JP5161578B2 - One-component curable composition - Google Patents

Description

In the present invention, an organic heavy group having a hydrogen group or a hydrolyzable group bonded to a silicon atom and having a silicon-containing group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). The present invention relates to a curable composition containing a coalescence.

An organic polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property of being obtained.

Among these polymers having reactive silicon groups, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a meth (acrylic acid) ester polymer are disclosed in Patent Document 1, Patent Document 2, and the like. It is already industrially produced and widely used for applications such as sealing materials, adhesives and paints.

These curable compositions containing an organic polymer having a reactive silicon group are cured using a silanol condensation catalyst and are usually carbon-carbon such as dibutyltin bis (acetylacetonate) and dibutyltin dilaurate. Organotin compounds having a tin bond are widely used. However, in recent years, organotin compounds are concerned about toxicity to living bodies as endocrine disrupting substances, and development of a catalyst having a practical curing rate instead of these has been demanded.

As this non-organotin compound, a dealcohol-free silicone composition using a titanium catalyst has already been marketed and is widely used in many applications. This technique is described in Patent Literature 3, Patent Literature 4, Patent Literature 5, and the like.

However, there are relatively few examples of adding a titanium catalyst to an organic polymer containing a reactive silicon group. Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Patent It is disclosed in Document 12, Patent Document 13, Patent Document 14, and Patent Document 15.

A curable composition containing an organic polymer containing a reactive silicon group is often used as an adhesive or a sealing material, and in that case, adhesion to various types of substrates is required. In order to ensure this adhesion, so-called aminosilane having a primary amino group and an alkoxy group in the molecule is usually used. However, when an organic polymer containing a reactive silicon group and a titanium catalyst are used to make a one-component curable composition by adding aminosilane, the adhesiveness is good, but the composition after storage for a certain period of time. If the viscosity of the product is improved and it is severe, it may harden in the container and cannot be used. Sealing materials and adhesives are not always used immediately after production, but are often stored for several months in warehouses or stores, and it is desired that their curability and viscosity be constant before and after storage. Yes.
JP-A-52-73998 Japanese Patent No. 1780140 Japanese Examined Patent Publication No. 39-27643 US Pat. No. 3,175,993 US Pat. No. 3,334,067 JP 58-17154 A JP-A-11-209538 JP-A-5-311063 JP 2001-302929 A JP 2001-302930 A JP 2001-302931 A JP 2001-302934 A JP 2001-348528 A Japanese Patent Laid-Open No. 2002-249672 JP 2003-165916 A

The present invention is a curable composition mainly composed of an organic polymer having a reactive silicon group, and has good curability and adhesiveness without using an organic tin compound that has been pointed out to be toxic. Another object of the present invention is to provide a curable composition that maintains good workability even after being stored for a long period of time.

As a result of intensive investigations to solve such problems, the present inventors have (A) an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, (B) a titanium catalyst, (C 1) A curable composition containing an epoxy group and a silane compound having an alkoxy group, and the composition does not contain an organic tin compound and a compound having a primary amino group. The present invention was completed by using a component-type curable composition.

The present invention will be described in detail below.

The main chain skeleton of the organic polymer (A) having a reactive silicon group used in the present invention is not particularly limited, and those having various main chain skeletons can be used.

Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. Copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers.

Furthermore, a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer are more preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

The glass transition temperature of the organic polymer as component (A) is not particularly limited, but is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and particularly preferably −20 ° C. or lower. . If the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease. The glass transition temperature is a value obtained by DSC measurement.

In addition, the (B) titanium catalyst of the present invention and (C) the silane compound having an epoxy group and having an alkoxy group have a tendency to decrease the deep curability of the composition obtained depending on the amount of addition. is there. Therefore, the polyoxyalkylene polymer and the (meth) acrylic acid ester polymer are particularly preferable because of their high moisture permeability and excellent deep section curability, and the polyoxyalkylene polymer is most preferable. Moreover, the curable composition containing a (meth) acrylic acid ester-type polymer is preferable from being excellent in adhesiveness and weather resistance. Considering the above balance, it is most preferable to use a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer in combination.

The reactive silicon group contained in the organic polymer having a reactive silicon group of the present invention is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by a reaction accelerated by a curing catalyst. is there. As the reactive silicon group, the general formula (4):
-SiR ⁶ _3-a X _a (4)
(In the formula, each R ⁶ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is independently a hydroxyl group or And a is a hydrolyzable group, and a is any one of 1, 2, and 3).

It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable from the viewpoint of mild hydrolysis and easy handling.

Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and when two or more hydrolyzable groups or hydroxyl groups are bonded to a reactive silicon group, May be the same or different.
In the general formula (4), a is preferably 2 or 3, more preferably 3, from the viewpoint of curability.

Specific examples of R ⁶ in the general formula (4) include, for example, 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, Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group, or the like. Of these, a methyl group is particularly preferred.

More specific examples of the reactive silicon group include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because of high activity and good curability. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. Further, the triethoxysilyl group is particularly preferable because the alcohol produced with the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

Introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method can be mentioned.

(B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Subsequently, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

(B) An organic polymer containing an unsaturated group obtained in the same manner as in the method (a) is reacted with a compound having a mercapto group and a reactive silicon group.

(C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group.

Among the above methods, the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is high in a relatively short reaction time. It is preferable because a conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. , Methyldimethoxysilane, phenyldimethoxysilane, alkoxysilanes such as 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyldiacetoxysilane Examples thereof include, but are not limited to, acyloxysilanes such as bis (dimethylketoximate) methylsilane and ketoxymatesilanes such as bis (cyclohexylketoximate) methylsilane. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the obtained organic polymer has high curability, storage stability, elongation characteristics, and tensile strength. Trimethoxysilane and 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane are preferable because they can increase the curing rate, and further use of a titanium catalyst which is a curing catalyst. It is preferable because the amount can be reduced.

As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Examples thereof include, but are not limited to, silane and mercaptomethyltriethoxysilane.

