JP6198180B2 - Two-component curable composition - Google Patents

Description

  The present invention relates to a two-component curable composition and a cured product obtained by curing the curable composition.

  Curable compositions containing a crosslinkable silicon group-containing organic polymer have already been industrially produced and are widely used in applications such as sealing materials, adhesives and paints. Usually, these curable compositions are cured using various metal catalysts, and are used for various applications depending on the type and amount of addition.

  As the catalyst, a reaction product of organotin and an ester compound is conventionally known (see, for example, Patent Documents 1 to 4). Among the ester compounds, in particular, a catalyst using a phthalate ester is generally used. This phthalate ester is stipulated as a VOC guideline formulation substance by the Ministry of Health, Labor and Welfare, and its existence has been pointed out. In recent years, catalyst design with non-phthalate esters has been demanded. In order to increase safety, a method using a dioctyltin compound instead of a dibutyltin compound has been proposed, but the dioctyltin compound has a problem that the reactivity is low and the curing rate is slow.

  On the other hand, Patent Document 5 discloses (A) a reactive silicon group-containing polyoxyalkylene polymer and (B) an alkyl acrylate monomer unit and / or methacryl having substantially one or more molecular chains. (C) 1-60 parts by weight of a curing agent for epoxy resin with respect to 100 parts by weight of a component obtained by mixing a polymer composed of acid alkyl ester monomer units at a mass ratio of 100/0 to 1/99, D) 0.1-20 parts by weight of silane coupling agent and (E) A agent containing 0.1-5 parts by weight of water, (F) 10-80 parts by weight of epoxy resin, and (G) condensation catalyst Disclosed is a two-component curable composition comprising 0.1 to 8 parts by weight of a B agent. In the examples, (G) bis (dibutyltin laurate oxide) is used as a condensation catalyst. ), Dibutyltin oxide The reaction of dialkyl phthalates, or an example of using dibutyltin bisacetylacetonate has been described as. However, since the curable composition described in Patent Document 5 uses a dibutyltin compound, there is a problem in safety, and since water is included as an essential component, storage stability may be lowered, and after storage There was a problem that the adhesive force may be reduced.

Japanese Patent Publication No. 1-58219 Japanese Patent No. 3062625 JP-A-8-337713 JP 2003-138151 A JP 2004-2225020 A

  The present invention has been made in view of the above-described problems of the prior art, and the present invention is a two-component curable composition that has high safety, can accelerate the curing speed, and has excellent storage stability. And a cured product obtained by curing the curable composition.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research. As a result, by using a reaction product obtained by reacting a specific dioctyltin compound and a specific alkoxysilane compound, the safety is high and the curing rate is high. It was found that a two-component curable composition having a fast curing property and an excellent storage stability can be obtained.

  That is, the two-component curable composition of the present invention comprises an agent A containing an epoxy resin and a liquid tin-based curing catalyst, and an agent B containing a crosslinkable silicon group-containing organic polymer and an epoxy resin curing agent. A liquid curable composition, wherein the liquid tin-based curing catalyst is one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxy represented by the following formula (1): It is a reaction product obtained by reacting with a silane compound, and the amount of the epoxy resin is 10 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. A compounding quantity is 0.1-20 mass parts, and the compounding quantity of the said hardening | curing agent for epoxy resins is 1-60 mass parts, It is characterized by the above-mentioned.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, or an epoxycycloalkyl group, preferably a phenyl group or a vinyl group, and more preferably a phenyl group. preferable. R ² is a methyl group or a phenyl group. a is 0 or 1 (provided that, when R ¹ is an alkyl group having 6 to 20 carbon atoms, a is 0); R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogen; A plurality of R ³ groups may be the same or different.

  Moreover, it is preferable that the alkoxysilane compound is diphenyl dialkoxysilane.

  The (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer having a crosslinkable silicon group, a (meth) acrylic polymer having a crosslinkable silicon group, and a saturated hydrocarbon having a crosslinkable silicon group. It is preferable that it is 1 or more types selected from the group which consists of a system polymer.

  The cured product of the present invention is obtained by curing the two-component curable composition of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the safety | security can be accelerated | stimulated and a cure rate can be accelerated | stimulated, The curable composition excellent in the storage stability and sclerosis | hardenability, and the hardened | cured material formed by hardening this curable composition are provided. be able to. Moreover, according to this invention, the curable composition excellent in adhesiveness can be obtained.

  Embodiments of the present invention will be described below, but these are exemplarily shown, and it goes without saying that various modifications are possible without departing from the technical idea of the present invention.

  The two-component curable composition of the present invention is a two-component type comprising an agent A containing an epoxy resin and a liquid tin-based curing catalyst, and an agent B containing a crosslinkable silicon group-containing organic polymer and an epoxy resin curing agent. A curable composition, wherein the liquid tin-based curing catalyst is one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate, and an alkoxysilane compound represented by the formula (1) The amount of the epoxy resin is 10 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer, and the amount of the liquid tin curing catalyst is 0.1-20 mass parts, and the compounding quantity of the said hardening | curing agent for epoxy resins is 1-60 mass parts.

  As the epoxy resin, conventionally known ones can be widely used, and there is no particular limitation. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin and these are hydrogenated. Epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, novolac type epoxy resin, urethane modified epoxy resin having urethane bond, fluorinated epoxy resin, rubber modified epoxy resin ( Examples thereof include flame retardant epoxy resins such as polybutadiene, SBR, NBR, and CTBN modified epoxy resin, and tetrabromobisphenol A glycidyl ether. These epoxy resins may be used alone or in combination of two or more.

