JP6872975B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition having improved durability and a cured product obtained by curing the curable composition.

Polyoxyalkylene-based polymers having a reactive silyl group are known as moisture-reactive polymers, and are contained in many industrial products such as adhesives, sealants, coating materials, paints, and adhesives, and are used in a wide range of fields. It is used in. The polyoxyalkylene polymer having such a reactive silyl group has a wide range of application because it has a relatively low viscosity at room temperature and is easy to handle, and the cured product obtained after the reaction also exhibits good elasticity. ..

The sealing material is generally used for the purpose of filling joints and gaps between various members to provide watertightness and airtightness. Therefore, since it is extremely important to follow the site of use for a long period of time, it is required that the cured product has excellent resilience and durability as physical properties. In particular, sealing materials for working joints (kasagi, around glass, around window frames / sashes, curtain walls, various exterior panels) of buildings with large fluctuations in joint width, sealing materials for direct glazing, sealing materials for double glazing, etc. The composition used as a sealing material for the SSG method is required to have excellent resilience and durability.

On the other hand, it is known that two or more kinds of polymers having different molecular weights are blended as a polyoxyalkylene polymer having a reactive silyl group used as a sealing material. In particular, low molecular weight components having a molecular weight of 6000 or less are used for reducing the viscosity, substituting a plasticizer that causes contamination around the sealing portion or the surface coating film, improving the tear strength, and the like (Patent Documents 1 to 6). ..

Japanese Unexamined Patent Publication No. 05-059267 Japanese Unexamined Patent Publication No. 09-095619 Japanese Unexamined Patent Publication No. 05-065406 International Publication WO2005 / 0733222 Japanese Unexamined Patent Publication No. 2011-11125 Japanese Unexamined Patent Publication No. 2013-194197

An object of the present invention is to provide a curable composition having improved durability and a cured product obtained by curing the curable composition.

In order to solve the above problems, the present inventor conducted a diligent study and found that 100 parts by weight of a polyoxyalkylene polymer having a reactive silyl group of 50,000 or less and having a number average molecular weight of more than 6,000. It has been found that durability is improved by preparing a curable composition containing 1 to 4 parts by weight of a polyoxyalkylene polymer having a reactive silyl group having an average molecular weight of 1,000 or more and 6,000 or less. , The present invention has been completed.

That is, the present invention
(I). 100 parts by weight of a polyoxyalkylene polymer (A) having a number average molecular weight of more than 6,000 and a reactive silyl group of 50,000 or less,
1 to 4 parts by weight of a polyoxyalkylene polymer (B) having a reactive silyl group having a number average molecular weight of 1,000 or more and 6,000 or less.
The present invention relates to a curable composition containing.

(II). (A) The curable composition according to (I), wherein the number average molecular weight of the components is 10,000 or more and 50,000 or less.

(III). (B) The curable composition according to (I) or (II), wherein the component has an average of more than 1.0 reactive silyl groups per molecule.

(IV). (B) The curable composition according to any one of (I) to (III), wherein the component has an average of more than 1.2 reactive silyl groups per molecule.

(V). The curable composition according to any one of (I) to (IV), wherein the component (A) has an average of more than 1.0 reactive silyl groups per molecule.

(VI). The curable composition according to any one of (I) to (V), wherein the reactive silyl group of the component (A) and / or the component (B) is the general formula (1).
−SiR ¹ _3-a X _a (1)
{In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, which may independently have a heteroatom-containing group or a substituent composed of a halogen atom. X is independently a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. }
(VII). The curable composition according to any one of (I) to (VI), wherein the component (A) and / or the component (B) is a polyoxypropylene-based polymer.

(VIII). The curable composition according to any one of (I) to (VII), further containing 0.5 parts by weight or more of the antioxidant (C).

(IX). The present invention relates to a cured product obtained by curing the curable composition according to any one of (I) to (VIII).

(X). A functional group capable of introducing a reactive silicon group into 100 parts by weight of the polyoxyalkylene polymer (a) having a functional group capable of introducing a reactive silicon group and having a number average molecular weight of more than 6,000 and 50,000 or less. Reactive silyl obtained by mixing 1 to 4 parts by weight of the polyoxyalkylene polymer (b) having a number average molecular weight of 1,000 or more and 6,000 or less, and then introducing a reactive silicon group. The present invention relates to a method for producing a polyoxyalkylene polymer having a group.

According to the present invention, a curable composition having improved durability and a cured product obtained by curing the curable composition can be obtained.

Hereinafter, the present invention will be described in detail.
In the present invention, 100 parts by weight of a polyoxyalkylene polymer (A) {also referred to as a polyoxyalkylene polymer (A)} having a number average molecular weight of more than 6,000 and a reactive silyl group of 50,000 or less. , Contains 1 to 4 parts by weight of a polyoxyalkylene polymer (B) {also referred to as a polyoxyalkylene polymer (B)} having a reactive silyl group having a number average molecular weight of 1,000 or more and 6,000 or less. Concers about curable compositions.

<< Polyoxyalkylene polymer (A) >>
In the present invention, the polyoxyalkylene polymer (A) having a number average molecular weight of more than 6,000 and having a reactive silyl group of 50,000 or less is used.

<Reactive silyl group>
The reactive silyl group of the polyoxyalkylene polymer (A) may be located at either the terminal or side chain of the polymer, but at least one is preferably at the terminal, and more preferably at the terminal only.

The number of reactive silyl groups contained in one molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0 on average, more preferably more than 1.2. It is more preferable to have more than 1.5 pieces. The upper limit is preferably 4 or less, and more preferably 3 or less.

As the reactive silyl group, the general formula (1):
−Si (R ¹ ) _3-a (X) _a (1)
{In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, which may independently have a heteroatom-containing group or a substituent composed of a halogen atom. X is independently a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. } Is preferred.

Examples of R ¹ 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; a methyl halide group such as a chloromethyl group; Examples thereof include an alkoxymethyl group such as a methyl group, but a methyl group, a chloromethyl group, and a methoxymethyl group are preferable.

Examples of X include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like. Among these, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.

Specific examples of the reactive silicon group (Si (R ¹ ) _3-a (X) _a ) of the polyoxyalkylene polymer (A) include a trichlorosilyl group, a dichloromethylsilyl group, and a chlorodimethylsilyl group. Dichlorophenylsilyl group, trimethoxysilyl group, triethoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, ethyldimethoxysilyl group, methoxydimethylsilyl group, ethoxydimethylsilyl group, dimethoxyphenylsilyl group, dimethoxyethylsilyl group, (Chloromethyl) dimethoxysilyl group, (chloromethyl) diethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N-diethylaminomethyl) dimethoxysilyl group, (N, N) -Diethylaminomethyl) diethoxysilyl group, triacetoxysilyl group, diacetoxymethylsilyl group, diacetoxyphenylsilyl group Tris (2-propenyloxy) silyl group, bis (dimethylketoximate) methylsilyl group, bis (cyclohexylketoxy) Mate) Methylsilyl group and the like can be mentioned, but the present invention is not limited thereto. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it shows high activity and a cured product having good mechanical properties can be obtained. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are particularly preferable, and from the viewpoint of stability, a methyldimethoxysilyl group, a methyldiethoxysilyl group, and a triethoxysilyl group. Is particularly preferable, and from the viewpoint of safety, a methyldiethoxysilyl group and a triethoxysilyl group are particularly preferable, and a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable because they are easy to produce.