As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Although silane etc. are mentioned, it is not limited to these.

A silane compound in which three hydrolyzable groups are bonded to one silicon atom such as trimethoxysilane may undergo a disproportionation reaction. As the disproportionation reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups such as trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthesis method (b) or (c) may be used. preferable.

On the other hand, general formula (5):
H- (SiR ⁷ ₂ O) _m SiR ⁷ ₂ -R ⁸ -SiX ₃ (5)
(In the formula, X is the same as above. 2m + 2 R ^{7 s} are each independently a monovalent hydrocarbon group, and are monovalent hydrocarbon having 1 to 20 carbon atoms from the standpoint of availability and cost. A monovalent hydrocarbon group having 1 to 8 carbon atoms is more preferable, and a monovalent hydrocarbon group having 1 to 4 carbon atoms is particularly preferable, and R ⁸ is a divalent organic group. From the viewpoints of property and cost, a divalent hydrocarbon group having 1 to 12 carbon atoms is preferable, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon having 2 carbon atoms is preferable. The group is particularly preferred, and m is an integer of 0 to 19, and 1 is preferred from the viewpoint of availability and cost.) The disproportionation reaction does not proceed. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), the silane compound represented by the general formula (5) should be used. Is preferred. Specific examples of the silane compound represented by the general formula (5) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (tri Methoxysilyl) propyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane, and the like.

The organic polymer having a reactive silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to 50,000. And particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity. Although not particularly limited, specifically, the number average molecular weight and molecular weight distribution are, for example,
Liquid feeding system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Can be measured as a value in terms of polystyrene.

In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the average number of reactive silicon groups contained in the organic polymer is at least 1, preferably 1, It is good to have 1-5 pieces. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The reactive silicon group may be at the end of the main chain or the side chain of the organic polymer molecular chain, or at both ends. In particular, when the reactive silicon group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high. It becomes easy to obtain a rubber-like cured product exhibiting a low elastic modulus.

The polyoxyalkylene polymer essentially has the general formula (6):
—R ⁹ —O— (6)
(Wherein R ⁹ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁹ in the general formula (6) is the number of carbon atoms. 2 to 4 linear or branched alkylene groups are preferred. Specific examples of the repeating unit represented by the general formula (6) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used as a sealing material or the like, a material composed of a (co) polymer having a propylene oxide monomer unit as a main component, such as a polyoxypropylene polymer, is amorphous or relatively low. It is preferable from the point of viscosity.

As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, or a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization with a transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,559 , U.S. Pat. No. 3,427,256, U.S. Pat. No. 3,427,334, U.S. Pat. No. 3,427,335, and the like. Polymerization method using a catalyst comprising a polyphosphazene salt, Such polymerization method using a catalyst comprising a phosphazene compound exemplified in 060722 JP, including but not limited in particular.

The method for producing a polyoxyalkylene polymer having a reactive silicon group according to the present invention is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A-50-156599, and 54-6096. 55-13767, 55-13468, 57-164123, Japanese Patent Publication No. 3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307 No. 4, U.S. Pat. No. 4,960,844, etc., and JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632. Japanese Patent Laid-Open Nos. 3-72527, 3-47825, and 8-231707. The number has been proposed an average molecular weight of 6,000 or more, but Mw / Mn molecular weight distribution can be exemplified narrow polyoxyalkylene polymer with a high molecular weight of 1.6 or less, but it is not particularly limited thereto.

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

On the other hand, the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trimethyl (meth) acrylate Fluoromethylethyl, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoro (meth) acrylate Methyl, (meth) acrylic acid (Trifluoromethylmethyl), 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (Meth) acrylic acid monomers such as (meth) acrylic acid 2-perfluorohexadecylethyl are listed. In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer is preferable from the physical property of a product. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer. In applications such as general construction, a butyl acrylate monomer is more preferred from the viewpoint that physical properties such as low viscosity of the blend, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. On the other hand, in applications that require oil resistance, such as automobile applications, copolymers based on ethyl acrylate are more preferred. This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low temperature characteristics (cold resistance). Therefore, in order to improve the low temperature characteristics, a part of ethyl acrylate is converted into butyl acrylate. It is also possible to replace it. However, as the ratio of butyl acrylate is increased, its good oil resistance is impaired. Therefore, for applications requiring oil resistance, the ratio is preferably 40% or less, and more preferably 30% or less. More preferably. It is also preferable to use 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, or the like in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics and the like without impairing oil resistance. However, since heat resistance tends to be inferior due to the introduction of an alkoxy group having an ether bond in the side chain, when heat resistance is required, the ratio is preferably 40% or less. In accordance with various uses and required purposes, it is possible to obtain suitable polymers by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40-50 / 20 by weight) 30/30 to 20). In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to carry out by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a large degree of freedom in designing initiators and catalysts ( The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive silicon group include chain transfer described in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. A production method using a free radical polymerization method using an agent is disclosed. Japanese Patent Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

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

These organic polymers having a reactive silicon group may be used alone or in combination of two or more. Specifically, an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group can also be used.

A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541, Although proposed in Japanese Patent Laid-Open Nos. 63-112642, 6-172631, and 11-116763, the invention is not particularly limited thereto. A preferred specific example has a reactive silicon group and a molecular chain substantially having the following general formula (7):
—CH ₂ —C (R ¹⁰ ) (COOR ¹¹ ) — (7)
(Wherein R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkyl group having 1 to 8 carbon atoms) and a (meth) acrylic acid ester having an alkyl group having 1 to 8 carbon atoms A monomer unit and the following general formula (8):
—CH ₂ —C (R ¹⁰ ) (COOR ¹² ) — (8)
(Wherein R ¹⁰ is the same as above, and R ¹² represents an alkyl group having 9 or more carbon atoms) represented by a (meth) acrylate monomer unit having an alkyl group having 9 or more carbon atoms And a copolymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group.