  Among these epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxies from the balance of workability, curability, adhesive strength, adherend versatility, water resistance, durability, etc. Resin, bisphenol S-type epoxy resin, epoxy resin hydrogenated with these, aliphatic epoxy resin, novolac-type epoxy resin, urethane-modified epoxy resin having urethane bond, fluorinated epoxy resin, rubber-modified epoxy resin, tetrabromobisphenol A Flame retardant epoxy resins such as glycidyl ether are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, epoxy resins hydrogenated with these, novolac type epoxy resin Urethane-modified epoxy resins having urethane bond, a rubber-modified epoxy resin is more preferable.

  The molecular weight of the epoxy resin is not particularly limited, but the number average molecular weight is preferably 300 to 1000, and more preferably 350 to 600.

  In the curable composition of the present invention, the mixing ratio of the epoxy resin is 10 to 200 parts by mass of the epoxy resin with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer, and 20 to 150. A mass part is preferable and 50-120 mass parts is more preferable.

  The liquid tin-based curing catalyst is a reaction product obtained by reacting at least one tin compound selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound represented by the following formula (1). It is a thing.

R ¹ R ² _a Si (OR ³ ) _3-a (1)
In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, or an epoxycycloalkyl group, and the stability of the liquid tin-based curing catalyst is improved. Therefore, a phenyl group, a vinyl group, or an alkyl group having 6 to 20 carbon atoms is preferable, a phenyl group or a vinyl group is more preferable, and a phenyl group is particularly preferable.
R ² is a methyl group or a phenyl group, and it is more preferable that R ¹ and R ² are both phenyl groups because the curing rate can be increased. a is 0 or 1 (provided that a is 0 when R ¹ is an alkyl group having 6 to 20 carbon atoms).
R ³ is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogenated hydrocarbon group, preferably a methyl group or an ethyl group, and a plurality of R ³ are the same. It can be different.

  Examples of the alkoxysilane compound include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Epoxy group-containing silanes such as trimethoxysilane; vinyl group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylisopropoxysilane; hexyltrimethoxysilane, hexyltriethoxysilane, decyltri Alkylsilanes having an alkyl group having 6 to 20 carbon atoms such as methoxysilane; phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenylmethyldimethoxysilane, diphenyldi Examples include phenyl group-containing silanes such as toxisilane and diphenyldiethoxysilane, and phenyl group-containing silanes, vinyl group-containing silanes, and alkyl silanes having an alkyl group having 6 to 20 carbon atoms are preferable. And vinyl group-containing silanes are more preferable, and diphenyl dialkoxysilane is particularly preferable in terms of curing rate.

As the dioctyl tin carboxylate, a known dioctyl tin carboxylate can be used, and there is no particular limitation, but a dioctyl tin carboxylate having a structure represented by the following formula (2) is preferable.

In the formula (2), n is 1 to 4, and R ¹¹ and R ¹² are each a monovalent organic group. For example, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, a cyclo An alkynyl group, an aryl group, an aralkyl group, etc. are mentioned, An alkyl group or an alkenyl group is preferable. The carbon number of R ¹¹ and R ¹² is not particularly limited, but is preferably 1 to 21, more preferably 1 to 17, and still more preferably 1 to 11.

  The dioctyltin carboxylate may be a commercially available dioctyltin carboxylate, or obtained by reacting dioctyltin oxide with at least one organic acid selected from the group consisting of monocarboxylic acids and monocarboxylic anhydrides. The reaction product obtained may be used. Alternatively, dioctyl tin oxide, an organic acid, and an alkoxysilane compound represented by the formula (1) may be added simultaneously to obtain a reaction product that is a liquid tin-based curing catalyst of the present invention.

  As the monocarboxylic acid, a saturated carboxylic acid and / or an unsaturated carboxylic acid can be used, but a saturated fatty acid having 2 to 22 carbon atoms, an unsaturated fatty acid having 2 to 22 carbon atoms, and an aroma having 7 to 22 carbon atoms. A group carboxylic acid or naphthenic acid is preferable, and a saturated fatty acid having 2 to 22 carbon atoms is particularly preferable. Similarly, as the monocarboxylic acid anhydride, a saturated carboxylic acid anhydride and / or an unsaturated carboxylic acid anhydride can be used, but a saturated fatty acid anhydride having 2 to 22 carbon atoms and an unsaturated carbon having 2 to 22 carbon atoms can be used. Saturated fatty acid anhydrides and aromatic carboxylic acid anhydrides having 7 to 22 carbon atoms are preferred.

In the present invention, the reaction conditions of one or more tin compounds selected from the group consisting of the dioctyl tin oxide and dioctyl tin carboxylate and the alkoxysilane compound represented by the following formula (1) are not particularly limited. from 0.20 to 1.40 mole of tin atoms of the tin compound with respect to OR ³ group 1 mole of the alkoxysilane compound, preferably suitable which are reacted in a range of 0.25 to 1.10. If it is less than 0.20 mol, there is a possibility that a sufficient curing rate cannot be obtained under room temperature conditions and low temperature conditions. Further, sufficient deep part curability may not be obtained. Furthermore, when a curing catalyst is used for the curable composition, the rubber hardness of the resulting cured product tends to increase, and the elongation of the film of the cured product tends to decrease, such being undesirable. When it exceeds 1.40 mol, it becomes difficult to dissolve the dioctyltin oxide and the alkoxysilane compound, and even if dissolved, the stability of the liquid tin-based curing catalyst tends to decrease. In addition, when this curing catalyst is used in a curable composition, the compatibility with the polymer (A) tends to decrease particularly under low temperature conditions, and a sufficient curing rate may not be obtained under low temperature conditions. Therefore, it is not preferable.

