. Furthermore, 6.90 g of fully nitrogen gas-substituted mercaptomethyltrimethoxysilane was additionally added to the flask over 5 minutes with stirring. After the addition of a total of 6.90 g of mercaptomethyltrimethoxysilane, the reaction was allowed to proceed for 4 hours while further cooling and heating so that the temperature of the contents in the flask under stirring could be maintained at 90 ° C. After a total of 8 hours and 5 minutes of reaction, the temperature of the reaction product is returned to room temperature, and 20.00 g of a benzoquinone solution (95% THF solution) is added to the reaction product to terminate the polymerization, and vinyl system having trimethoxysilyl group Polymer A13 was obtained. The peak top molecular weight was 2000, and the molecular weight distribution was 1.6. The trimethoxysilyl group contained by H < ¹ > -NMR measurement was 1.00 per molecule.

  In Table 3, the compounding quantity of each compounding substance is shown by g.

Synthesis Example 14
As shown in Table 4, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and BF ₃ diethyl ether complex (Tokyo, Japan) The mixture was charged with 2.4 g of Kasei Co., Ltd., and heated to 50 ° C. 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 A2 obtained in Synthesis Example 2 and 5 g of toluene were placed. After stirring for 30 minutes at 23 ° C., the temperature was raised to 110 ° C. and stirring under reduced pressure was performed for 2 hours to remove toluene. In this container, 4.0 g of the mixture obtained earlier was slowly dropped under a nitrogen stream, and after completion of dropping, the reaction temperature was raised to 120 ° C., and the reaction was allowed to react for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove the unreacted material. A polyoxyalkylene polymer B1 having a fluorosilyl group at its end (hereinafter referred to as a fluorinated polymer B1) was obtained. The ¹ H-NMR spectrum (measured in CDCl ₃ solvent using NMR400 manufactured by Shimazu Co., Ltd.) of the obtained fluorinated polymer B1 was measured. The silylmethylene (-CH ₂ -Si) of the polymer A2 as a raw material was measured. Peak (m, 0.63 ppm) disappeared, and a broad peak appeared on the lower magnetic field side (0.7 ppm).

Synthesis Example 15
As shown in Table 4, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and replaced with nitrogen gas, and BF ₃ diethyl ether complex was produced under a nitrogen stream. 4 g was added and heated to 50 ° C. 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 A5 obtained in Synthesis Example 5 and 5 g of toluene were placed. After stirring for 30 minutes at 23 ° C., the temperature was raised to 110 ° C. and stirring under reduced pressure was performed for 2 hours to remove toluene. In this container, 4.0 g of the mixture obtained earlier was slowly dropped under a nitrogen stream, and after completion of dropping, the reaction temperature was raised to 120 ° C., and the reaction was allowed to react for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove the unreacted material. A polyoxyalkylene polymer B2 having a fluorosilyl group at its terminal (hereinafter referred to as fluorinated polymer B2) was obtained. The ¹ H-NMR spectrum (measured in CDCl ₃ solvent using NMR400 manufactured by Shimazu Co., Ltd.) of the obtained fluorinated polymer B2 was measured to find that the silylmethylene (-CH ₂ -Si) of the polymer A5 which is a raw material Peak (m, 0.63 ppm) disappeared, and a broad peak appeared on the lower magnetic field side (0.7 ppm).