As R ^{11 in the} general formula (7), for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, etc. are used. More preferably, an alkyl group of 1 to 2 is mentioned. The alkyl group of R ¹¹ may alone, or may be a mixture of two or more.

R ^{12 in the} general formula (8) is, for example, a long chain having 9 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, behenyl group, etc., usually 10-30, preferably 10-20. Of the alkyl group. The alkyl group of R ¹² is same as in the case of R ^11, alone may be, or may be a mixture of two or more.

The molecular chain of the (meth) acrylic acid ester copolymer is substantially composed of monomer units represented by the formulas (7) and (8). The term “substantially” as used herein refers to the copolymer. It means that the sum of the monomer units of formula (7) and formula (8) present therein exceeds 50% by weight. The sum of the monomer units of formula (7) and formula (8) is preferably 70% by weight or more.

The abundance ratio of the monomer unit of the formula (7) and the monomer unit of the formula (8) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40 by weight.

Examples of monomer units other than those represented by formula (7) and formula (8) that may be contained in the copolymer include acrylic acid such as acrylic acid and methacrylic acid; acrylamide, methacrylamide, N-methylolacrylamide, Amide group such as N-methylol methacrylamide, epoxy group such as glycidyl acrylate and glycidyl methacrylate, monomer containing amino group such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate; other acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, Examples thereof include monomer units derived from vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like.

Furthermore, as a method for producing an organic polymer obtained by blending a (meth) acrylic acid ester-based polymer having a reactive silicon functional group, there is also a polyoxypropylene-based polymer having a reactive silicon group. A method of polymerizing a (meth) acrylic acid ester monomer below can be used. This manufacturing method is specifically disclosed in each publication such as JP-A-59-78223, JP-A-60-228516, and JP-A-60-228517, but is limited thereto. It is not a thing.

On the other hand, the main chain skeleton of the organic polymer of the present invention may contain other components such as a urethane bond component as long as the effects of the invention are not significantly impaired.

Although it does not specifically limit as said urethane bond component, The group (henceforth an amide segment) produced | generated by reaction of an isocyanate group and an active hydrogen group can be mentioned.

The amide segment has the general formula (9):
—NR ¹³ —C (═O) — (9)
(R ¹³ represents a hydrogen atom or a substituted or unsubstituted organic group).

Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (9).

An example of an industrially easy production method of an organic polymer having an amide segment and a reactive silicon group is as follows. An organic polymer having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to produce a polyurethane-based main polymer. After forming a polymer having an isocyanate group at the chain end, or at the same time, all or a part of the isocyanate group may be represented by the general formula (10)
W-R ¹⁴ -SiR ⁶ _3-c X _c (10)
(In the formula, R ⁶ , X and c are the same as described above. R ¹⁴ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (unsubstituted or mono-substituted). Can be mentioned. Examples of known production methods of organic polymers related to this production method include Japanese Patent Publication No. 46-12154 (U.S. Pat. No. 3,632,557) and Japanese Patent Publication No. 58-109529 (U.S. Pat. No. 4,374,237). Description), Japanese Patent Application Laid-Open No. 62-13430 (U.S. Pat. No. 4,645,816), Japanese Patent Application Laid-Open No. 8-53528 (Japanese Patent Application Publication No. 0676403), Japanese Patent Application Laid-Open No. 10-204144 (Europe). (Patent Application Publication No. 0831108), Japanese translations of PCT publication No. 2003-508561 (U.S. Pat. No. 6,1979,912), JP-A-6-2111879 (U.S. Pat. No. 5,364,955), JP-A-10-53637. Gazette (U.S. Pat. No. 5,757,751), Japanese Patent Laid-Open No. 11-100197, Japanese Patent Laid-Open No. 2000-1695. 4, No. 2000-169545, No. 2002-212415, No. 3313360, U.S. Pat. No. 4,067,844, U.S. Pat. No. 3,711,445, JP-A No. 2001-323040, Etc.

Further, the organic polymer having an active hydrogen-containing group at the terminal is represented by the general formula (11)
O = C = N-R ¹⁴ -SiR ⁶ _3-c X _c (11)
(However, in the formula, R ⁶ , R ¹⁴ , X, and c are the same as described above.) A compound produced by reacting with a reactive silicon group-containing isocyanate compound can be mentioned. Examples of known production methods of organic polymers related to this production method include JP-A Nos. 11-279249 (US Pat. No. 5,990,257) and JP-A No. 2000-119365 (US Pat. No. 6,046,270). JP, 58-29818 (U.S. Pat. No. 4,345,053), JP-A-3-47825 (U.S. Pat. No. 5,068,304), JP-A-11-60724, JP-A 2002-2002. No. 155145, JP-A 2002-249538, WO 03/018658, WO 03/059981, and the like.

Examples of the organic polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer (polyether polyol) having a hydroxyl group at the terminal and a polyacrylic polyol. Among these, polyether polyol is more preferable because the organic polymer obtained has low viscosity and good workability, and good adhesion and deep part curability. Polyacryl polyol is more preferable because the cured product of the obtained organic polymer has good weather resistance and heat resistance.

As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxyl groups per molecular terminal in terms of the total molecular average are preferred. Specifically, an alkylene oxide produced by using a conventional alkali metal catalyst, an initiator such as a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex or cesium, and an alkylene oxide. An oxyalkylene polymer produced by reacting with oxyalkylene.

Among the above polymerization methods, a polymerization method using a double metal cyanide complex is an oxyalkylene polymer having a lower degree of unsaturation, a narrower molecular weight distribution, a lower viscosity, and a high acid resistance and high weather resistance. Is preferable because it can be obtained.

Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure. Specifically, Alfon UH-2000, UH-2130, etc. manufactured by Toagosei Co., Ltd. may be mentioned.

Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .

Although there is no limitation in particular as a silicon compound of General formula (10), when it illustrates concretely, (gamma) -aminopropyl trimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyl trimethoxysilane, (gamma)-( N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, (N-cyclohexylaminomethyl) triethoxysilane, (N-cyclohexylaminomethyl) diethoxymethylsilane, (N-phenylaminomethyl) tri Examples include amino group-containing silanes such as methoxysilane; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (European Patent Application Publication No. 0831108). As described in JP-A No. 2000-169544 and JP-A No. 2000-169545, Michael addition reaction products of various α, β-unsaturated carbonyl compounds and primary amino group-containing silanes. Alternatively, a Michael addition reaction product of various (meth) acryloyl group-containing silanes and primary amino group-containing compounds can also be used as the silicon compound of the general formula (10).

The reactive silicon group-containing isocyanate compound represented by the general formula (11) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triexylsilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiexylsilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate and the like. Further, as described in JP-A-2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting the silicon compound of the general formula (10) with an excess of the polyisocyanate compound is also available. Moreover, it can use as a reactive silicon group containing isocyanate compound of General formula (11).

When there are many amide segments in the main chain skeleton of the organic polymer of the present invention, the viscosity of the organic polymer becomes high, and a composition with poor workability may be obtained. On the other hand, the amide segment in the main chain skeleton of the organic polymer tends to improve the curability of the composition of the present invention. When an organic polymer having an amide segment in the main chain skeleton is used as the component (A), the composition combined with the component (B) of the present invention has a faster curing property while using a non-organotin catalyst. Is preferable. Accordingly, when the main chain skeleton of the organic polymer contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 7, and particularly preferably 2 to 5. . When the number is less than 1, the curability may not be sufficient, and when the number is more than 10, the organic polymer may have a high viscosity, resulting in a poor workability composition.

In the present invention, a titanium catalyst is used as the component (B). This titanium catalyst functions as a curing catalyst for the organic polymer as component (A).
Conventionally, organic tin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate have been used as curing catalysts for organic polymers having a reactive silicon group as component (A). Toxicity of these organic tin compounds Has been pointed out. Since the organotin compound increases the toxicity or the burden on the environment depending on the amount of the organotin compound, the composition of the present invention is characterized by substantially not containing the organotin compound. Here, “substantially does not contain” means that the content of the organotin compound with respect to 100 parts by weight of the organic polymer (A) is 0.5 parts by weight or less. The content of the organotin compound is preferably 0.1 parts by weight or less, and more preferably 0.01 parts by weight or less. Particularly preferably, it does not contain any organic tin compound.
Here, the “organotin compound” in the present invention refers to a compound having a direct bond between carbon and tin, and has a general formula R ¹⁵ _n SnY _4-n (n = 1 to 4, R ¹⁵ is an alkyl group, an aryl group) Y represents a functional group such as halogen, OH, OR ¹⁶ , OCOR ¹⁶ or the like (R ¹⁶ is a functional group such as an alkyl group or an aryl group). .

By using the titanium catalyst (B) of the present invention, a curable composition having almost the same curing characteristics as when an organotin compound is used can be obtained. Moreover, compared with the case where other hardening catalysts, such as an organic tin catalyst, are used, the adhesiveness with respect to hard-to-adhere organic type adherends, such as an acrylic resin, can be improved.

A compound such as TiO ₂ that does not function as a curing catalyst for the component (A) is not included in the component (B) of the present invention.

The titanium catalyst is a compound having a titanium atom bonded to a hydroxyl group or a substituted or unsubstituted alkoxy group. As a preferred specific example of the titanium catalyst, a general formula (1):
Ti (OR ¹ ) ₄ (1)
(In the formula, R ¹ is an organic group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Even though four R ^{1 s} are the same, And may be different from each other). Among these, titanium alkoxide can be exemplified as a representative compound. In addition, as the compound represented by the general formula (1), a part or all of four OR ¹ groups in the general formula (1) are represented by the general formula (12):
-OCOR ¹⁷ (12)
(Wherein, R ¹⁷ is an organic group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and a titanium carboxylate which is an acyloxy group represented by It is done.

Moreover, as a titanium catalyst other than the titanium catalyst represented by the general formula (1), the general formula (13):
TiX ¹ _4-a (OR ¹⁸ ) _a (13)
(In the formula, X ¹ is a halogen atom, and (4-a) pieces of X ¹ may be the same or different from each other. R ¹⁸ is an organic group, more preferably the number of carbon atoms. 1 to 20 substituted or unsubstituted monovalent hydrocarbon group, and a R ¹⁸ may be the same or different from each other, and a is any one of 1, 2, and 3. .) Is a halogenated titanium alkoxide.

Among these, titanium alkoxide is preferable from the viewpoints of stability to moisture and curability.

Among the titanium catalysts represented by the general formula (1), a titanium chelate is preferable, and among them, the general formula (2):

[Wherein, n R ^{2 s} are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. (4-n) pieces of R ³ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. (4-n) A ¹ and (4-n) A ² are each independently —R ⁴ or —OR ⁴ (wherein R ⁴ is substituted or unsubstituted having 1 to 8 carbon atoms) Of the monovalent hydrocarbon group). n is 0, 1, 2, or 3. ] A titanium chelate represented by the general formula (3):

(Wherein R ³ , A ¹ , and A ² are the same as described above. R ⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.) , (A) Compatibility with component, high catalytic activity, and storage stability are more preferable. The titanium chelate of the general formula (2) is particularly preferable because of its high catalytic activity. Titanium chelates in which n in the general formula (2) is 2 are most preferable because they have relatively low crystallinity (melting point), good workability, and high catalytic activity.

Of the compounds represented by the general formula (1), specific examples of titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraallyl oxide, titanium tetra n-propoxide, titanium tetraisopropoxide, Titanium tetra n-butoxide, titanium tetraisobutoxide, titanium tetra sec-butoxide, titanium tetra t-butoxide, titanium tetra n-pentyl oxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, Titanium tetraoctyl oxide, titanium tetrakis (2-ethylhexyl oxide), titanium tetradecyloxy , Titanium tetradodecyl oxide, titanium tetrastearyl oxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyl oxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolato), titanium bis ( 2-ethylhexyloxy) bis (2-ethyl-1,3-hexanediolato), titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide), Titanium tetrakis (2-ethoxyethoxide), titanium butoxide trimethoxide, titanium dibutoxide dimethoxide, titanium butoxide triethoxide, titanium dibutoxide diethoxide, titanium Umbutoxide triisopropoxide, titanium dibutoxide diisopropoxide, titanium tetraphenoxide, titanium tetrakis (o-chlorophenoxide), titanium tetrakis (m-nitrophenoxide), titanium tetrakis (p-methylphenoxide), titanium tetrakis (trimethylsilyl) Oxide), and the like.