<Main chain structure>
The main chain structure of the polyoxyalkylene polymer (A) may be linear or may have a branched chain.

Examples of the main chain structure of the polyoxyalkylene polymer (A) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-. Examples thereof include a polyoxybutylene copolymer, but polyoxyethylene and polyoxypropylene are preferable, and polyoxypropylene is more preferable.

The number average molecular weight of the polyoxyalkylene polymer (A) is determined from the polystyrene-equivalent molecular weight in GPC, and is larger than 6,000 and 50,000 or less. It is more preferably 10,000 or more and 50,000 or less, and particularly preferably 10,000 or more and 30,000 or less. If the number average molecular weight is less than 6,000, the required rubber elasticity of the cured product may not be obtained, and if it exceeds 50,000, the viscosity becomes high, which tends to be inconvenient in terms of workability.

The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less. , 1.4 or less is particularly preferable, and 1.3 or less is most preferable. The molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Method for synthesizing polyoxyalkylene polymer (A)>
Next, a method for synthesizing the polyoxyalkylene polymer (A) will be described.

The polyoxyalkylene polymer (A) is a hydroxyl group-terminated polyoxyalkylene polymer by a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex. After obtaining, (i) a method of converting the hydroxyl group of the obtained hydroxyl group-terminated polyoxyalkylene polymer into a carbon-carbon unsaturated group and then adding a silane compound by a hydrosilylation reaction, (ii) is obtained. It is preferable to obtain the polyoxyalkylene polymer (A) by a method of reacting the hydroxyl group-terminated polyoxyalkylene polymer with a compound having both a group that reacts with the hydroxyl group and a reactive silyl group. Of the above two methods, the method (i) is more preferable because the reaction is simple, the amount of the reactive silyl group introduced is adjusted, and the physical properties of the obtained reactive silyl group-containing polymer are stable.

The initiator having a hydroxyl group has one or more hydroxyl groups such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, and polypropylene monoalkyl ether. Things can be mentioned.

Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.

Examples of the carbon-carbon unsaturated group used in the method (i) include a vinyl group, an allyl group, and a metharyl group. Of these, the allyl group is preferable.

As a method for converting the hydroxyl group of (i) into a carbon-carbon unsaturated group, an alkali metal salt is allowed to act on the hydroxyl group terminal-containing polymer, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of causing.

Examples of the halogenated hydrocarbon compound used in the method (i) include vinyl chloride, allyl chloride, metallic chloride, vinyl bromide, allyl bromide, metallic bromide, vinyl iodide, allyl iodide, and metallic iodide. Be done.

Examples of the hydrosilane compound used in the method (i) include halogenated silanes such as trichlorosilane, dichloromethylsilane, chlorodimethylsilane, and dichlorophenylsilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, and ethyl. Dimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, dimethoxyphenylsilane, dimethoxyethylsilane, (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, ( Alkoxysilanes such as N, N-diethylaminomethyl) dimethoxysilane, (N, N-diethylaminomethyl) diethoxysilane; asyloxysilanes such as triacetoxysilane, diacetoxymethylsilane, diacetoxyphenylsilane; bis (dimethyl) Examples thereof include ketoximate silanes such as ketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane, and isopropenyloxysilanes (deacetone type) such as tris (2-propenyloxy) silane.

The hydrosilylation reaction used in method (i) is accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used. For example, a carrier such as alumina, silica, or carbon black on which platinum is supported, platinum chloride acid; a platinum chloride acid complex composed of platinum chloride acid and alcohol, aldehyde, ketone, or the like; a platinum-olefin complex [for example, Pt (CH). ₂ = CH ₂ ) ₂ (PPh ₃ ), Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ]; Platinum-vinylsiloxane complex [Pt {(vinyl) Me ₂ SiOSiMe ₂ (vinyl)}, Pt {Me (vinyl) SiO} ₄ ]; Platinum-phosphine complex [Ph (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ ]; Platinum-phosphite complex [Pt {P (OPh) ₃ } ₄ ] and the like can be used.

Examples of the compound having both a hydroxyl group-reacting group and a reactive silicon group that can be used in the method (ii) include 3-isocyanappropyltrimethoxysilane, 3-isocyanuppropyldimethoxymethylsilane, and 3-isocyanuppropyltriethoxysilane. Isoisocyanates such as isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane; 3-glycidoxypropyl Examples thereof include epoxysilanes such as trimethoxysilane and 3-glycidoxypropyldimethoxymethylsilane.

<< Polyoxyalkylene polymer (B) >>
In the present invention, a polyoxyalkylene polymer (B) having a reactive silyl group having a number average molecular weight of 1,000 or more and 6,000 or less is used. Durability is improved by adding 1 to 4 parts by weight of the polyoxyalkylene polymer (B).

<Reactive silyl group>
The reactive silyl group of the polyoxyalkylene polymer (B) may be located at either the terminal or side chain of the polymer, but at least one is preferably at the terminal, and more preferably at the terminal only.

The number of reactive silyl groups contained in one molecule of the polyoxyalkylene polymer (B) is preferably more than 1.0 on average, more preferably more than 1.2. It is more preferable to have more than 1.5 pieces. The upper limit is preferably 4 or less, and more preferably 3 or less.

As the reactive silyl group, the same reactive silyl group described in the above polyoxyalkylene polymer (A) can be used.

<Main chain structure>
As the main chain structure of the polyoxyalkylene polymer (B), the same main chain structure as that of the polyoxyalkylene polymer (A) can be used.

The number average molecular weight of the polyoxyalkylene polymer (B) is determined from the polystyrene-equivalent molecular weight in GPC and is 1,000 or more and 6,000 or less. It is more preferably 2,000 or more and 6,000 or less, and particularly preferably 2,000 or more and 5,000 or less. If the number average molecular weight is less than 1,000, the required rubber elasticity of the cured product may not be obtained, and if it exceeds 6,000, the effect of durability may be reduced.

The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (B) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less. , 1.4 or less is particularly preferable, and 1.3 or less is most preferable. The molecular weight distribution of the polyoxyalkylene polymer (B) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

<Method for synthesizing polyoxyalkylene polymer (B)>
The polyoxyalkylene polymer (B) can be obtained by the same method as the method for synthesizing the polyoxyalkylene polymer (A) described above.

Further, the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) can be synthesized separately and then blended, but have a number average molecular weight having a functional group into which a reactive silicon group can be introduced. Is larger than 6,000 and has 100 parts by weight of a polyoxyalkylene polymer of 50,000 or less and a functional group into which a reactive silicon group can be introduced, and has a number average molecular weight of 1,000 or more and 6,000 or less. It can also be obtained by a synthetic method in which 1 to 4 parts by weight of an oxyalkylene polymer is mixed and then a reactive silicon group is introduced. In this case, the number of reactive silyl groups per terminal of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B) becomes equal, and a well-balanced cured product can be obtained. preferable.

<Amount of polyoxyalkylene polymer (B) added>
The amount of the polyoxyalkylene polymer (B) added is 1 to 4 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A). .. If the amount added is more than 4 parts by weight, the durability is lowered.

<Antioxidant (C)>
It is preferable to use an antioxidant (antioxidant) in the composition of the present invention. The use of antioxidants can further increase the durability of the cured product.