Synthesis Example 16
As shown in Table 4, the flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and BF ₃ diethyl ether complex was produced under a nitrogen stream. 3 g was added and heated to 50 ° C. Subsequently, a mixture of 3.6 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 SAT010 and 5 g of toluene were placed. After stirring for 30 minutes at 23 ° C., the temperature was raised to 110 ° C. and stirring under reduced pressure was performed for 2 hours to remove toluene. The mixture obtained in the previous step was slowly added dropwise to 8.9 g of this mixture under a nitrogen stream, and after completion of the addition, the reaction temperature was raised to 120 ° C., and reaction was performed for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove the unreacted material. A polyoxyalkylene polymer B3 having a fluorosilyl group at its end (hereinafter referred to as fluorinated polymer B3) was obtained. The ¹ H-NMR spectrum (measured in CDCl ₃ solvent using NMR400 manufactured by Shimazu Co., Ltd.) of the obtained fluorinated polymer B2 was measured to give silyl methylene (-CH ₂ -Si) of SAT 010 as a raw material The corresponding peak (m, 0.63 ppm) disappeared, and a broad peak appeared on the lower magnetic field side (0.7 ppm).

Synthesis Example 17
As shown in Table 4, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and BF ₃ diethyl ether complex 28 under nitrogen stream. The mixture was charged with 80 g and heated to 50 ° C. Subsequently, a mixture of 18.56 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 vinyl polymer A13 obtained in Synthesis Example 13 and 5 g of toluene were placed. After stirring for 30 minutes at 23 ° C., the temperature was raised to 110 ° C. and stirring under reduced pressure was performed for 2 hours to remove toluene. In the vessel, 47.36 g of the mixture obtained earlier was slowly dropped under a nitrogen stream, and after completion of the dropping, the reaction temperature was raised to 120 ° C., and the reaction was allowed to react for 30 minutes. After completion of the reaction, vacuum degassing was performed to remove the unreacted material. A vinyl polymer B4 having a fluorosilyl group at its end (hereinafter referred to as fluorinated polymer B4) was obtained. The ¹ H-NMR spectrum (measured in CDCl ₃ solvent using NMR400 manufactured by Shimazu Co., Ltd.) of the obtained fluorinated polymer B4 was measured. The silylmethylene (-CH ₂ ) of the vinyl polymer A13 as a raw material was measured. The peak (m, 0.63 ppm) corresponding to —Si) disappeared, and a broad peak appeared on the lower magnetic field side (0.7 ppm ̃).

In Table 4, the compounding quantity of each compounding substance is shown by g. The polyoxyalkylene polymers A2 and A5 are the polyoxyalkylene polymers A2 and A5 obtained in Synthesis Examples 2 and 5, respectively, and the vinyl polymer A13 is the vinyl polymer A13 obtained in Synthesis Example 13. It is. Details of other compounding substances are as follows.
SAT 010: A trade name manufactured by Kaneka Corporation, a dimethoxysilyl group-containing polyoxyalkylene polymer.

(Composition example 18)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, 9.47 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C1.

(Composition example 19)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, with a nitrogen flow, 14.21 g of octylic acid is gradually dropped with a syringe. Thereafter, the temperature was raised to 50 ° C., and the mixture was stirred for 2 hours to obtain a synthetic salt C2.

(Composition example 20)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, 18.95 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Thereafter, the temperature was raised to 50 ° C., and the mixture was stirred for 2 hours to obtain a synthetic salt C3.

(Composition example 21)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, 37.89 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Thereafter, the temperature was raised to 50 ° C., and the mixture was stirred for 2 hours to obtain a synthetic salt C4.

(Composition example 22)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, with a nitrogen flow, 41.68 g of octylic acid is gradually dropped by a syringe. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C5.

(Composition example 23)
As shown in Table 5, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was made to have an ice bath and a nitrogen flow to make a DBU with a syringe. Inject 20 g of Subsequently, 47.36 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C6.

  In Table 5, the compounding quantity of each compounding substance is shown by g.

(Composition example 24)
As shown in Table 6, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was ice bathed and the nitrogen flow was used to flow the DBU with a syringe. Inject 20 g of Subsequently, 5.68 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C7.

(Composition example 25)
As shown in Table 6, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was ice bathed and the nitrogen flow was used to flow the DBU with a syringe. Inject 20 g of Subsequently, 56.84 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C8.