Specific examples of titanium carboxylate in which some or all of four OR ¹ groups in general formula (1) are groups represented by general formula (12) include titanium acrylate triisopropoxide, titanium methacrylate. Triisopropoxide, titanium dimethacrylate diisopropoxide, titanium isopropoxide trimethacrylate, titanium hexanoate triisopropoxide, titanium stearate triisopropoxide, and the like.

Specific examples of the halogenated titanium alkoxide of the general formula (13) include titanium chloride triisopropoxide, titanium dichloride diisopropoxide, titanium isopropoxide trichloride, titanium bromide triisopropoxide, titanium fluoride triiso Examples thereof include propoxide, titanium chloride triethoxide, and titanium chloride tributoxide.

Specific examples of the titanium chelate of the general formula (2) or the general formula (3) include titanium dimethoxide bis (ethyl acetoacetate), titanium dimethoxide bis (acetylacetonate), titanium diethoxide bis (ethyl acetoacetate). ), Titanium diethyl bis (acetylacetonate), titanium diisopropoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (methyl acetoacetate), titanium diisopropoxide bis (t-butyl acetoacetate), Titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexanoate), Titanium diisopropoxide bis (ethyl-3-oxo-4,4,4-trifluorobutanoate), Titanium diiso Isopro Xidobis (acetylacetonate), titanium diisopropoxide bis (2,2,6,6-tetramethyl-3,5-heptanedionate), titanium di-n-butoxide bis (ethylacetoacetate), titanium di- n-butoxide bis (acetylacetonate), titanium diisobutoxide bis (ethyl acetoacetate), titanium diisobutoxide bis (acetylacetonate), titanium di-t-butoxide bis (ethyl acetoacetate), titanium di-t- Butoxide bis (acetylacetonate), titanium di-2-ethylhexoxide bis (ethylacetoacetate), titanium di-2-ethylhexoxide bis (acetylacetonate), titanium bis (1-methoxy-2-propoxy) D) Bi (Ethyl acetoacetate), titanium bis (3-oxo-2-butoxide) bis (ethylacetoacetate), titanium bis (3-diethylaminopropoxide) bis (ethylacetoacetate), titanium triisopropoxide (ethylacetoacetate) , Titanium triisopropoxide (diethyl malonate), titanium triisopropoxide (allyl acetoacetate), titanium triisopropoxide (methacryloxyethyl acetoacetate), 1,2-dioxyethane titanium bis (ethyl acetoacetate) 1,3-dioxypropane titanium bis (ethyl acetoacetate), 2,4-dioxypentane titanium bis (ethyl acetoacetate), 2,4-dimethyl-2,4-dioxypentane Titanium bis (ethyl acetoacetate), Titanium diisopropoxide bis (triethanolaminate), Titanium tetrakis (ethyl acetoacetate), Titanium tetrakis (acetylacetonate), Titanium bis (trimethylsiloxy) bis (ethyl acetoacetate), Titanium And bis (trimethylsiloxy) bis (acetylacetonate). Among these, titanium diethoxide bis (ethyl acetoacetate), titanium diethoxide bis (acetylacetonate), titanium diisopropoxide bis (ethylacetoacetate), titanium diisopropoxide bis (acetylacetonate), titanium di Butoxide bis (ethyl acetoacetate) and titanium dibutoxide bis (acetylacetonate) are preferable from the viewpoint of availability and catalytic activity. Titanium diethoxide bis (ethyl acetoacetate), titanium diisopropoxide bis (ethyl acetoacetate) ), Titanium dibutoxide bis (ethyl acetoacetate) is more preferred, and titanium diisopropoxide bis (ethyl acetoacetate) is most preferred. Titanium diisopropoxide bis (ethyl acetoacetate) is commercially available from Matsumoto Pharmaceutical Co., Ltd. under the trade name Olga-Tix TC-750, and from DuPont Co., Ltd. under the trade name Tizer DC, and is easily available.

Specific examples of titanium catalysts other than those described above include titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzene sulfonate) isopropoxide, dihydroxy titanium bis-lactate, and the like.

Specific examples of the chelating reagent capable of forming the chelate ligand of the titanium chelate include β-diketones such as acetylacetone, 2,2,4,4-tetramethyl-3,5-heptanedione, and methyl acetoacetate. , Ethyl acetoacetate, t-butyl acetoacetate, allyl acetoacetate, acetoacetic acid (2-methacryloxyethyl), methyl 3-oxo-4,4-dimethylhexanoate, 3-oxo-4,4,4-trifluoro Β-ketoesters such as ethyl butanoate; β-diesters such as dimethyl malonate and diethyl malonate; are preferred from the viewpoint of curability. Among these, β-diketone and β-ketoester are more preferable from the viewpoint of curability and storage stability, and β-ketoester is particularly preferable. From the viewpoints of curability, storage stability and availability, acetylacetone, methyl acetoacetate and ethyl acetoacetate are more preferred, and ethyl acetoacetate is particularly preferred. When two or more chelate ligands are present, each chelate ligand may be the same or different.

As a method of adding the titanium chelate, besides directly adding the titanium chelate exemplified above, a titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium dichloride diisopropoxide, ethyl acetoacetate, etc. The chelating reagent may be added to the composition of the present invention and chelated in the composition.