  The temperature condition of the reaction is not particularly limited, but it is preferably heated at 70 ° C to 140 ° C, more preferably 80 ° C to 120 ° C. The reaction rate can be increased by setting the reaction temperature to 70 ° C. or higher. Moreover, by making reaction temperature 140 degrees C or less, side reactions, such as thermal decomposition and gelatinization, can be prevented. The reaction time is not particularly limited, but is preferably 1 hour to 5 hours, and more preferably 1 hour to 3 hours. By this reaction, a liquid tin-based curing catalyst that is liquid at normal temperature (for example, 23 ° C.) can be obtained.

  The reaction between the tin compound and the alkoxysilane compound may be performed by reacting one or more tin compounds selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound, and dioctyltin. An oxide, an organic acid, and an alkoxysilane compound may be reacted. The carboxylic acid ester by-produced in the reaction between dioctyltin carboxylate and the alkoxysilane compound may or may not be removed, but is preferably used after being removed. By removing the by-produced carboxylic acid ester, the curing rate of the curable composition using the liquid tin-based curing catalyst of the present invention can be further increased.

  The liquid tin-based curing catalyst may further contain other compounding substances such as a diluent and a plasticizer, and particularly preferably contains a diluent. There is no particular limitation on the timing of adding other compounding substances such as a diluent, and it may be before or after the reaction between the tin compound and the alkoxysilane compound, but it is preferable to add the diluent before or during the reaction. By compounding the diluent, the stability of the liquid tin-based curing catalyst can be improved. As the diluent, a diluent described later is preferably used. In the reaction, the alkoxysilane compound may be used alone or in combination of two or more.

  In the curable composition of the present invention, the blending ratio of the liquid tin-based curing catalyst is such that the blending amount of the liquid tin-based curing catalyst is 0.1 to 20 with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. It is a mass part, 0.5-10 mass parts is preferable and 1-8 mass parts is more preferable.

  As the crosslinkable silicon group-containing organic polymer, those having various main chain skeletons can be used, and on average, one molecule has 0.8 or more crosslinkable silicon groups and is mainly composed. Organic polymers whose chain is not polysiloxane are preferred.

Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester 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, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: 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-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers.

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

  The crosslinkable silicon group of the (A) organic polymer used in the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by the following general formula (3) is preferable.

In the formula (3), R ²¹ represents 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 ^21. ₃ represents a triorganosiloxy group represented by SiO— (R ²¹ is the same as above), and when two or more R ²¹ are present, they may be the same or different. X represents a hydroxyl group or a hydrolyzable group, and when two or more X exist, they may be the same or different. d represents 0, 1, 2, or 3, and e represents 0, 1, or 2, respectively. Moreover, p in the following general formula (4) need not be the same. p shows the integer of 0-19. However, d + (sum of e) ≧ 1 is satisfied.

The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and d + (sum of e) is preferably in the 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, there may be about 20 silicon atoms.

  As the crosslinkable silicon group, a crosslinkable silicon group represented by the following general formula (5) is preferable because it is easily available.

In the formula (5), R ²¹ and X are the same as those described above, and d is an integer of 1, 2 or 3. In view of curability, in order to obtain a curable composition having a sufficient curing rate, in the above formula (5), d is preferably 2 or more, more preferably 3.

Specific examples of R ²¹ include an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ²¹ ₃ SiO—. And triorganosiloxy group. Of these, a methyl group is preferred.

  It does not specifically limit as a hydrolysable group shown by said X, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxyl group, an amide group, and an aminooxy group are more preferable. An alkoxyl group is particularly preferred from the viewpoint of mild hydrolysis and easy handling. Among alkoxyl groups, those having fewer carbon atoms have higher reactivity, and the reactivity decreases as the number of carbon atoms increases in the order of methoxy group> ethoxy group> propoxy group. Although it can be selected according to the purpose and use, a methoxy group or an ethoxy group is usually used.

Specific examples of the crosslinkable silicon group include trialkoxysilyl groups [—Si (OR) ₃ ] such as trimethoxysilyl group and triethoxysilyl group, dialkoxy such as methyldimethoxysilyl group and methyldiethoxysilyl group. silyl groups ^[-SiR 21 _{(OR) 2]} and the like. Here, R is an alkyl group such as a methyl group or an ethyl group.

  Further, the crosslinkable silicon group may be used alone or in combination of two or more. The crosslinkable silicon group can be present in the main chain, the side chain, or both.

  The number of silicon atoms forming the crosslinkable silicon group is one or more, but 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 its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the average number of crosslinkable silicon groups contained in the organic polymer is 0.8 or more in one molecule of the polymer. 1.1 to 5 may be present. If 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 develop good rubber elastic behavior. The crosslinkable silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. 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 is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer is essentially a polymer having a repeating unit represented by the following general formula (6).
-R ²² -O- (6)
In the general formula (6), R ²² 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 (6) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H5) 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 be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferable because it is amorphous or has a relatively low viscosity.

  As a method for synthesizing a polyoxyalkylene polymer, for example, polymerization using an alkali catalyst such as KOH, for example, organic aluminum as disclosed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623 A polymerization method using an organoaluminum-porphyrin complex catalyst obtained by reacting a compound with a porphyrin, such as a polymerization method using a double metal cyanide complex catalyst described in JP-B-46-27250 and JP-B-59-15336, etc. However, it is not particularly limited. A polyoxyalkylene system having a narrow molecular weight distribution with a high molecular weight having a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less according to a polymerization method using an organic aluminum-porphyrin complex catalyst or a polymerization method using a double metal cyanide complex catalyst A polymer can be obtained.

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

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

  As a specific example of the polymer reaction method, a hydrosilane or mercapto compound obtained by allowing a hydrosilane having a crosslinkable silicon group or a mercapto compound having a crosslinkable silicon group to act on an unsaturated group-containing polyoxyalkylene polymer to form a crosslinkable silicon group The method of obtaining the polyoxyalkylene type polymer which has this can be mention | raise | lifted. An unsaturated group-containing polyoxyalkylene polymer is obtained by reacting an organic polymer having a functional group such as a hydroxyl group with an organic compound having an active group and an unsaturated group that are reactive with the functional group, A polyoxyalkylene-based polymer having can be obtained.