(Composition example 26)
As shown in Table 6, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was ice bathed and the nitrogen flow was used to flow the DBU with a syringe. Inject 20 g of Subsequently, 14.98 g of trifluoroacetic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain a synthetic salt C9.

  In Table 6, the compounding quantity of each compounding substance is shown by g.

Example 1
As shown in Table 7, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 14 5 g of the fluorinated polymer B1 obtained in 5 and 5 g of the fluorinated polymer B2 obtained in Synthesis Example 15, 1 g of U-CAT SA 102, 1 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 and degassing stirring at 25 ° C. A curable composition was obtained. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 8.

(Example 2)
As shown in Table 7, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 50 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 and Synthesis Example 4 20 g of the polyoxyalkylene polymer A4 obtained in the above, 30 g of the vinyl polymer A7 obtained in Synthesis Example 7, 1 g of the fluorinated polymer B1 obtained in Synthesis Example 14, 1 g of U-CAT SA 102, 1 g of KBM 1003 Then, 3 g of KBM 603 and 3 g of KBM 903 were added, followed by degassing and stirring at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 8.

(Example 3)
As shown in Table 7, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 50 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 3 10 g of the polyoxyalkylene polymer A3 obtained in the above, 40 g of the polymer A6 obtained in Synthesis Example 6, 3 g of the fluorinated polymer B1 obtained in Synthesis Example 14, 1 g of U-CAT SA 102, 1 g of KBM 1003, KBM 603 3 g, and 3 g of KBM 903 were added, and degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 8.

(Example 4)
As shown in Table 7, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 20 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 50 g of the polyoxyalkylene polymer A2 obtained in the above, 30 g of the polymer A8 obtained in Synthesis Example 8, 1 g of the fluorinated polymer B1 obtained in Synthesis Example 14 and 1 g of the fluorinated polymer B2 obtained in Synthesis Example 15 Then, 1 g of U-CAT SA102, 1 g of KBM 1003, 3 g of KBM 603, and 3 g of KBM 903 were added, and the mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 8.

In Table 7, the compounding quantity of each compounding substance is shown by g. Polymers A1 to A4 are polyoxyalkylene polymers A1 to A4 obtained in Synthesis Examples 1 to 4, respectively, and polymer A6 is a polyoxyalkylene polymer obtained in Synthesis Example 6 and a vinyl polymer The polymers A7 to A8 are vinyl polymers A7 to A8 obtained in Synthesis Examples 7 to 8, respectively, and fluorinated polymers B1 and B2 are Synthesis Examples 14 and 15, respectively. The obtained fluorinated polymers B1 and B2. Details of other compounding substances are as follows.
U-CAT SA102: trade name of San-Apro Co., Ltd., DBU-octylate (reactant of DBU (1,8-diazabicyclo [5.4.0] undec-7-ene) with octylic acid).
KBM 1003: trade name of Shin-Etsu Chemical Co., Ltd., vinyltrimethoxysilane.
KBM 603: trade name N- 2 (aminoethyl) -3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
KBM 903: trade name of Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane.

(Example 5)
As shown in Table 9, 100 g of the vinyl polymer A9 obtained in Synthesis Example 9 was obtained in Synthesis Example 15 in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser. 1.5 g of the fluorinated polymer B2, 1 g of U-CAT SA 102, 1 g of KBM 1003, 3 g of KBM 603 and 3 g of KBM 903 were deaerated and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 10.

(Example 6)
As shown in Table 9, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 60 g of the polyoxyalkylene polymer A2 obtained in Synthesis Example 2 and Synthesis Example 10 40 g of the vinyl polymer A10 obtained in the above, 1.5 g of the fluorinated polymer B2 obtained in Synthesis Example 15, 1 g of U-CAT SA 102, 1 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 and removed at 25 ° C. The mixture was stirred with air to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 10.