The amount of the titanium catalyst (B) is preferably about 2 to 20 parts by weight, more preferably about 4 to 15 parts by weight, and particularly preferably about 6 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). . When the blending amount of the component (B) is less than 2 parts by weight, a practical curing rate may not be obtained, and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (B) exceeds 20 parts by weight, the pot life tends to be too short and the workability tends to deteriorate.

Although a titanium catalyst is used as the curing catalyst of the present invention, other curing catalysts can be used in combination to such an extent that the effects of the present invention are not reduced. Specific examples include carboxylic acid metal salts such as tin 2-ethylhexanoate, tin versatate, and bismuth 2-ethylhexanoate. Tin 2-ethylhexanoate and tin versatate are divalent inorganic tins, not organic tin compounds.

In the present invention, a silane compound having an epoxy group and an alkoxy group is used as the component (C). The alkoxy group is present on a silicon atom. Specific examples of the component (C) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl). Examples include epoxy group-containing silanes such as ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

Among these, in order to ensure good adhesion, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferable, and among them, γ- Glycidoxypropyltrimethoxysilane is particularly preferred.

The compounding amount of the silane compound having an epoxy group which is the component (C) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer of the component (A). preferable. When the blending amount of the component (C) is less than 0.1 parts by weight, it is difficult to obtain sufficient adhesiveness, while when it exceeds 20 parts by weight, the curability becomes too long.

To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent other than the component (C) can be added as an adhesion promoter. Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and (isocyanatemethyl) trimethoxysilane. , (Isocyanatemethyl) dimethoxymethylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane and other isocyanate group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ -Mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane, mercaptomethy Mercapto group-containing silanes such as rutrimethoxysilane and mercaptomethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl- Carboxysilanes such as γ-aminopropyltrimethoxysilane; vinyl such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane Type unsaturated group-containing silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate sila such as tris (3-trimethoxysilylpropyl) isocyanurate Mention may be made of a kind, and the like. Moreover, the condensate which condensed the said silane partially can also be used. Examples of the reaction product of the silane coupling agent include a reaction product of aminosilane and epoxysilane, a reaction product of aminosilane and isocyanate silane, and a partial condensate of various silane coupling agents. It is necessary not to remain.

Usually, a silane compound having a primary amino group and an alkoxy group in the molecule is used as an adhesiveness-imparting agent for a sealing material or an adhesive. From virtually no use. However, it may be used as long as the storage stability is not lowered. The amount of the silane compound having a primary amino group and an alkoxy group is 0.5 wt. Parts by weight or less, preferably 0.1 parts by weight or less, more preferably 0.01 parts by weight or less. Particularly preferably, it is not contained.

A silane coupling agent having a secondary amino group and / or a tertiary amino group is preferably used because it can improve the adhesion to the base without deteriorating storage stability. Specifically, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (3-trimethoxysilylpropyl) amine, N Amino group-containing silanes such as ethyl-γ-aminoisobutyltrimethoxysilane; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3- Dimethylbutylidene) -3- (trimethoxysilyl) -1-propyl Ketimines type silanes such as Pan'amin like. Among these, bis (3-trimethoxysilylpropyl) amine and N-ethyl-γ-aminoisobutyltrimethoxysilane are particularly preferable in terms of further improving curability.

The silane coupling agent, the reaction product of the silane coupling agent, or the compound other than the silane coupling agent used in the present invention is usually added in an amount of 0. It is used in the range of 1 to 20 parts by weight. In particular, it is preferably used in the range of 0.5 to 10 parts by weight. When the amount of the silane coupling agent used is less than 0.1 parts by weight, the viscosity of the one-component curable composition may increase in the container when stored for a long period of time, or it may become hard to use. On the other hand, if it exceeds 20 parts by weight, the curing rate may be very slow.

The effects of the silane coupling agent added to the curable composition of the present invention include various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Although it does not specifically limit as a specific example of compounds other than a silane coupling agent, For example, an epoxy resin, a phenol resin, sulfur, alkyl titanates, aromatic polyisocyanate etc. are mentioned. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

Moreover, the compound which has only a hydrolyzable silicon group as a functional group can be used, These are compounds which can function as a dehydrating agent, a crosslinking agent, or a physical property modifier. The component is not particularly limited as long as it is a compound having only a reactive silicon group as a functional group and a molecular weight of 100 to 1000, and various compounds can be used.

Specific examples include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra Tetraalkoxysilane (tetraalkyl silicate) such as i-butoxysilane and tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, butyl Trialkoxysilanes such as trimethoxysilane and phenyltrimethoxysilane; dialkoxysilanes such as dimethyldimethoxysilane, diethyldimethoxysilane and diphenyldimethoxysilane; Trimethyl methoxy silane, mono-alkoxysilanes such as triphenyl silane; dimethyl isopropenoxysilane silane, alkyl isopropenoxysilane silane such as methyltrimethoxysilane isopropenoxysilane silane; and their partial hydrolysis condensates thereof.

As the partially hydrolyzed condensate of the organosilicate compound, a commercially available product can be used. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).
In the present invention, a compound containing a primary amino group is substantially not used. Here, “substantially free” means an amount that does not decrease the storage stability of the curable composition of the present invention, and specifically, 1 to 100 parts by weight of the organic polymer (A). It means that the content of the compound having a secondary amino group is 0.5 parts by weight or less. The content of the compound having a primary amino group is preferably 0.1 parts by weight or less, and more preferably 0.01 parts by weight or less. Particularly preferably, it is not contained at all.

A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenol resin and vinylidene chloride Examples include fillers such as resin organic microballoons, PVC powder, PMMA powder, and the like; fibrous fillers such as asbestos, glass fibers, and filaments. When the filler is used, the amount used is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the polymer of component (A).

As described in JP-A No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, sealed in a bag made of an airtight material, and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, the storage stability can be further improved.

Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Can be obtained. The surface of silicon dioxide fine powder is generally a silanol group (-SiOH), and (-SiO-hydrophobic group) is generated by reacting organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol group present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and if used in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in an amount of 5 to 200 parts by weight per 100 parts by weight of the organic polymer (A) having a reactive silicon group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5-300 μm is preferable.