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

  Specific examples of the polyoxyalkylene polymer having a crosslinkable silicon group include JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. No. 57-164123, JP-B No. 3-2450, JP-A No. 2005-213446, No. 2005-306891, International Publication No. WO2007-040143, US Pat. No. 3,632,557, No. 4,345,053, The ones proposed in the publications such as 4,960,844 can be listed.

  The above polyoxyalkylene polymers having a crosslinkable silicon group may be used alone or in combination of two or more.

  The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) Diene compounds such as butadiene and isoprene are homopolymerized, or copolymerized with the olefin compounds. After that, it can be obtained by a method such as hydrogenation. However, isobutylene polymers and hydrogenated polybutadiene polymers are easy to introduce functional groups at the terminals, control the molecular weight, and the number of terminal functional groups. Therefore, an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. Those containing at least mass% are preferred, those containing at least 80 mass% are more preferred, and those containing from 90 to 99 mass% are particularly preferred.

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

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silicon group include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 63-254149, Japanese Patent Publication No. 64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

  The above saturated hydrocarbon polymer 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 (meth) 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, tetramethylpiperidinyl (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, etc. Alicyclic (meth) acrylic acid ester monomers; phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, hydroxyethylated o-phenylphenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxydiethyl Aromatic (meth) acrylic acid ester monomers such as ethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenylthioethyl (meth) acrylate; 2-methoxy (meth) acrylate, (meth) acrylic acid (Meth) acrylate 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 monomers such as tildimethoxymethylsilane and methacryloyloxymethyldiethoxymethylsilane; (meth) acrylic acid derivatives such as ethylene oxide adducts of (meth) acrylic acid; (meth) acrylic Trifluoromethyl methyl acid, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, (meth ) Perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) 2-perfluorohexylethyl acrylate , Fluorine-containing (meth) acrylate monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, 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 and dialkyl esters of maleic acid; fumaric acid, monoalkyl 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, cyclohexyl Maleimide monomers such as maleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferably, it is a (meth) acrylic acid ester-based polymer using one or two or more (meth) acrylic acid alkyl ester monomers and optionally using other (meth) acrylic acid monomers, By using the group-containing (meth) acrylic acid ester monomer together, the number of silicon groups in the (meth) acrylic acid ester polymer (A) can be controlled. A methacrylic acid ester polymer composed of a methacrylic acid ester monomer is particularly preferred because of its good adhesiveness. Moreover, when performing viscosity reduction, a softness | flexibility provision, and tackiness provision, it is suitable to use an acrylate ester monomer timely. 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 polymer is not particularly limited, and known polymerization methods (for example, JP-A-63-112642, JP-A-2007-230947, JP-A-2001-40037). And a radical polymerization method using a radical polymerization reaction is preferable. As the radical polymerization method, a radical polymerization method (free radical polymerization method) in which a predetermined monomer unit is copolymerized using a polymerization initiator or a reactive silyl group is introduced at a controlled position such as a terminal. Possible controlled radical polymerization methods are mentioned. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a controlled radical polymerization method.

  Examples of the controlled radical polymerization method include a free radical polymerization method and a living radical polymerization method using a chain transfer agent having a specific functional group, and an addition-fragmentation chain transfer (RAFT) polymerization method, Living radical polymerization methods such as a radical polymerization method using a transition metal complex (Transition-Metal-Mediated Living Radical Polymerization) are more preferable. 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 (Japanese Patent Laid-Open No. 2001-40037) are also suitable.

  The (meth) acrylic acid ester-based polymer having a crosslinkable silicon group may be used alone or in combination of two or more.

  These organic polymers having a crosslinkable silicon group may be used alone or in combination of two or more. Specifically, it comprises a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth) acrylic acid ester polymer having a crosslinkable silicon group. An organic polymer obtained by blending two or more selected from the group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a crosslinkable silicon group and a (meth) acrylic acid ester polymer having a crosslinkable silicon group is disclosed in JP-A-59-122541. Although proposed in Japanese Laid-Open Patent Publication No. 63-112642, Japanese Laid-Open Patent Publication No. 6-172631, and Japanese Laid-Open Patent Publication No. 11-116763, the invention is not particularly limited thereto.
Preferable specific examples include a crosslinkable silicon group and a molecular chain substantially having the following general formula (7):
—CH ₂ —C (R ²⁵ ) (COOR ²⁶ ) — (7)
(Wherein R ²⁵ represents a hydrogen atom or a methyl group, R ²⁶ represents an alkyl group having 1 to 5 carbon atoms), and a (meth) acrylate monomer unit represented by the following general formula (8):
^{_{-CH 2 -C (R 25) (}} COOR 27) - ··· (8)
(Wherein R ²⁵ is the same as described above, and R ²⁷ represents an alkyl group having 6 or more carbon atoms). A copolymer comprising a (meth) acrylate monomer unit is represented by a crosslinkable silicon group. It is a method of blending and producing a polyoxyalkylene polymer.

As R < ²⁶ > of the said General formula (7), C1-C5, such as a methyl group, an ethyl group, a propyl group, n-butyl group, t-butyl group etc., Preferably it is 1-4, More preferably, it is 1-. 2 alkyl groups. The alkyl group of R ²⁶ may alone, or may be a mixture of two or more.