(Example 7)
As shown in Table 9, 80 g of the polyoxyalkylene polymer A7 obtained in Synthesis Example 7 in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser and Synthesis Example 11 20 g of the vinyl polymer A11 obtained in the above, 0.1 g of the fluorinated polymer B2 obtained in Synthesis Example 15, 1 g of U-CAT SA 102, 1 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 and removed at 25 ° C. The mixture was stirred with air to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 10.

(Example 8)
As shown in Table 9, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 20 g of the polyoxyalkylene polymer A1 obtained in Synthesis Example 1 and Synthesis Example 2 50 g of polyoxyalkylene polymer A2 obtained in the above, 30 g of the vinyl polymer A12 obtained in Synthesis Example 12 and 1.0 g of the fluorinated polymer B1 obtained in Synthesis Example 14 obtained in Synthesis Example 15 0.5 g of polymer B2, 1 g of U-CAT SA102, 1 g of KBM 1003, 3 g of KBM 603 and 3 g of KBM 903 are added and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 10.

  In Table 9, the compounding quantity of each compounding substance is shown by g. Polymers A1 and 2 are polyoxyalkylene polymers A1 and A2 obtained in Synthesis Examples 1 and 2, respectively, and polymers A7 and A9 to A12 are vinyl compounds obtained in Synthesis Examples 7 and 9 to 12, respectively. The details of the other compounding materials are the same as in Table 7 for polymers A7 and A9 to A12.

(Example 9)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymerized polymer B2 1.5 g, U-CAT SA 102 1 g, F320 20 g, FTR 6100 30 g, Irganox 245 3 g, N-12 7 g, KBM 1003 0.5 g, KBM 603 3 g, KBM 903 3 g, The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 10)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymerized polymer B2 1.5 g, U-CAT 1102 1 g, F320 20 g, FTR 6100 30 g, Irganox 245 3 g, N-12 7 g, KBM 1003 0.5 g, KBM 603 3 g, KBM 903 3 g, The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 11)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymerized polymer B2 1.5g, U-CAT SA1 1g, F320 20g, FTR 6100 30g, Irganox 245 3g, N-12 7g, KBM 1003 0.5g, KBM 603 3g, KBM 903 3g, The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 12)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1 g of fluorinated polymer B1, 0.5 g of fluorinated polymer B2 obtained in Synthesis Example 15, 0.1 g of U-CAT SA1, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, and 3 g of KBM 903 were added, and degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 13)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymer B2 1.5 g, U-CAT SA1 0.5 g, F320 20 g, FTR 6100 30 g, Irganox 245 3 g, N-12 7 g, KBM 1003 0.5 g, KBM 603 3 g, KBM 903 3 g The mixture was charged and degassed at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 14)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 1.5 g of the polymer B2, 2 g of U-CAT SA102, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

(Example 15)
As shown in Table 11, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 1.5 g of the polymer B2, 5 g of U-CAT SA102, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 12.

In Table 11, the compounding quantity of each compounding substance is shown by g. The details of the compounding substances are as follows. The details of the compounding substances other than the following are the same as in Table 7.
U-CAT 1102: trade name of San-Apro Co., Ltd. DBN-octylic acid salt (reactant of DBN (1,5-diazabicyclo [4.3.0] -5-nonene) with octylic acid).
U-CAT SA1: trade name of San-Apro Co., Ltd. DBU-phenol salt (reaction product of DBU and phenol).
F320: trade name of Gantz Chemical Co., Ltd., fine particles of alkyl methacrylate copolymer.
FTR 6100: trade name of Mitsui Chemical Co., Ltd., aromatic aliphatic hydrocarbon copolymer.
Irganox 245: trade name of Ciba Specialty Chemicals Ltd., triethylene glycol-bis “3- (3-T-butyl-5-methyl-4-hydroxyphenol) propionate.
N-12: trade name of JX Nippon Oil & Energy Co., Ltd., nomaldodecane.

(Example 16)
As shown in Table 13, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 1.5 g of the polymer B2, 4 g of U-CAT SA102, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 14.