Examples of the antioxidant include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based, but hindered phenol-based agents are particularly preferable.

Examples of hindered phenol-based antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α). -Methylbenzyl) phenol, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3) -Methyl-6-tert-butylphenol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol [3- (3,5-di-t-butyl-4-hydroxy) Phenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3] -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) , 3,5-Di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4) -Hydroxy-benzyl) benzene, bis (3,5-di-t-butyl-4-hydroxy-benzylphosphonate ethyl) calcium, tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate , 2,4-bis [(octylthio) methyl] -O-cresol, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2, 4-Di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazol, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3, 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-) t-Butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazole-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxy Phenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-Butylphenyl-3,5-di-t-Butyl-4-hydroxybenzoate and others,

And so on.

These hindered phenolic antioxidants, or other antioxidants, are commercially available under the following trade names. Adeka Stub AO-30, Adeka Stub AO-40, Adeka Stub AO-50, Adeka Stub AO-60, Adeka Stub AO-80, Adeka Stub AO-330, Adeka Stub AO-611, Adeka Stub AO-612, Adeka Stub AO -613, ADEKA STAB AO-512, ADEKA STAB AO-15, ADEKA STAB AO-18, ADEKA STAB AO-37, IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1035, IRGANOX manufactured by BASF Japan. -1076, IRGANOX-1098, IRGANOX-1135, IRGANOX-1330, IRGANOX-1425WL, IRGANOX-1520L, IRGANOX-1726, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH, Sumitomo Chemical Co., Ltd. Sumilizer GM, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM- S, Sumilizer WX-R, Sumilizer WX-RC, Naugard XL-1 manufactured by Universal Co., Ltd.

The amount of the antioxidant used is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more, based on 100 parts by weight of the polyoxyalkylene polymer (A). The upper limit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 3 parts by weight or less.

<< Other additives >>
In addition to the polyoxyalkylene polymer (A), the polyoxyalkylene polymer (B), and the antioxidant (C), the composition of the present invention contains a silanol condensation catalyst, a filler, and adhesiveness as additives. Adapters, plasticizers, solvents, diluents, silicates, anti-sags, light stabilizers, UV absorbers, property modifiers, tackifier resins, epoxy group-containing compounds, photocurable substances, oxygen curable substances, A surface improving agent, an epoxy resin, another resin, a flame retardant, and a foaming agent may be added. Further, various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposing agents, lubricants, pigments, mold inhibitors and the like. Be done.

<Silanol condensation catalyst>
The purpose of the present invention is to promote the reaction of hydrolyzing and condensing the reactive silyl groups of the polyoxyalkylene polymer (A) and the polyoxyalkylene polymer (B), and to extend or crosslink the polymer. A silanol condensation catalyst may be used.

It is already known that a large number of catalysts can be used as the silanol condensation catalyst, and examples thereof include organotin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, and inorganic acids.

Specific examples of the organic tin compound include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), and dibutyltin bis (dibutyltin bis). Ethyl maleate), dibutyl tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (Ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonylphenoxide), dibutenyl tin oxide, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), dioctyl tin bis (acetyl) Acetnate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dioctyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, etc. Be done. Due to the growing concern about the environment in recent years, it is preferable to use dioctyltin compounds over dibutyltin compounds.

Specific examples of the metal carboxylate salt include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, Examples thereof include manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate. As the carboxylic acid group, the following carboxylic acids and various metals can be combined. As the metal species, divalent tin, bismuth, divalent iron, trivalent iron, zirconium and titanium are preferable because of their high activity, and divalent tin is most preferable.

Specific examples of amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, Aliphatic primary amines such as cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamilamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, disetylamine , Distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine and other aliphatic secondary amines; triamylamine, trihexylamine, trioctylamine and other aliphatic tertiary amines; triallylamine, Aliper unsaturated amines such as oleylamine; aromatic amines such as aniline, laurylaniline, stearylaniline, triphenylamine; pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylaminopyridine) , 2-Hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholin, N-methylmorpholin, piperidine, 2-piperidin methanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1, 4,5,6-Tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 6- (dibutylamino) -1,8-diazabicyclo [5,4,0] undecene-7 (DBA-DBU), 6- (2-Hydroxypropyl) -1,8-diazabicyclo [5,4,5] undec-7-ene (OH-DBU), OH-DBU hydroxyl groups were modified by urethanization or the like. Compounds, nitrogen-containing heterocyclic compounds such as 1,5-diazabicyclo [4,3,0] nonen-5 (DBN), 1,4-diazabicyclo [2,2,2] octane (DABCO), aziridine; DBU Phenol salt (specifically, trade name: U-CAT SA1 (manufactured by San-Apro)), DBU octylate (specifically, trade name: U-CAT SA102 (manufactured by San-Apro)), DBU p-toluene Sulfonate (specifically, trade name: U-CAT SA506 (manufactured by San-Apro)), DBN octylate (ingredients) Physically, salts derived from nitrogen-containing heterocyclic compounds such as trade name: U-CAT 1102 (manufactured by San-Apro), and other amines include monoethanolamine, diethanolamine, triethanolamine, 3 -Hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2- (2-) Aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- Amines such as (1-piperazinyl) ethylamine, xylylene diamine, 2,4,6-tris (dimethylaminomethyl) phenol; guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanide, 1-o-trilbiguanide And biguanides such as 1-phenylbiguanide.

Among these, amidines such as 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, DBN; guanidines such as guanidine, phenylguanidine, diphenylguanidine; butylbiguanides, 1 Biguanides such as -o-tolylbiguanide and 1-phenylbiguanide are preferable because they show high activity, and aryl group-substituted biguanides such as 1-o-tolylbiguanide and 1-phenylbiguanide can be expected to have high adhesiveness. preferable.

Further, although the amine compound is basic, the amine compound having a pKa value of the conjugate acid of 11 or more is preferable because of its high catalytic activity, and 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBN and the like are particularly preferable because the pKa value of the conjugate acid is 12 or more and exhibits high catalytic activity.

In the present invention, as the amine compound used in the silanol condensation catalyst, an amino group-containing silane coupling agent (sometimes referred to as aminosilane) and a ketimine compound that produces the amine compound by hydrolysis can also be used.

Specific examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, pivalic acid, 2,2-dimethylbutyric acid, and 2,2-diethylbutyric acid. Examples thereof include 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, and versatic acid. 2-Ethylhexanoic acid, neodecanoic acid, and versatic acid have high activity and are preferable from the viewpoint of availability. Derivatives of the above carboxylic acids such as carboxylic acid anhydrides, alkylcarboxylic acids, amides, nitriles and acyl halides can also be used.

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonate) diisopropoxytitanium, and diisopropoxytitanium bis (ethylacetatete). , Aluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetacetate), diisopropoxyaluminum ethylacetate, zirconium compounds such as zirconium tetrakis (acetylacetonate), hafnium compounds such as tetrabutoxyhafnium. Kind is mentioned.

Other silanol condensation catalysts include organic sulfonic acids such as trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride ethylamine complex and the like. Boron trifluoride complex; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1,2,3,3,3-hexafluoro-1-diethylaminopropane (MEC81) , Commonly known as Ishikawa Reagent), potassium hexafluorophosphate, Na ₂ SiF ₆ , K ₂ SiF ₆ , (NH ₄ ) ₂ SiF _6, and other fluorine anion-containing compounds.