The composition of the present invention is an adhesive for exterior wall joints, exterior wall tiles, and exterior wall tiles, such as sizing boards, especially ceramic sizing boards, because the cured product has good chemical resistance. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, is blended in the composition of the present invention, the cured product is in harmony with such a high-quality outer wall. However, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.

The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and a material having an appropriate size is used according to the material and pattern of the outer wall. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. In the case of a scaly substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.

A preferable finishing method and the like are described in JP-A-9-53063.

Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. As described in JP-A-10-251618, preferred diameters, blending amounts, materials, and the like of the balloon are as follows.

The balloon is a spherical filler with a hollow inside. Examples of the balloon material include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, and saran, but are not limited thereto. In addition, an inorganic material and an organic material can be combined, or a plurality of layers can be formed by stacking. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon may be surface treated with a silane coupling agent.

The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. The thing of about 0.2 mm-5.0 mm and about 0.5 mm-5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with a particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, and JP-A-9-53063. No. 10-251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the adhesive part using this composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and Plays the role of peeling. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

Even when the composition of the present invention contains particles of cured sealant, the cured product can form irregularities on the surface and improve the design. The preferable diameter, blending amount, material and the like of the cured sealant particles are as follows as described in JP-A-2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

A tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclohexane. Pentadiene-phenol resin, coumarone indene 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, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

The tackifying resin is used in an amount of 5 to 1,000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the organic polymer (A).

A plasticizer can be added to the composition of the present invention. By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; and epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

Moreover, a polymeric plasticizer can be used. When a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used. Furthermore, the drying property (also referred to as paintability) when an 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 plasticizer obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; Are 1000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxyl groups of these polyether polyols are ester groups, ethers Polyethers such as derivatives converted into groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like, but are not limited thereto is not.

Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure. Specific examples include Alfon UP-1000, UP-1010, UP-1020, UP-1110 and the like manufactured by Toagosei Co., Ltd.

The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, and specifically, the value of Mw / Mn (weight average molecular weight / number average molecular weight) is preferably less than 1.80. The value of Mw / Mn is more preferably 1.70 or less, further preferably 1.50 or less, and most preferably 1.30 or less.

The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion). Specifically, although not particularly limited, specifically, the number average molecular weight, the molecular weight distribution is, for example,
Liquid feeding system: Tosoh HLC-8120GPC
Column: Tosoh TSK-GEL H type Solvent: THF
Can be measured as a value in terms of polyethylene.

The polymer plasticizer may not have a reactive silicon group, but may have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a reactive silicon group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the polymer of component (A).

A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

The amount of the plasticizer used is 0 to 150 parts by weight, preferably 0 to 120 parts by weight, and more preferably 0 to 100 parts by weight with respect to 100 parts by weight of the polymer of component (A). When the amount of the plasticizer exceeds 150 parts by weight, the mechanical strength of the cured product is insufficient.

You may add the compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by a hydrolysis as needed to the curable composition of this invention. This compound has the effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mentioned. In addition, derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, which generate a silicon compound that generates R ³ SiOH such as trimethylsilanol by hydrolysis, trimethylol described in JP-A-11-241029 Mention may be made, for example, of a compound of a polyhydric alcohol having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol or sorbitol, which generates a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis. (R ³ is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.)

The can also include compounds that produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

The compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis is 0.1-20 weight part with respect to 100 weight part of organic polymers (A) which have a reactive silicon group, Preferably it is 0. Used in the range of 5 to 10 parts by weight.

A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent 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 rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group.

A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness and 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 very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of Toagosei Co., Ltd.)

Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The photocurable material is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. When the amount is less than 1 part by weight, there is no effect of improving the weather resistance, and when the amount exceeds 20 parts by weight, the cured product tends to be too hard and tends to crack.

An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (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, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate. The amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 100 parts by weight based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the 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 JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

It is desirable to use an antioxidant in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Specific examples of the hindered phenol-based antioxidant include IRGANOX 1010, IRGANOX 1076, IRGANOX 245 (all are manufactured by Ciba Specialty Chemicals Co., Ltd.); Denka Kogyo Co., Ltd.).

Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944FDL, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-63, ADK STAB LA-67, ADK STAB LA-68 (all manufactured by Asahi Denka Kogyo Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 A hindered amine light stabilizer shown in Life Tech Co., Ltd. or a benzoate light stabilizer shown in TINUVIN 120 (Ciba Specialty Chemicals Co., Ltd.) can also be used. The amount of the antioxidant and the light stabilizer used is preferably in the range of 0.1 to 10 parts by weight, more preferably 100 parts by weight of the organic polymer (A) having a reactive silicon group. 0.2 to 5 parts by weight.

An ultraviolet absorber can be used in the composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. Parts by weight. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

An epoxy resin can be added to the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester 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 Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferable examples include bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of these epoxy resins and the organic polymer (A) having a reactive silicon group is in the range of (A) / epoxy resin = 100/1 to 1/100 in terms of weight ratio. When the ratio of (A) / epoxy resin is less than 1/100, it is difficult to obtain an effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of (A) / epoxy resin exceeds 100/1. And the intensity | strength of organic type polymer cured material will become inadequate. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The component (A) is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of the hardened | cured material of (A) component, it is good to use 1-200 weight part of epoxy resins with respect to 100 weight part of (A) component, More preferably, 5-100 weight part is used. .

When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. As the epoxy resin curing agent that can be used, a commonly used epoxy resin curing agent can be used, but a compound having a primary amino group cannot be used. Specifically, tripropylamine, N, N-dimethylpropylamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-methylpyrrolidine, N, N′-dimethylpiperazine, benzyldimethylamine, Tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; Carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols; phenols; carboxylic acids; diketone complex of aluminum or zirconium Compounds such as compounds can be exemplified, but limited to these Not intended to be. Further, the curing agents may be used alone or in combination of two or more.