(Example 17)
As shown in Table 13, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 Polymerized polymer B1 0.5g, U-CAT SA102 2g, F320 20g, FTR 6100 30g, Irganox 245 3g, N-12 7g, KBM 1003 0.5g, KBM 603 3g, KBM 903 3g, The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 14.

(Example 18)
As shown in Table 13, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 10 g of the polymer B2, 0.5 g of U-CAT SA102, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 14.

(Example 19)
As shown in Table 13, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 15 g of the polymer B2, 0.1 g of U-CAT SA102, 20 g of F320, 30 g of FTR 6100, 3 g of Irganox 245, 7 g of N-12, 0.5 g of KBM 1003, 3 g of KBM 603, 3 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 14.

  In Table 13, the compounding amount of each compounding substance is shown by g. The details of the formulated materials are the same as in Tables 7 and 11.

Example 20
As shown in Table 15, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymer B2 1.5g, U-CAT SA102 1g, Sherets 200 20g, Whiteton SB 40g, Irganox 245 3g, N-12 7g, KBE 1003 1g, KBM 603 3g, KBM903 3g The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 16.

(Example 21)
As shown in Table 15, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 15 Polymerized polymer B2 1.5g, U-CAT SA1 10g, Whiteton SB 100g, RY200 10g, Irganox 245 3g, N-12 7g, KBM3103C 1g, KBM603 3g, KBM903 3g, The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 16.

(Example 22)
As shown in Table 15, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, the weight obtained in 40 g of the polymer A2 obtained in Synthesis Example 2 and in Synthesis Example 6 0.5 g of the fluorinated polymer B2 obtained in Synthesis Example 15 with 60 g of the combined A6 and 1 g of the fluorinated polymer B obtained in Synthesis Example 14 and 1.5 g of U-CAT SA 102, 250 g of BW 53, and Whitene SB 30 g, 10 g of R972, 1 g of Noclac CD, 3 g of Irganox 245, 25 g of benzyl alcohol, 1 g of KBM 1003, 3 g of KBM 603, and 3 g of KBM 903 were deaerated and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 16.

(Example 23)
As shown in Table 15, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water-cooled condenser, the weight obtained in 40 g of the polymer A2 obtained in Synthesis Example 2 and in Synthesis Example 6 60 g of the combined A6 and 1.5 g of the fluorinated polymer B2 obtained in Synthesis Example 15 and 1.5 g of U-CAT SA 102, 100 g of Sealets 200, 100 g of Whiteton SB, 10 g of RY 200, 5 g of R972 and LA72 2 g, Irganox 245 2 g, N-12 15 g, KBM 3103 C 5 g, KBM 603 3 g, and KBM 903 were added, and degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 16.

In Table 15, the compounding amount of each compounding substance is shown by g. The details of the compounding substances are as follows. The details of the compounding substances other than the following are the same as in Tables 7 and 11.
BW53: trade name of Nippon Light Metal Co., Ltd., aluminum hydroxide, average particle diameter 50 μm.
Sealets 200: trade name of Maruo Calcium Co., Ltd., colloidal calcium carbonate, surface fatty acid treatment.
Whiteton SB: trade name of Shiraishi Kogyo Co., Ltd., crushed calcium carbonate.
RY200: trade name of Nippon Aerosil Co., Ltd., dry silica.
R972: trade name of Nippon Aerosil Co., Ltd., dry silica.
Nocl CD: trade name of Ouchi Development Co., Ltd. 4,4′-bis (α, α-dimethylbenzyl) diphenylamine.
LA 72: trade name of Adeka Co., Ltd., hindered amine light stabilizer.
Benzyl alcohol: manufactured by Tokyo Kasei Co., Ltd.
KBM3103C: trade name manufactured by Shin-Etsu Chemical Co., Ltd., decyltrimethoxysilane.
KBE 1003: trade name of Shin-Etsu Chemical Co., Ltd., vinyltriethoxysilane.