Photoacid generators and photobase generators that generate acids and bases with light can also be used as silanol condensation catalysts. Examples of the photoacid generator include triarylsulfonium salts such as p-phenylbenzylmethylsulfonium salt, p-hydroxyphenylbenzylmethylsulfonium salt, triphenylsulfonium salt, and diphenyl [4- (phenylthio) phenyl] sulfonium salt, 4,4. -Bis [di (β-hydroxyethoxy) phenylsulfonio] phenisulfide bishexafluoroantimonate, diphenyliodonium salt, bis (4-tert-butylphenyl) iodonium salt, (4-tert-butoxyphenyl) phenyliodonium salt, Onium salt-based photoacid generators such as iodonium salts such as (4-methoxyphenyl) phenyliodonium salt, benzointosylate, pyrogalloltrimesylate, nitrobenzyl-9,10-diethoxyanthracen-2-sulfonate, N-( Trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept- Sulphonic acid derivatives such as 5-en-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthylimide, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) Diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-kisilylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethyl) Examples thereof include diazomethanes such as sulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and phenylsulfonyl (benzoyl) diazomethane, carboxylic acid esters, and iron arene complexes.

The silanol condensation catalyst may be used in combination with two or more different catalysts. For example, by using the amine compound and the carboxylic acid in combination, the effect of improving the reactivity may be obtained. .. The catalytic activity can also be enhanced by using an acid such as a carboxylic acid in combination with a phosphonium salt compound such as tetrabutylphosphonium hydroxide. In addition, the reactivity may be improved by using a halogen-substituted aromatic compound such as pentafluorophenol or pentafluorobenzaldehyde in combination with an amine compound.

The amount of the silanol condensation catalyst used is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and 0. 01 to 10 parts by weight is particularly preferable. If the blending amount of the silanol condensation catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, if the blending amount of the silanol condensation catalyst exceeds 20 parts by weight, the reaction rate is too fast, so that the usable time of the composition is shortened, which tends to deteriorate workability and storage stability.

<Filler>
Various fillers can be added to the composition of the present invention. As fillers, reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, molten silica, dolomite, silicic anhydride, hydrous silicic acid, and carbon black; heavy calcium carbonate, collagen carbonate, Like resin powder such as magnesium carbonate, silica soil, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, active zinc flower, PVC powder, PMMA powder, etc. Fillers: Fibrous fillers such as asbestos, glass fibers and filaments.

The amount of the filler used is preferably 1 to 400 parts by weight, particularly preferably 10 to 300 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

In order to improve the workability (sharpness, etc.) of the composition, an organic balloon or an inorganic balloon may be added. These fillers can be surface-treated, only one type may be used, or two or more types may be mixed and used. In order to improve workability (sharpness, etc.), the particle size of the balloon is preferably 0.1 mm or less. In order to make the surface of the cured product matte, 5 to 300 μm is preferable.

The balloon is a spherical filler having a hollow inside. Balloons can be added for the purpose of reducing the weight (lower specific density) of the composition. Examples of the material of this balloon include, but are not limited to, inorganic materials such as glass, silas, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran. , A plurality of types can be mixed, an inorganic material and an organic material can be combined, or laminated to form a plurality of layers.

Further, the heat-expandable fine-grained hollow body described in JP-A-2004-51701 or JP-A-2004-66749 can be used. The heat-expandable fine-grained hollow body is a polymer outer shell material (vinylidene chloride-based copolymer, acrylonitrile-based copolymer, or vinylinlinden chloride-acrylonitrile copolymer) containing a low-boiling compound such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape (coalescence). By heating the adhesive portion of the adhesive containing the heat-expandable fine-grained hollow body, the gas pressure inside the shell of the heat-expandable fine-grained hollow body increases, and the polymer outer shell material softens, resulting in a dramatic expansion in volume. And plays a role of peeling off the adhesive interface. By adding the heat-expandable fine-grained hollow body, an adhesive composition that can be easily peeled off without breaking the material by simply heating when not needed, and can be peeled off by heat without using any organic solvent can be obtained.

<Adhesive imparting agent>
An adhesiveness-imparting agent can be added to the composition of the present invention.

As the adhesiveness-imparting agent, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltris (2-propoxy) silane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropyl. Methyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltriisopropoxysilane, N-β- (β-aminoethyl) aminoethyl-γ-aminopropyltri Methoxysilane, N-6-aminohexyl-γ-aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane , N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxy Amino group-containing silanes such as methylsilane, (phenylaminomethyl) trimethoxysilane, bis (3-trimethoxysilylpropyl) amine, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; γ- Isocyanate groups such as isocyanate propyltrimethoxysilane, γ-isocyanoxidetriethoxysilane, γ-isocyanuspropylmethyldiethoxysilane, γ-isocyanoxidepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane Containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiet Mercapto group-containing silanes such as xysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxy group-containing silanes such as trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane, N- Carboxyl silanes such as β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane Vinyl-type unsaturated group-containing silanes such as γ-chloropropyltrimethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanuratesilanes such as tris (trimethoxysilyl) isocyanurate; methyl (N-dimethoxymethylsilylmethyl) carbamate , Carbamate silanes such as methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate; (methoxymethyl) dimethoxymethylsilane, (methoxymethyl) ) Alkoxy group-containing silanes such as trimethoxysilane, (ethoxymethyl) trimethoxysilane, (phenoxymethyl) trimethoxysilane; 3- (trimethoxysilyl) propyl anhydride succinic acid, 3- (triethoxysilyl) propyl anhydride succinic acid. Examples thereof include silanes containing acid anhydrides such as acids. In addition, these partial condensates and derivatives obtained by modifying them, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, are also silane cups. It can be used as a ring agent.

The above silane coupling agents may be used alone or in combination.

Further, reactants of various silane coupling agents can also be used. Reaction products include isocyanate silane and hydroxyl group-containing compound, isocyanate silane and amino group-containing compound reaction product; amino silane and acrylic group-containing compound, methacryl group-containing compound reaction product (Michael addition reaction product); amino silane and epoxy group. Examples thereof include a reaction product with a containing compound, a reaction product with an epoxysilane and a carboxylic acid group-containing compound, and a reaction product with an amino group-containing compound. Reactants of silane coupling agents such as isocyanate silane and amino silane, amino silane and (meth) acrylic group-containing silane, amino silane and epoxy silane, and amino silane and acid anhydride-containing silane can also be used.

Specific examples of the adhesive imparting agent other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate and the like. The adhesive-imparting agent may be used alone or in combination of two or more. By adding these adhesiveness-imparting agents, the adhesiveness to the adherend can be improved.

The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

<Plasticizer>
A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity and slump property of the composition and the mechanical properties such as hardness, tensile strength and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include phthalate compounds such as dibutylphthalate, diisononylphthalate (DINP), diheptylphthalate, di (2-ethylhexyl) phthalate, diisodecylphthalate (DIDP), and butylbenzylphthalate; bis (2-ethylhexyl). ) -1,4-benzenedicarboxylate and other terephthalate compounds (specifically, trade name: EASTMAN168 (manufactured by EASTMAN CHEMICAL)); non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically) Specifically, trade name: Hexamol DINCH (manufactured by BASF); aliphatic polyvalent carboxylic acid ester compounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, and tributyl acetylcitate; butyl oleate. , Unsaturated fatty acid ester compounds such as methyl acetyllicinolate; alkyl sulfonic acid phenyl esters (specifically, trade name: Mesamol (manufactured by LANXESS)); phosphate ester compounds such as tricresyl phosphate and tributyl phosphate; Trimerit Examples thereof include acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated phthalate; process oils; epoxidized soybean oil, epoxy plasticants such as benzyl epoxystearate, and the like.