R ^{27 in the} general formula (8) is, for example, 2-ethylhexyl group, lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group and the like having 6 or more carbon atoms, usually 7 to 30, preferably 8 to 20 Long chain alkyl groups. The alkyl group of R ²⁷ is same as in the case of R ^26, alone may be, or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (7) and (8). The term “substantially” as used herein refers to the copolymer. It means that the sum of the monomer units of the formula (7) and the formula (8) present therein exceeds 50% by mass. The sum of the monomer units of the formulas (7) and (8) is preferably 70% by mass or more.
The abundance ratio of the monomer unit of the formula (7) and the monomer unit of the formula (8) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40, by mass ratio.

  Examples of monomer units other than the formulas (7) and (8) that may be contained in the copolymer (hereinafter also referred to as other monomer units) include α such as acrylic acid and methacrylic acid. , Β-unsaturated carboxylic acids; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether, etc. And other monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

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

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

  Organic polymers formed by blending a saturated hydrocarbon polymer having a crosslinkable silicon group and a (meth) acrylic acid ester copolymer having a crosslinkable silicon group are disclosed in JP-A-1-168774 and JP-A-2000-. Although it is proposed in Japanese Patent No. 186176, etc., it is not particularly limited thereto.

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

  When two or more kinds of polymers are blended and used, a saturated hydrocarbon polymer having a crosslinkable silicon group and / or a crosslink with respect to 100 parts by mass of the polyoxyalkylene polymer having a crosslinkable silicon group. It is preferable to use 10-200 mass parts of (meth) acrylic acid ester-type polymer which has a crystalline silicon group, and it is more preferable to use 20-80 mass parts.

  As the epoxy resin curing agent, known epoxy resin curing agents can be widely used and are not particularly limited. For example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylene. Aliphatic amines such as diamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, oleylamine, etc .; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1 , 2-diaminocyclohexane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabi (B) Alicyclic amines such as [5,4,0] undecene-7 (DBU); aromatic amines such as metaphenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone; -Aliphatic amines such as xylylenediamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine and other amines having an ether bond Hydroxyl group-containing amines such as diethanolamine and triethanolamine; Acid anhydrides such as trahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, dodecyl succinic anhydride; polyamide obtained by reacting dimer acid with polyamines such as diethylenetriamine and triethylenetetramine Polyamide amines such as polyamides using polycarboxylic acids other than dimer acid; Imidazoles such as 2-ethyl-4-methylimidazole; Dicyandiamide; Polyoxypropylene systems such as polyoxypropylene diamine and polyoxypropylene triamine Amines; Phenols; Epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannich-modified amines obtained by reacting the above amines with formalin and phenols, Michael addition-modified amines Modified amines such as min and ketimine; amine salts such as 2-ethylhexanoate of 2,4,6-tris (dimethylaminomethyl) phenol, and the like. Among these curing agents for epoxy resins, 2,4,6-tris (dimethylaminomethyl) phenol and polyoxypropylene diamine are preferable from the viewpoint of curability and physical property balance. These curing agents may be used alone or in combination of two or more.

  In the curable composition of the present invention, the blending ratio of the curing agent for epoxy resin is such that the blending amount of the curing agent for epoxy resin is 1 to 60 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. 2-50 mass parts is preferable, and 4-40 mass parts is more preferable.

  The curable composition of the present invention includes, in addition to the above-described components, other curing catalysts, fillers, diluents, water, ultraviolet absorbers, antioxidants, anti-aging agents, and adhesion imparting agents as necessary. , Physical property modifiers, plasticizers, thixotropic agents, dehydrating agents (storage stability improvers), flame retardants, tackifiers, anti-sagging agents, colorants, radical polymerization initiators, etc. Other compatible polymers may be blended.

  As the other curing catalyst, known curing catalysts can be widely used as long as they do not affect the performance of the curable composition, and are not particularly limited. For example, organometallic compounds and amines can be mentioned. In particular, it is preferable to use a silanol condensation catalyst. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; dibutyltin diacetyl Chelate compounds such as acetonate, dibutyltin diethyl acetoacetate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin dimethylmer Rate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin Dialkyltin dicarboxylates such as ridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, dioctyltin diisooctylmalate; Reaction products of dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide and ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate; and tetravalent compounds such as oxy derivatives (stannoxane compounds) of these dialkyl tin compounds Tin compounds; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and tin ferzatic acid; or reaction products and mixtures of these with amine compounds such as laurylamine Monoalkyltin compounds such as monobutyltin compounds such as monobutyltin trisoctoate and monobutyltin triisopropoxide and monooctyltin compounds; lead organic acids such as lead octylate and lead naphthenate; bismuth octylate, neodecanoic acid Examples include bismuth organic acids such as bismuth and bismuth rosinate; other acidic catalysts and basic catalysts known as silanol condensation catalysts.

  By blending the diluent, physical properties such as viscosity can be adjusted. As the diluent, known diluents can be widely used, and are not particularly limited. For example, saturated hydrocarbon solvents such as normal paraffin and isoparaffin, linearlen dimer (trade name of Idemitsu Kosan Co., Ltd.), etc. α-olefin derivatives, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, diacetone alcohol, ethyl acetate, butyl acetate, amyl acetate, Examples include various solvents such as ester solvents such as cellosolve acetate, citrate solvents such as acetyltriethyl citrate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

  In consideration of both safety and dilution effect of the curable composition of the present invention, a saturated hydrocarbon solvent is preferable as the diluent, and normal paraffin and isoparaffin are more preferable. The normal paraffin and isoparaffin preferably have 10 to 16 carbon atoms. Specifically, N-11 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, carbon number 11, flash point 68 ° C), N-12 (normal paraffin, manufactured by JX Nippon Oil & Energy Corporation, 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.

  Examples of the filler include reinforcing fillers such as fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide. Further, fillers such as calcium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, glass balloon, shirasu balloon, organic balloon, organic fiber and inorganic fiber can be used.