(Example 24)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the fluorinated polymer B1, 1.0 g of the synthetic salt C1, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 25)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 Polymerized polymer B1 1.0 g, synthetic salt C2 1.0 g, Irganox 245 3.0 g, N-12 2.0 g, KBM 1003 1.50 g, KBM 603 3.0 g, KBM 903 3.0 g The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 26)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the polymer B1, 1.0 g of the synthetic salt C3, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 27)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the polymerizing polymer B1, 1.0 g of the synthetic salt C4, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 28)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the polymer B1, 1.0 g of the synthetic salt C5, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 29)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the fluorinated polymer B1, 1.0 g of the synthetic salt C6, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

(Example 30)
As shown in Table 17, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of esterification polymer B1, 3.0 g of synthetic salt C6, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, the storage stability test, the surface curing test and the adhesion test of the curable composition are shown in Table 18.

  In Table 17, the compounding quantity of each compounding substance is shown by g. Synthetic salts C1 to C6 are synthetic salts C1 to C6 obtained in Synthesis Examples 18 to 23, respectively. Other details of the compounding substance are the same as those of Tables 7 and 11 in the details of the compounding substance.

(Example 31)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe, and a water cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 16 Of polymerizing polymer B3, 1.0 g of synthetic salt C3, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

(Example 32)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the polymer B1, 1.0 g of synthetic salt C7, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

(Example 33)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 Polymerized polymer B1 1.0 g, synthetic salt C8 1.0 g, Irganox 245 3.0 g, N-12 2.0 g, KBM 1003 1.50 g, KBM 603 3.0 g, KBM 903 3.0 g The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

(Example 34)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 0.1 g of fluorinated polymer B1, 0.3 g of fluorinated polymer B3 obtained in Synthesis Example 16, 0.5 g of U-CAT SA 102, 0.5 g of U-CAT SA1, 3.0 g of Irganox 245, N 2.0 g of -12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 were added, and degassing and stirring were carried out at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

(Example 35)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 17 0.5g Polymerized Polymer B4, 1.0g Synthetic Salt C3, 3.0g Irganox 245, 2.0g N-12, 1.50g KBM 1003, 3.0g KBM 603, 3.0g KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

(Example 36)
As shown in Table 19, in a 300 mL flask equipped with a stirrer, a thermometer, a nitrogen inlet, a monomer charging pipe and a water-cooled condenser, 100 g of the polymer A6 obtained in Synthesis Example 6 and the fluorine obtained in Synthesis Example 14 1.0 g of the polymerizing polymer B1, 1.0 g of the synthetic salt C9, 3.0 g of Irganox 245, 2.0 g of N-12, 1.50 g of KBM 1003, 3.0 g of KBM 603, 3.0 g of KBM 903 The mixture was degassed and stirred at 25 ° C. to obtain a curable composition. The results of the curing test, storage stability test, surface curing test and adhesion test of the curable composition are shown in Table 20.

  In Table 19, the compounding amount of each compounding substance is shown by g. The fluorinated polymers B3 and B4 are the fluorinated polymers B3 and B4 obtained in Synthesis Examples 16 and 17, respectively, and the synthetic salts C7 to C9 are the synthetic salts C7 to C9 obtained in Synthesis Examples 24 to 26, respectively, and others The details of the compounding ingredients of are the same as in Tables 7, 11 and 17.

(Comparative Examples 1 to 8)
A curable composition was obtained in the same manner as in Example 1 except that the blended materials were changed as shown in Table 21. Each measurement was performed with respect to the obtained curable composition. The results are shown in Table 22.

  In Table 21, the compounding amount of each compounding substance is shown by g. The details of the formulated materials are the same as in Tables 7 and 11.