Moreover, a polymer plasticizer can be used. When a high molecular plasticizer is used, the initial physical properties can be maintained for a long period of time as compared with the case where a low molecular plasticizer is used. Further, the drying property (paintability) when the alkyd paint is applied to the cured product can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; Polyester-based plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid, and phthalic acid and divalent alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; Further, polyether polyols such as 1,000 or more polyethylene glycols, polypropylene glycols, polytetramethylene glycols, or derivatives such as derivatives obtained by converting the hydroxy groups of these polyether polyols into ester groups, ether groups, etc .; Polystyrenes such as poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like can be mentioned. In addition, various polymers can be imparted with physical properties by copolymerizing a monomer containing a reactive group. For example, it is known that the use of polybutadiene grafted with maleic acid improves the adhesiveness improving effect and the elastic recovery rate.

The amount of the plasticizer used is preferably 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, and particularly preferably 20 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A). If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 300 parts by weight, the mechanical strength of the cured product will be insufficient. The plasticizer may be used alone or in combination of two or more. Further, the low molecular weight plasticizer and the high molecular weight plasticizer may be used in combination. In addition, these plasticizers can also be blended at the time of producing the polymer.

<Solvent, diluent>
Solvents or diluents can be added to the compositions of the present invention. The solvent and diluent are not particularly limited, but aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers and the like can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher, due to the problem of air pollution when the composition is used indoors. .. The above solvent or diluent may be used alone or in combination of two or more.

<Sylicate>
A silicate can be added to the composition of the present invention. This silicate acts as a cross-linking agent and has a function of improving the resilience, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. Furthermore, it also has the effect of improving adhesiveness, water resistance, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane and alkylalkoxysilane or their partially hydrolyzed condensates can be used.

Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkylsilicates) such as silane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

The partially hydrolyzed condensate of tetraalkoxysilane is more preferable because the effect of improving the restorability, durability, and creep resistance of the present invention is greater than that of tetraalkoxysilane.

Examples of the partially hydrolyzed condensate of the tetraalkoxysilane include those obtained by adding water to the tetraalkoxysilane by a usual method and partially hydrolyzing and condensing the tetraalkoxysilane. Further, as the partially hydrolyzed condensate of the organosilicate compound, a commercially available product can be used. Examples of such a condensate include methyl silicate 51 and ethyl silicate 40 (both manufactured by Corcote Co., Ltd.).

When silicate is used, the amount used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

<Sauce preventive agent>
If necessary, a sagging inhibitor may be added to the composition of the present invention in order to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when a rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or an organic fiber as described in JP-A-2003-155389 is used, the thixophilicity is high. A composition having good workability can be obtained. These anti-sauce agents may be used alone or in combination of two or more.

The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. The use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, but hindered amine-based compounds are particularly preferable.

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

<UV absorber>
An ultraviolet absorber can be used in the composition of the present invention. The use of UV absorbers can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, but benzotriazole-based compounds are particularly preferable, and commercially available names such as tinubin P, tinubin 213, tinubin 234 and tinubin 326, Examples thereof include chinubin 327, chinubin 328, chinubin 329, and chinubin 571 (all manufactured by BASF). 2- (2H-1,2,3-benzotriazole-2-yl) -phenolic compounds are particularly preferred. Further, it is preferable to use a phenol-based or hindered phenol-based antioxidant, a hindered amine-based photostabilizer, and a benzotriazole-based ultraviolet absorber in combination.

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

<Physical characteristic adjuster>
If necessary, a physical property adjusting agent for adjusting the tensile properties of the cured product produced may be added to the curable composition of the present invention. The physical property adjusting agent is not particularly limited, and for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane and phenyltrimethoxysilane. Arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; tris (trimethylsilyl) borate, tris (triethyl) Examples thereof include trialkylsilylborates such as silyl) borate; silicone varnishes; polysiloxanes and the like. By using the physical property adjusting agent, the hardness of the composition of the present invention when cured can be increased, or conversely, the hardness can be decreased to achieve elongation at break. The above-mentioned physical property adjusting agent may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis has an action of lowering the modulus of the cured product without aggravating the stickiness of the surface of the cured product. Particularly, a compound that produces trimethylsilanol is preferable. Examples of the compound that produces a compound having a monovalent silanol group in the molecule by hydrolysis include the compounds described in JP-A-5-117521. Further, a compound that is a derivative of an alkyl alcohol such as hexanol, octanol, and decanol and that produces a silicon compound that produces a silane monool such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029. Examples thereof include compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups, such as propane, glycerin, pentaerythritol, and sorbitol, and that produce silicon compounds that produce silane monool by hydrolysis.

The amount of the physical property adjusting agent used is preferably 0.1 to 10 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A).

<Adhesive-imparting resin>
To the present invention, a tackifier resin can be added for the purpose of enhancing the adhesiveness and adhesion to the base material, or if necessary. The adhesive-imparting resin is not particularly limited, and a commonly used resin can be used.

Specific examples include terpene resins, aromatic-modified terpene resins and hydrogenated terpene resins obtained by hydrogenating them, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, and xylene-phenols. Resin, cyclopentadiene-phenol resin, kumaron inden resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon) Resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like. These may be used alone or in combination of two or more.

The styrene-based block copolymer and its hydrogen additive are not particularly limited, and are, for example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylene. Examples thereof include butylene-styrene block copolymer (SEBS), styrene-ethylenepropire-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

Among these, a terpene-phenol resin is preferable because it has high compatibility with the polyoxyalkylene-based polymers (A) and (B) and a high adhesion effect can be obtained. On the other hand, when the color tone is important, a hydrocarbon resin is preferable.

The amount of the tackifier resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, and preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). More preferred. If it is less than 2 parts by weight, it is difficult to obtain the effect of adhesion and adhesion to the substrate, and if it exceeds 100 parts by weight, the viscosity of the composition becomes too high and handling may be difficult.

<Compound containing epoxy group>
In the composition of the present invention, a compound containing an epoxy group can be used. The use of a compound having an epoxy group can enhance the resilience of the cured product. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate. , Epoxy butyl steerate and the like. Of these, E-PS is particularly preferable. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).

<Photocurable substance>
A photocurable substance can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a fairly short time due to the action of light, resulting in a physical change such as hardening. Many known compounds of this type include organic monomers, oligomers, resins, and compositions containing them, and any commercially available compound can be adopted. As a typical example, unsaturated acrylic compounds, polyvinyl chlorides, azide resins and the like can be used.

The unsaturated acrylic compound is a monomer, an oligomer or a mixture thereof having one or several acrylic or methacrylic unsaturated groups, and is a propylene (or butylene, ethylene) glycol di (meth) acrylate or neopentyl. Examples thereof include monomers such as glycol di (meth) dimethacrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245, (Trifunctional) Aronix M305. , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (polyfunctional) Aronix M-400, and the like, and in particular, compounds containing an acrylic functional group. Is preferable, and a compound containing three or more of the same functional groups on average in one molecule is preferable (all Aronix are products of Toa Synthetic Chemical Industry Co., Ltd.).