  When it is desired to obtain a cured product having high strength by using these fillers, mainly fume silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and If a filler selected from activated zinc white is used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer, preferable results are obtained. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used. If it uses in the range of 5-500 mass parts with respect to 100 mass parts of the said polymers, a preferable result will be obtained. These fillers may be used alone or in combination of two or more.

  The antioxidant is used to prevent oxidation of the curable composition to improve weather resistance and heat resistance, and examples thereof include hindered amine-based and hindered phenol-based antioxidants. It is done.

  The ultraviolet absorber is used to improve the weather resistance by preventing photodegradation of the curable composition, for example, ultraviolet absorption of benzotriazole, triazine, benzophenone, benzoate, etc. Agents and the like.

  The anti-aging agent is used to prevent heat deterioration of the curable composition and improve heat resistance. For example, an anti-aging agent such as an amine-ketone type and an aromatic secondary amine type are used. Antiaging agents, benzimidazole type antiaging agents, thiourea type antiaging agents, phosphorous acid type antiaging agents and the like can be mentioned.

  The plasticizer is added for the purpose of improving elongation properties after curing or adjusting the hardness to reduce the modulus. The type of the plasticizer is not particularly limited. For example, phthalates such as diisoundecyl phthalate; aliphatic dibasic esters such as dioctyl adipate; glycol esters such as diethylene glycol dibenzoate Aliphatic esters such as butyl oleate; Phosphate esters such as tricresyl phosphate; Epoxy plasticizers such as epoxidized soybean oil; Polyester plasticizers; Polyethers such as polypropylene glycol derivatives Polyoxyethylene alkyl ethers such as tetraethylene glycol diethyl ether; polystyrene oligomers such as poly-α-methylstyrene; hydrocarbon oligomers such as polybutadiene; chlorinated paraffins; UP-1080 ( Acrylic plasticizers such as Toagosei Co., Ltd., UP-1110 (Toagosei Co., Ltd.), UP-1061 (Toagosei Co., Ltd.); UP-2000 (Toagosei Co., Ltd.) ), UHE-2012 (manufactured by Toagosei Co., Ltd.) and the like; hydroxyl group-containing acrylic plasticizers such as UC-3510 (manufactured by Toagosei Co., Ltd.); carboxyl group-containing acrylic polymers such as UG-4000 (Toagosei) Epoxy group-containing acrylic polymers such as Synthetic Co., Ltd .; less than 0.8, such as US-6110 (manufactured by Toagosei Co., Ltd.), US-6120 (manufactured by Toagosei Co., Ltd.), preferably Examples include acrylic polymers having less than 0.4 silyl groups; oxyalkylene resins having less than 0.8, preferably less than 0.4 silyl groups.

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

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

  Examples of the flame retardant include metal hydroxides such as aluminum hydroxide and magnesium hydroxide; phosphorus flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide flame retardants such as antimony trioxide; Flame retardants; chlorine flame retardants and the like.

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

  If the adhesiveness-imparting agent is added too much, the modulus of the cured product is increased, and if it is too small, the adhesiveness is lowered. Therefore, 0.1 to 15 parts by mass with respect to 100 parts by mass of the crosslinkable silicon group-containing organic polymer. It is preferable to add part, more preferably 0.5 to 10 parts by weight.

  The tackifier is preferable for improving the wettability to the adherend and increasing the peel strength. Examples include, but are not limited to, petroleum resin-based, rosin / rosin ester-based, acrylic resin-based, terpene resin, hydrogenated terpene resin and its phenolic resin copolymer, phenol / phenol novolac resin-based tackifier resin, etc. It is not something.

  The curable composition of the present invention can be cured at normal temperature by moisture in the atmosphere, and is suitably used as a normal temperature moisture-curable curable composition, but if necessary, curing is accelerated by heating as appropriate. You may let them.

  The curable composition of the present invention can be used as an adhesive, a sealing material, an adhesive material, a coating material, a potting material, a paint, a putty material, a primer, and the like. Since the curable composition of the present invention is excellent in adhesiveness, storage stability, and curability, it is particularly preferable to use it as an adhesive, but for various other buildings, automobiles, civil engineering, electric / electronics. It can be used for fields.

  The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.

(Production Examples 1-12)
Each material was charged in a flask equipped with a cooling pipe at the blending ratio shown in Table 1, and stirred in a nitrogen atmosphere at 100 ° C. for 2 hours to obtain tin-based curing catalysts B1 to B12 that were liquid at 23 ° C.

In Table 1, the compounding quantity of each compounding substance is shown by a mass part. Details of each compounding substance are as follows.
* 1) Dioctyltin oxide: trade name “Neostan U-800P”, manufactured by Nitto Kasei Co., Ltd.
* 2) Diphenyldimethoxysilane: Trade name “Shin-Etsu Silicone KBM-202SS”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 3) Phenylmethyldimethoxysilane: Trade name “Shin-Etsu Silicone KBM-102”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 4) Phenyltrimethoxysilane: Trade name “Shin-Etsu Silicone KBM-103”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 5) Vinyltrimethoxysilane: trade name “Shin-Etsu Silicone KBM-1003”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 6) Decyltrimethoxysilane: Trade name “Shin-Etsu Silicone KBM-3103C”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 10) 3-Glycidoxypropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 17) Vinyltriethoxysilane: Trade name “Shin-Etsu Silicone KBE-1003”, manufactured by Shin-Etsu Chemical Co., Ltd.

(Production Example 13)
A four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 30.0 g (0.08 mol) of dioctyltin oxide (Neostan U-800P), 4.1 g (0.04 mol) of acetic anhydride and 200 g of toluene, After reacting at 112 ° C. for 2 hours to obtain dioctyltin carboxylate, toluene was distilled off under reduced pressure. Next, 10.0 g (0.04 mol) of diphenyldimethoxysilane (Shin-Etsu Silicone KBM-202SS) was added and stirred and reacted at 120 ° C. for 3 hours, and then the produced methyl acetate was distilled off to obtain a pale yellow transparent tin-based curing catalyst. B13 was obtained.