(Comparative Example 1)
As shown in Table 23, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was vacuum degassed and then replaced with nitrogen gas, and the flask was ice bathed and nitrogen flow was used to flow lauryl with a syringe. Inject 20 g of amine. Subsequently, 15.56 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was adjusted to 50 ° C., and stirring was performed for 2 hours to obtain comparative synthetic amine salt 1.

(Comparative Synthesis Example 2)
As shown in Table 23, a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser was evacuated under reduced pressure and then purged with nitrogen gas, and the flask was ice bathed and the triethylamine flowed with nitrogen flow. Inject 20 g of Subsequently, 28.50 g of octylic acid is gradually dropped by a syringe while flowing nitrogen. Stir in an ice bath for 10 minutes and then at room temperature for 30 minutes. After stirring at room temperature, the temperature was raised to 50 ° C. and stirred for 2 hours to obtain comparative synthetic amine salt 2.

  In Table 23, the compounding quantity of each compounding substance is shown by g.

(Comparative Examples 9 to 10)
A curable composition was obtained in the same manner as in Example 1 except that the blended materials were changed as shown in Table 24. Each measurement was performed with respect to the obtained curable composition. The results are shown in Table 25.

  In Table 24, the compounding amount of each compounding substance is shown by g. Comparative synthetic amine salts 1 and 2 are comparative synthetic amine salts 1 and 2 obtained in Comparative Synthetic Examples 1 and 2, respectively. The details of the other compounding substances are the same as in Tables 7 and 11.

As shown in Tables 1 to 20, the moisture-curable curable composition of the present invention is extremely excellent in quick curing with a TFT of 10 minutes or less, and has storage stability, surface curing, adhesiveness, and adhesion. The rise in strength was also good.
On the other hand, as shown in Comparative Examples 1 and 2, the curable compositions not containing the component (C) had poor start-up adhesion and it was difficult to achieve both quick curing and storage stability. Moreover, as shown to the comparative example 3, the curable composition which does not mix | blend a component (B) was bad in the start-up adhesiveness, storage stability, and surface-hardening property. Furthermore, as shown in Comparative Example 4, the curable composition using DBU instead of the component (C) is inferior in storage stability and surface curability, and rises as compared with the curable composition of the present invention. Adhesion was also bad.

Claims (9)

(A) Organic polymers containing an average of 0.8 or more crosslinkable silicon groups in one molecule (excluding those having Si-F bond),
(B) a silicon compound having a Si—F bond, and (C) a reaction product obtained by reacting an amidine with an acid ,
The crosslinkable silicon group of the organic polymer (A) is a group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and which can be crosslinked by forming a siloxane bond,
The (A) organic polymer is at least one selected from the group consisting of saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers,
The above-mentioned amidine used in the above-mentioned (C) reaction product is a cyclic diamine compound having an amidine skeleton,
Moisture-curable curable composition characterized in that the acid used for the reaction product (C) is at least one selected from the group consisting of carboxylic acids, phenols, sulfonic acids and acid anhydrides thereof. object.   The moisture according to claim 1, wherein the amidine is 1,8-diazabicyclo (5.4.0) undecene-7 and / or 5-diazabicyclo (4.3.0) nonene-5. Curable curable composition.   The moisture-curable curable composition according to claim 1 or 2, wherein the reaction product (C) is obtained by reacting 0.1 to 3 moles of acid with 1 mole of amidine.   The moisture-curable curable composition according to any one of claims 1 to 3, wherein the acid used for the reaction product (C) is a carboxylic acid.   The moisture curable curing according to any one of claims 1 to 4, wherein the compound (B) having a Si-F bond is a fluorinated polymer having a number average molecular weight of 1,000 to 100,000. Sex composition.   An article comprising the moisture-curable composition according to any one of claims 1 to 5 as an adhesive.   An architectural member comprising the moisture-curable composition according to any one of claims 1 to 5.   An automobile part comprising the moisture-curable composition according to any one of claims 1 to 5.   An electric / electronic component comprising the moisture-curable composition according to any one of claims 1 to 5.