Examples of vinyl polysilicates include a photosensitive resin having a cinnamoyl group as a photosensitive group, obtained by esterifying polyvinyl alcohol with cinnamic acid, and many vinyl polysilicate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group, and is usually a rubber photosensitive liquid to which a diazide compound is added as a photosensitive agent, as well as a "photosensitive resin" (March 17, 1972). Publication, published by the Publishing Department of the Printing Society, pp. 93-, pp. 106-, pp. 117-), and these may be used alone or in combination, and a sensitizer may be added as necessary. Can be done. The effect may be enhanced by adding a sensitizer such as a ketone or a nitro compound or an accelerator such as an amine.

The photocurable substance is preferably used in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, 0.1 part by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A). Below 20 parts by weight, the cured product tends to be too hard and cracks tend to occur.

<Oxygen curable substance>
An oxygen-curable substance can be used in the composition of the present invention. An example of an unsaturated compound that can react with oxygen in the air is an oxygen-curable substance that reacts with oxygen in the air to form a cured film near the surface of the cured product, which causes stickiness on the surface and dust on the surface of the cured product. It acts to prevent the adhesion of dust and dirt. Specific examples of the oxygen-curable substance include dry oils such as diene oil and diene oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with the dry oils. , Silicon resin; polymers of 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers such as NBR and SBR obtained by copolymerizing a liquid polymer or a monomer such as acrylonitrile or styrene having copolymerizability with these diene compounds so that the diene compound is the main component. Further, these various modified products (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, vernicia oil and liquid diene-based polymers are particularly preferable. In addition, the effect may be enhanced by using a catalyst that promotes the oxidative curing reaction or a metal dryer in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.

The amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer (A). Is. If the amount used is less than 0.1 parts by weight, the improvement of contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in Japanese Patent Application Laid-Open No. 3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.

<Surface improver>
A surface improving agent can be added to the composition of the present invention. Examples of the surface improving material include long-chain alkylamines such as laurylamine, 2,2'-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, and tris (2,4-di-t-butylphenyl). ) Phosphite and other phosphorus compounds, oxazolidine compounds, etc. can be mentioned.

The amount of the surface improving agent used is preferably in the range of 0.3 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).

<Epoxy resin>
An epoxy resin can be used in combination with the composition of the present invention. The composition to which the epoxy resin is added is particularly preferable as an adhesive, particularly an adhesive for outer wall tiles. Examples of the epoxy resin include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame-retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, and bisphenol A. Glycidyl ether type epoxy resin with propylene oxide adduct, p-oxybenzoate glycidyl ether type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohols such as glycerin, hydrandin type epoxy resin, petroleum resin, etc. Examples thereof include epoxidized products of unsaturated polymers, but the present invention is not limited to these, and commonly used epoxy resins can be used. Those containing at least two epoxy groups in the molecule are preferable because they have high reactivity during curing and the cured product easily forms a three-dimensional network. More preferable ones include bisphenol A type epoxy resins and novolak type epoxy resins.

The ratio of these epoxy resins to the polyoxyalkylene polymer (A) used is in the range of (A) / epoxy resin = 100/1 to 1/100 by weight. When the ratio of (A) / epoxy resin is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of (A) / epoxy resin exceeds 100/1. Then, the strength of the cured polymer product becomes insufficient. The preferable usage ratio cannot be unconditionally determined because it varies depending on the use of the curable resin composition and the like, but for example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the epoxy resin cured product. It is preferable to use 1 to 100 parts by weight, more preferably 5 to 100 parts by weight of the polyoxyalkylene polymer (A) with respect to 100 parts by weight of the epoxy resin. On the other hand, when improving the strength of the cured product, it is preferable to use 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of the epoxy resin with respect to 100 parts by weight of the polyoxyalkylene polymer (A). ..

When an epoxy resin is added, it is natural that a curing agent that cures the epoxy resin can be used in combination with the composition of the present invention. The epoxy resin curing agent that can be used is not particularly limited, and a generally used epoxy resin curing agent can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidin, m-xylylene diamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly. Primary and secondary amines such as ethers; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Classes; dicyandiamides; boron trifluorinated complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecinyl anhydride, pyromellitic anhydride, chlorenic anhydride and the like; alcohols Compounds such as, but not limited to, phenols; carboxylic acids; diamine complex compounds of aluminum or zirconium can be exemplified. Further, the curing agent may be used alone or in combination of two or more.

When an epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

Ketimine can be used as a curing agent for the epoxy resin. Ketimine exists stably in the absence of moisture, is decomposed into primary amines and ketones by moisture, and the generated primary amine becomes a room temperature curable curing agent for epoxy resins. A one-component composition can be obtained by using ketimine. Such ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

Known amine compounds and carbonyl compounds may be used for the synthesis of ketimine. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, etc. Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino) Polyvalent amines such as ethyl) amines and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyltriethoxysilane, N- (β) -Aminoethyl) -γ-aminopropyltrimethoxysilane, aminosilanes such as N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; and the like can be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone. , Methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone and other aliphatic ketones; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane; and the like can be used.

When an imino group is present in ketimine, the imino group may be reacted with a styrene oxide; a glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; a glycidyl ester or the like.

These ketimines may be used alone or in combination of two or more, and 1 to 100 parts by weight are used with respect to 100 parts by weight of the epoxy resin, and the amount used is the type of epoxy resin and ketimine. Depends on.

<< Preparation of curable composition >>
The curable composition of the present invention can be prepared as a one-component type in which all the compounding components are compounded and sealed in advance and cured by the humidity in the air after construction, and a curing catalyst and a filler are separately used as a curing agent. , Plasticizer, water and the like may be blended, and the blending material and the organic polymer composition may be mixed before use to prepare a two-component type or a multi-component system having three or more components.

When the curable composition is a one-component type, all the compounding components are pre-blended. Therefore, the moist-containing compounding components are either dehydrated and dried in advance before use, or dehydrated by decompression or the like during compounding and kneading. Is preferable. When the curable composition is a multi-component type, it is not necessary to add a silanol condensation catalyst to the main agent containing an organic polymer having a reactive silicon group, so that even if the compounding agent contains a small amount of water. Although there is little concern about an increase in viscosity or gelation of the formulation, dehydration drying is preferable when long-term storage stability is required. As a dehydration and drying method, a heat drying method is preferable for a solid substance such as powder, a vacuum dehydration method for a liquid substance, or a dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is preferable. is there. Further, a small amount of the isocyanate compound may be blended and the isocyanate group may be reacted with water for dehydration. Alternatively, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water to dehydrate. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -By adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane, the storage stability is further improved.

The amount of the dehydrating agent, particularly the silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5, based on 100 parts by weight of the polyoxyalkylene polymer (A). The range of 10 parts by weight is preferable.

The method for preparing the composition of the present invention is not particularly limited. For example, the above-mentioned components are blended and kneaded at room temperature or heat using a mixer, roll, kneader, etc., or the components are used in a small amount of a suitable solvent. Ordinary methods such as dissolving and mixing can be adopted.