(Synthesis Example 1)
A methanol solution of sodium methoxide (NaOMe) was added to polyoxypropylene diol to distill off the methanol, and allyl chloride was further added to convert the terminal hydroxyl group to an allyl group. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added to react with trimethoxysilane, and the number average molecular weight in terms of PPG (polypropylene glycol) is about 25,000, and 1.5 per molecule. Polyoxypropylene polymer P1 having a number of terminal trimethoxysilyl groups was obtained.

(Synthesis Example 2)
Add a methanol solution of sodium methoxide (NaOMe) to polyoxypropylene diol having a molecular weight smaller than that of the polyoxypropylene diol used in Synthesis Example 1 to distill off the methanol, and then add allyl chloride to remove the terminal hydroxyl group. Converted to the base. Unreacted allyl chloride was removed by devolatilization under reduced pressure, and the resulting metal salt was extracted and removed with water to obtain polyoxypropylene having an allyl group at the terminal. To the resulting allyl group-terminated polyoxypropylene, an isopropanol solution of a platinum vinylsiloxane complex is added to react with trimethoxysilane, and the number average molecular weight in terms of PPG is about 15000, and 1.5 terminal trioxyls per molecule. A polyoxypropylene polymer P2 having a methoxysilyl group was obtained.

(Synthesis Example 3)
In a flask, 40 parts by mass of ethyl acetate as a solvent, 59 parts by mass of methyl methacrylate, 25 parts by mass of 2-ethylhexyl methacrylate, 22 parts by mass of γ-methacryloxypropyltrimethoxysilane, and 0.1 part by mass of ruthenocene dichloride as a metal catalyst were added. The mixture was heated to 80 ° C. while introducing charged nitrogen gas. Next, 8 parts by mass of 3-mercaptopropyltrimethoxysilane was added to the flask and reacted at 80 ° C. for 6 hours. After cooling to room temperature, 20 parts by mass of a benzoquinone solution (95% THF solution) was added to terminate the polymerization. Distilling off the solvent and unreacted material, an acrylic ester system having a trimethoxysilyl group having a polystyrene-reduced mass average molecular weight of about 6000, Mw / Mn of 1.6, and Tg of 61.2 ° C. A polymer P3 was obtained.

(Examples 1 to 10)
Each compounding substance was mixed by the compounding ratio shown in Table 2, and it deaerated and stirred at 25 degreeC, and prepared A agent and B agent. The following measurements were performed on the obtained agent A and agent B. The results are shown in Table 3.

1) Tack free time (TFT)
According to JIS A1439 5.19, the touch drying time of the curable composition immediately after mixing the A agent and the B agent was measured (measurement condition: 23 ° C., 50% RH).

2) Storage stability test After preparation of agent A, the mixture was allowed to stand at 23 ° C. and 50% RH for 24 hours, and then the viscosity of agent A was measured using a BH type rotational viscometer in accordance with JIS K6833. (Measurement conditions: 23 ° C., 50% RH).
The agent A was filled in a glass bottle and left in a hot air circulation dryer adjusted to 50 ° C. After 4 weeks at 50 ° C., and allowed to stand at 23 ° C. and 50% RH for 24 hours, the viscosity was measured in the same manner as described above. The viscosity increase rate was calculated from the viscosity after storage and the initial viscosity, and evaluated according to the following evaluation criteria.
○: Thickening rate is 0.5 times or more and less than 2 times, ×: Thickening rate is less than 0.5 times or 2 times or more.

3) Tensile shear bond strength Tensile shear bond strength was measured using the obtained A agent and B agent. Adhesion conditions and measurement conditions are as follows.
Adherent: 5 mm thick mild steel plate 25 mm × 100 mm.
-Adhesive conditions A agent and B agent were measured so that it might become 1: 1 weight ratio, and it mixed on the conditions of 500 rpm of revolutions, and 1000 rpm of revolutions for 2 minutes using the vacuum planetary stirrer. The mixture was applied to the surface of the adherend, spread thinly, bonded together under the conditions of a temperature of 23 ° C. and a relative humidity of 50%, and pressed in two places with a 30 mm wide eyeball clip so that the thickness of the adhesive layer was 0.1 mm. . The bonding area was 12.5 mm × 25 mm. The bonded adherends were allowed to stand for 24 hours under the conditions of a temperature of 23 ° C. and a relative humidity of 50% to obtain test bodies for a tensile shear test.
-Measurement conditions About the obtained test body, the test shear rate was 50 mm / min and the tensile shear bond strength in 23 degreeC was measured.

In Table 2, the compounding quantity of each compounding substance is shown by g. Tin-based curing catalysts B1 to B4 are tin-based curing catalysts B1 to B4 obtained in Production Examples 1 to 4, respectively. Polymer P1 is polymer P1 obtained in Synthesis Example 1, and details of the compounding substances are as follows. It is as follows.
* 7) Bisphenol A type epoxy resin: trade name “jER828”, manufactured by Mitsubishi Chemical Corporation, number average molecular weight of about 370.
* 8) Hydrogenated bisphenol A type epoxy resin: Trade name “Adeka Resin EP-4080E”, manufactured by ADEKA Corporation, number average molecular weight of about 350.
* 9) Polyethylene glycol skeleton epoxy resin: Trade name “Adeka Resin ED-506”
, Manufactured by ADEKA Corporation, ethylene glycol diglycidyl ether, number average molecular weight of about 620.
* 10) KBM-403: 3-glycidoxypropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-403”, manufactured by Shin-Etsu Chemical Co., Ltd.
* 11) SAT200: A polymer whose main chain is polyoxypropylene and has a dimethoxysilyl group at the molecular end, trade name “Syryl SAT200”, manufactured by Kaneka Corporation.
* 13) EH30: 2,4,6-trisdimethylaminomethylphenol, trade name “Versamine EH-30”, manufactured by Cognis Japan.
* 14) KBM-603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, trade name “Shin-Etsu Silicone KBM-603”, manufactured by Shin-Etsu Chemical Co., Ltd.