The curable composition of the present invention is a moisture-reactive composition in which the reaction proceeds by moisture, but is a so-called dual-curable composition used in combination with a thermosetting resin, a photocurable resin, or a radiation-curable resin. Can also be used as. Specifically, a curable resin utilizing an en-thiol addition reaction, a radical polymerization reaction of a (meth) acrylic group, a ring-opening polymerization reaction of an epoxy group, an addition reaction by hydrosilylation, a urethanization reaction, etc. can be used in combination. it can.

<< Applications >>
The composition of the present invention is suitable for use as a curable composition or an adhesive composition, and is an adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a waterproof material, and a coating waterproof material. , Molding agent, anti-vibration material, anti-vibration material, soundproof material, foam material, paint, spray material, etc. The cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, and therefore, among these, it is more preferable to use it as a sealing material or an adhesive.

In addition, electrical / electronic component materials such as solar cell backside encapsulants, electrical / electronic components such as insulation coating materials for electric wires / cables, electrical insulation materials for equipment, acoustic insulation materials, elastic adhesives, binders, contact types. Adhesives, spray-type sealants, crack repair materials, tiled adhesives, asphalt waterproofing adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical adhesive sheets, medical equipment Sealing material, dental impression material, food packaging material, sealing material for joints of exterior materials such as sizing boards, coating material, anti-slip coating material, cushioning material, primer, conductive material for electromagnetic wave shielding, thermal conductive material, hot melt material , Electrical and electronic potting agents, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, and rustproof / waterproof sealing materials for wire-reinforced glass and laminated glass end faces (cut parts), automobile parts It can be used for various purposes such as liquid sealants used in large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, marine parts, electrical parts, and various mechanical parts. Taking an automobile as an example, it can be used in a wide variety of ways such as plastic covers, trims, flanges, bumpers, window mountings, interior members, and adhesive mounting of exterior parts. In addition, it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc., alone or with the help of primers, and can be used as various types of sealing and adhesive compositions. .. The curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stones, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, leather, textiles, fabrics, paper, board and rubber adhesives, reactive post-bridge pressure sensitive adhesives, direct It can also be used as a glazing sealant, a multi-layer glass sealant, an SSG method sealant, a building working joint sealant, a civil engineering material, and a bridge material. Furthermore, it can also be used as an adhesive material such as an adhesive tape or an adhesive sheet.

In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited thereto.

(Synthesis Example 1)
Polyoxypropylene triol having a number average molecular weight of 4,200 was used as an initiator, and propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight having a hydroxyl group at the terminal was 24,600 (terminal group equivalent molecular weight 17). , 400), polyoxypropylene (P-1) having a molecular weight distribution of Mw / Mn = 1.31 was obtained. After adding 3 parts by weight of polyoxypropylene triol having a number average molecular weight of 4200 to 100 parts by weight of (P-1), 1.2 molar equivalents of sodium methoxide with respect to the hydroxyl group was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-1) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-1), and 6.3 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal. The obtained polyoxypropylene having a dimethoxymethylsilyl group is polyoxypropylene (A-1) having a dimethoxymethylsilyl group having a number average molecular weight of 24,600 and a polyoxypropylene having a number average molecular weight of 4,200. It contained oxypropylene (B-1) in a ratio of 100: 3, and the number of silyl groups per molecule was 1.8.

(Synthesis Example 2)
To 500 g of (Q-1) obtained in Synthesis Example 1, 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added, and 6.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal. The obtained polyoxypropylene having a dimethoxymethylsilyl group is polyoxypropylene (A-2) having a dimethoxymethylsilyl group having a number average molecular weight of 24,600 and a polyoxypropylene having a number average molecular weight of 4,200. It contained oxypropylene (B-2) in a ratio of 100: 3, and the number of silyl groups per molecule was 1.9.

(Synthesis Example 3)
To 100 parts by weight of (P-1) obtained in Synthesis Example 1, 3 parts by weight of polyoxypropylene glycol having a number average molecular weight of 4,700 was added, and then 1.2 molar equivalents of sodium methoxide with respect to the hydroxyl group were added. Was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-2) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-2), and 6.2 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal. The obtained polyoxypropylene having a dimethoxymethylsilyl group is polyoxypropylene (A-3) having a dimethoxymethylsilyl group having a number average molecular weight of 24,600 and a polyoxypropylene having a dimethoxymethylsilyl group having a number average molecular weight of 4,700. It contains oxypropylene (B-3) in a ratio of 100: 3, the number of silyl groups per molecule of (A-3) is 1.9, and the number of silyl groups per molecule of (B-3) is 1.9. The number of was 1.25.

(Synthesis Example 4)
To 100 parts by weight of (P-1) obtained in Synthesis Example 1, 5 parts by weight of polyoxypropylene triol having a number average molecular weight of 4,200 was added, and then 1.2 molar equivalents of sodium methoxide with respect to the hydroxyl group were added. Was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-3) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-3), and 6.7 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal. The obtained polyoxypropylene having a dimethoxymethylsilyl group is polyoxypropylene (A-1) having a dimethoxymethylsilyl group having a number average molecular weight of 24,600 and a polyoxypropylene having a dimethoxymethylsilyl group having a number average molecular weight of 4,200. It contains oxypropylene (B-1) in a ratio of 100: 5.

(Synthesis Example 5)
To 100 parts by weight of (P-1) obtained in Synthesis Example 1, 5 parts by weight of polyoxypropylene glycol having a number average molecular weight of 4,700 was added, and then 1.2 molar equivalents of sodium methoxide with respect to the hydroxyl group were added. Was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-4) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-4), and 6.3 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene having a dimethoxymethylsilyl group at the terminal. The obtained polyoxypropylene having a dimethoxymethylsilyl group is polyoxypropylene (A-2) having a dimethoxymethylsilyl group having a number average molecular weight of 24,600 and a polyoxypropylene having a dimethoxymethylsilyl group having a number average molecular weight of 4,700. It contains oxypropylene (B-2) in a ratio of 100: 5.

(Synthesis Example 6)
To the hydroxyl group of (P-1) obtained in Synthesis Example 1, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-5) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-5), and 5.5 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (A-4) having a dimethoxymethylsilyl group at the terminal. The number of silyl groups per molecule of (A-4) obtained was 1.8.

(Synthesis Example 7)
To the hydroxyl group of polyoxypropylene glycol having a number average molecular weight of 4,700, 1.2 molar equivalents of sodium methoxide was added as a 28% methanol solution. After evaporating methanol by vacuum volatilization, 1.5 molar equivalents of allyl chloride was further added to the hydroxyl group of the obtained polymer to convert the terminal into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation to obtain a hexane solution. Further, 300 parts by weight of water was mixed and stirred, water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-6) having an allyl group at the terminal site was obtained. 21 μl of a platinum divinyldisiloxane complex solution (platinum 3 wt%) was added to 500 g of this polymer (Q-6), and 19.0 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (B-4) having a dimethoxymethylsilyl group at the terminal. The number of silyl groups per molecule of (B-4) obtained was 1.2.

(Example 1)
AZ6170 (Toray Dow Corning) with respect to 103 parts by weight of the polyoxypropylene having a dimethoxymethylsilyl group obtained in Synthesis Example 1 {100 parts by weight of the (A-1) component and 3 parts by weight of the (B-1) component}. Made by Tris ((trimethylsiloxy) methyl) propane) 0.5 parts by weight, TMSP (manufactured by Toray Dow Corning Co., Ltd .: trimethylphenoxysilane) 0.5 parts by weight, IRGANOX245 (BASF Japan Ltd.) , Hindered phenolic antioxidant) 0.2 parts by weight, Viscolite-OS (manufactured by Shiraishi Kogyo Co., Ltd .: surface-treated calcium carbonate) 160 parts by weight, Whiten SB (manufactured by Shiraishi Kogyo Co., Ltd .: heavy carbon dioxide) 60 parts by weight of calcium), 13 parts by weight of EMC-40 (manufactured by Nippon Phillite Co., Ltd .: hollow filler), 110 parts by weight of DINP (manufactured by J-Plus Co., Ltd .: diisononyl phthalate-based plasticizer), Sansosizer E-PS ( Shin Nihon Rikamasa: 19 parts by weight of di2-ethylhexyl epoxyhexahydrophthalate, 5.6 parts by weight of Disparon # 308 (manufactured by Kusumoto Kagaku Co., Ltd .: hydrogenated castor oil), Chinabin 326 (manufactured by BASF: 2- (5) -Chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol) 1 part by weight, Sanol LS770 (manufactured by Ciba Specialty Chemicals: Bis (2,2,6,6-tetramethyl-4-piperidyl)) Sevacate) 1 part by weight, Aronix M309 (manufactured by Toa Synthetic: 1,1,1-trimethylol propantriacrylic acid ester) 3.3 parts by weight as the main ingredient, Neostan U-28 3 parts by weight, 0.7 parts by weight of laurylamine , DINP 8 parts by weight, Whiten SB 19 parts by weight, ASP-170 (BASF: Kaolin) 6 parts by weight as a curing agent, DINP 4.4 parts by weight, Typake R820 (Ishihara Sangyo Co., Ltd .: Titanium oxide) 5.6 weight The part was prepared as a collar, and the main agent, the curing agent, and the collar were mixed and defoamed.

Using the obtained curable composition, an H-type test piece having a joint width of 12 mm was prepared, and after curing at 23 ° C. for 3 days + 50 ° C. for 4 days with reference to the 9030 durability test method of JIS A1439: 2010, 50 ° C. It was immersed in warm water for 4 hr and then dried in a 50 ° C. environment for 1 hr. The joints were compressed by + 30% for 3 days in a 90 ° C environment. After releasing the joints, the joints were held at 12 mm for 24 hours or more, and then repeated tests were carried out 200 times at ± 30% in an environment of 23 ° C. for determination. The durability was judged according to the following criteria.

(Durability judgment)
⊚: No change ~ Slight cracks at the sealant interface ○: Cracks with a depth of 1 mm or less at the sealant interface

(Example 2)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that the amount of IR245 was 1.0 part by weight. The results are shown in Table 1.

(Example 3)
Same as Example 1 except that 103 parts by weight of the polyoxypropylene having a dimethoxymethylsilyl group obtained in Synthesis Example 2 {100 parts by weight of the (A-2) component and 3 parts by weight of the (B-2) component} was used. A curable composition was prepared by the method of the above and evaluated. The results are shown in Table 1.

(Example 4)
Same as Example 1 except that 103 parts by weight of the polyoxypropylene having a dimethoxymethylsilyl group obtained in Synthesis Example 3 {100 parts by weight of the (A-3) component and 3 parts by weight of the (B-3) component} was used. A curable composition was prepared by the method of the above and evaluated. The results are shown in Table 1.

(Example 5)
A curable composition was prepared in the same manner as in Example 1 except that 100 parts by weight (A-4) obtained in Synthesis Example 6 and 3 parts by weight (B-4) obtained in Synthesis Example 7 were used. It was prepared and evaluated. The results are shown in Table 1.

(Comparative Example 1)
A curable composition was prepared and evaluated in the same manner as in Example 1 except that 100 parts by weight of the polyoxypropylene (A-4) having a dimethoxymethylsilyl group obtained in Synthesis Example 6 was used. The results are shown in Table 1.

(Comparative Example 2)
Same as Example 1 except that 105 parts by weight of the polyoxypropylene having a dimethoxymethylsilyl group obtained in Synthesis Example 4 {100 parts by weight of the (A-1) component and 5 parts by weight of the (B-1) component} was used. A curable composition was prepared by the method of the above and evaluated. The results are shown in Table 1.

(Comparative Example 3)
Same as Example 1 except that 105 parts by weight of the polyoxypropylene having a dimethoxymethylsilyl group obtained in Synthesis Example 5 {100 parts by weight of the (A-2) component and 5 parts by weight of the (B-2) component} was used. A curable composition was prepared by the method of the above and evaluated. The results are shown in Table 1.

(Comparative Example 4)
The same method as in Example 1 was used except that 100 parts by weight of polyoxypropylene (A-4) having a dimethoxymethylsilyl group and 3 parts by weight of polyoxypropylene glycol having a number average molecular weight of 4700 obtained in Synthesis Example 6 were used. A curable composition was prepared and evaluated. The results are shown in Table 1.

Examples 1 to 5 in which 3 parts by weight of the polyoxyalkylene polymer (B) having a reactive silyl group having a number average molecular weight of 1,000 or more and 6,000 or less was added were not added (Comparative Example 1). , 4) Durability is improved as compared with the addition of 5 parts by weight (Comparative Examples 2 and 3).

Claims (10)

100 parts by weight of a polyoxyalkylene polymer (A) having a number average molecular weight of more than 6,000 and a reactive silyl group of 50,000 or less,
1 to 4 parts by weight of a polyoxyalkylene polymer (B) having a reactive silyl group having a number average molecular weight of 1,000 or more and 6,000 or less.
Curable composition containing. (A) The curable composition according to claim 1, wherein the number average molecular weight of the components is 10,000 or more and 50,000 or less. The curable composition according to claim 1 or 2, wherein the component (B) has an average of more than 1.0 reactive silyl groups per molecule. The curable composition according to any one of claims 1 to 3, wherein the component (B) has an average of 1.2 or more reactive silyl groups per molecule. The curable composition according to any one of claims 1 to 4, wherein the component (A) has an average of more than 1.0 reactive silyl groups per molecule. The curable composition according to any one of claims 1 to 5, wherein the reactive silyl group of the component (A) and / or the component (B) is the general formula (1).
−SiR ¹ _3-a X _a (1)
{In the formula, R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, which may independently have a heteroatom-containing group or a substituent composed of a halogen atom. X is independently a hydroxyl group or a hydrolyzable group. a indicates 1, 2, or 3. }
The curable composition according to any one of claims 1 to 6, wherein the component (A) and / or the component (B) is a polyoxypropylene-based polymer. The curable composition according to any one of claims 1 to 7, further containing 0.5 parts by weight or more of the antioxidant (C). A cured product obtained by curing the curable composition according to any one of claims 1 to 8. A functional group capable of introducing a reactive silicon group into 100 parts by weight of the polyoxyalkylene polymer (a) having a functional group capable of introducing a reactive silicon group and having a number average molecular weight of more than 6,000 and 50,000 or less. Reactive silyl obtained by mixing 1 to 4 parts by weight of the polyoxyalkylene polymer (b) having a number average molecular weight of 1,000 or more and 6,000 or less, and then introducing a reactive silicon group. A method for producing a polyoxyalkylene polymer having a group.