(Examples 11 to 20)
Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 4. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 5.

  In Table 4, the compounding quantity of each compounding substance is shown by g. Tin-based curing catalysts B5 to 8 are tin-based curing catalysts B5 to 8 obtained in Production Examples 5 to 8, respectively, and details of each compounding substance are the same as in Table 2.

(Examples 21 to 25)
Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 6. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 7.

  In Table 6, the compounding quantity of each compounding substance is shown by g. Tin-based curing catalysts B9 and B are tin-based curing catalysts B9 and 10 obtained in Production Examples 9 and 10, respectively, and the details of each compounding substance are the same as in Table 2.

(Examples 26 to 32)
Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 8. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 9.

In Table 8, the compounding quantity of each compounding substance is shown by g, and the compounding quantity of the polymer P3 is shown by solid content. Tin-based curing catalysts B1, B11-B13 are tin-based curing catalysts B1, B11-B13 obtained in Production Examples 1, 11-13, respectively, and polymers P1-P3 are obtained in Synthesis Examples 1-3, respectively. The details of each compounding substance are the same as in Table 2 for polymers P1 to P3. Details of other compounding substances are as follows.
* 18) MA440: a mixture of a polymer having a main chain of polyoxypropylene and having a methyldimethoxysilyl group at the molecular end and a polymer having a main chain of a polymethacrylic acid ester and having a methyldimethoxysilyl group in the molecule; Product name “Cyrill MA440”, manufactured by Kaneka Corporation.
* 19) XMAP SA120S: (meth) acrylic acid ester copolymer having a methyldimethoxysilyl group, trade name “XMAP SA120S”, manufactured by Kaneka Corporation.
* 20) EP505S: A polymer containing 33% by mass of process oil, the main chain of which is polyisobutylene and having a methyldimethoxysilyl group at the molecular end, trade name “Epion EP505S”, manufactured by Kaneka Corporation.

(Comparative Examples 1-4)
Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 10. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 11.

In Table 10, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as those in Table 2, and details of other compounding substances are as follows.
* 15) U810: Dioctyltin dilaurate, trade name “Neostan U-810”, manufactured by Nitto Kasei Co., Ltd.
* 16) S-1: Reaction product of dioctyltin salt and normal ethyl silicate, trade name “Neostan S-1”, manufactured by Nitto Kasei Co., Ltd.

（比較例５〜１２）
表１２に示した如く配合物質を変更した以外は実施例１と同様の方法によりＡ剤及びＢ剤を得た。得られたＡ剤及びＢ剤に対し、実施例１と同様の方法により各測定を行った。結果を表１３に示した。

(Comparative Examples 5-12)
Agent A and Agent B were obtained in the same manner as in Example 1 except that the compounding substances were changed as shown in Table 12. Each measurement was performed by the method similar to Example 1 with respect to the obtained A agent and B agent. The results are shown in Table 13.

  In Table 12, the compounding quantity of each compounding substance is shown by g. Details of each compounding substance are the same as those in Tables 2, 8 and 10.

  As shown in Tables 2 to 9, in Examples 1 to 32, curable compositions having excellent storage stability and high curing speed and high curability were obtained. Moreover, the curable composition of this invention showed the outstanding adhesive performance.

Claims (6)

A two-component curable composition comprising an A agent containing an epoxy resin and a liquid tin-based curing catalyst, and a B agent containing a crosslinkable silicon group-containing organic polymer and an epoxy resin curing agent,
The liquid tin-based curing catalyst is a reaction product obtained by reacting at least one tin compound selected from the group consisting of dioctyltin oxide and dioctyltin carboxylate with an alkoxysilane compound represented by the following formula (1). Is a thing,
The amount of the epoxy resin is 10 to 200 parts by mass, the amount of the liquid tin-based curing catalyst is 0.1 to 20 parts by mass, and the epoxy resin is 100 parts by mass of the crosslinkable silicon group-containing organic polymer. A two-component curable composition characterized in that the amount of curing agent used is 1 to 60 parts by mass.
R ¹ R ² _a Si (OR ³ ) _3-a (1)
(In the formula (1), R ¹ is a phenyl group, a vinyl group, an alkyl group having 6 to 20 carbon atoms, a glycidoxyalkyl group, or an epoxycycloalkyl group, R ² is a methyl group or a phenyl group, a is 0 or 1 (provided that, when R ¹ is an alkyl group having 6 to 20 carbon atoms, a is 0); R ³ is a monovalent hydrocarbon group having 1 to 4 carbon atoms and a monovalent halogen; And a plurality of R ³ groups may be the same or different.)   The (A) crosslinkable silicon group-containing organic polymer is a polyoxyalkylene polymer having a crosslinkable silicon group, a (meth) acrylic polymer having a crosslinkable silicon group, and a saturated carbonization having a crosslinkable silicon group. The two-component curable composition according to claim 1, wherein the two-component curable composition is at least one selected from the group consisting of hydrogen polymers. The two-component curable composition according to claim 1 or 2, wherein R ^{1 in the} formula (1) is a phenyl group or a vinyl group. The two-component curable composition according to claim 1 or 2, wherein R ^{1 in the} formula (1) is a phenyl group.   The two-component curable composition according to any one of claims 1 to 4, wherein the alkoxysilane compound is diphenyl dialkoxysilane.   A cured product obtained by curing the two-component curable composition according to any one of claims 1 to 5.