When the 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 is well known as a latent curing agent for epoxy resins, reacts with moisture in the air, and decomposes to produce an amine compound. Ketimine obtained by reacting a compound having a primary amino group with methyl isobutyl ketone as a raw material is commercially available and can be easily obtained. Examples of ketimines include EpiCure H-3, EpiCure H-30 (all of which are products of Japan Epoxy Resin Co., Ltd.), Adeka Hardener EH-235R, Adeka Hardner EH-235R-2, Adeka Hardener EH. -235X (all of which are products of Asahi Denka Kogyo Co., Ltd.). These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. The said flame retardant may be used independently and may be used together 2 or more types.

The flame retardant is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of component (A).

In the composition of the present invention, a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketone solvents, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. In the case of using a solvent, 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 because of the problem of air pollution when the composition is used indoors. These solvents may be used alone or in combination of two or more.

However, when the amount of the solvent is large, toxicity to the human body may be increased, and volume shrinkage of the cured product may be observed. Accordingly, the blending amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and substantially contains the solvent with respect to 100 parts by weight of the organic polymer of the component (A). Most preferably not.

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, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, An ant-proofing agent, a solvent, a fungicide, etc. are mentioned. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in this specification include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Application Laid-Open No. 63-254149, Japanese Patent Application Laid-Open No. 64-22904. No. 5, JP-A-2001-72854, etc.

In the one-component curable composition of the present invention, all the components are preliminarily blended and stored, and cured by moisture in the air after construction. Since it is a one-component curable composition in which all the ingredients are blended in advance, it is preferable that the ingredients containing moisture be used after being dehydrated and dried in advance, or dehydrated by decompression during compounding and kneading. . As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl By adding an alkoxysilane compound such as methyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane, the storage stability is further improved.

The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 100 parts by weight of organic polymer (A) having a reactive silicon group, preferably A range of 0.5 to 10 parts by weight is preferred.

The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

The one-component curable composition of the present invention does not use a harmful organotin compound and is excellent in curability, adhesiveness and storage stability.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Polymerization of propylene oxide using a polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of about 25,500 having a terminal hydroxyl group (manufactured by Tosoh as a liquid feeding system) HLC-8120GPC was used, the column was a Tosoh TSK-GEL H type, and the solvent was a polypropylene oxide (P-1) having a molecular weight in terms of polystyrene measured using THF. Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide (P-1) was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group to allyl. Converted to the base. Unreacted allyl chloride was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. As a result, a bifunctional polypropylene oxide (P-2) having a number average molecular weight of about 25,500 having an allyl group at the end was obtained.

Reaction with 1.1 parts by weight of trimethoxysilane for 5 hours at 90 ° C. with 100 parts by weight of the obtained allyl-terminated polypropylene oxide (P-2) as a catalyst using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex. To obtain a trimethoxysilyl group-terminated polyoxypropylene polymer (A-1). ^{As a} result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal trimethoxysilyl groups was 1.3 on average per molecule.

(Synthesis Example 2)
With respect to 100 parts by weight of allyl-terminated polypropylene oxide (P-2) obtained in Synthesis Example 1, a platinum vinylsiloxane complex having a platinum content of 3 wt% and an isopropanol solution of 150 ppm as a catalyst, the following chemical formula:
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ C ₂ H ₄ Si (OCH ₃ ) ₃
And the following chemical formula:
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH (CH ₃ ) Si (OCH ₃ ) ₃
A trimethoxysilyl group-terminated polyoxypropylene polymer (A) modified with dimethyldisiloxane by reacting with 2.1 parts by weight of a 84/16 (mol ratio) mixed solution with a silane compound represented by the formula -2) was obtained. The resulting trimethoxysilyl group-terminated polyoxypropylene polymer (A-2) has the following chemical formula:
_{-Si (CH 3) 2 OSi (} CH 3) 2 C 2 H 4 Si (OCH 3) 3
And a group represented by the following chemical formula:
_{-Si (CH 3) 2 OSi (} CH 3) 2 CH (CH 3) Si (OCH 3) 3
The molar ratio of (a) / (b) is 84/16. In addition, as a result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal trimethoxysilyl groups was about 1.2 on average per molecule.

(Synthesis Example 3)
After removing oxygen from the system by putting 200 g of isobutanol into a four-necked flask equipped with a stirrer, a heating device, a thermometer, and a nitrogen gas inlet, and stirring while bubbling nitrogen gas for 20 minutes, Heated to 105 ° C. A mixture of 264 g of butyl acrylate, 56 g of methyl methacrylate, 62 g of stearyl methacrylate, 18 g of γ-methacryloxypropyltrimethoxysilane and 60 g of isobutanol was used as a polymerization initiator, and 4.0 g of V-59 manufactured by Wako Pure Chemical Industries, Ltd. was used. The dissolved solution was added dropwise over 4 hours. Thereafter, a solution in which 0.4 g of V-59 was dissolved in 20 g of isobutanol was added to perform post-polymerization for 2 hours, and then cooled to room temperature to complete the polymerization. An acrylic polymer (A-3) having a solid content concentration of 60% and a number average molecular weight of 10,000 by gel permeation chromatography (polystyrene conversion) was obtained.

Example 1
Surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., trade name: Baiyinhua CCR) 50 with respect to 100 parts by weight of the trimethoxysilyl group-terminated polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 Parts by weight, heavy calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Whiten SB) 50 parts by weight, sagging inhibitor (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500), hindered phenol-based oxidation 1 part by weight of an inhibitor (Ciba Specialty Chemicals Co., Ltd., trade name: Irganox 1010), 1 part by weight of a benzoate UV absorber (Sumitomo Chemical Co., Ltd., trade name: Sumisorb 400), hindered amine light 3 parts paint after weighing, mixing and kneading thoroughly 1 part by weight of stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS-765) Dispersed through 3 times Lumpur. Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or lower, and γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Toray Dow Corning Co., Ltd.) as an adhesion-imparting agent. 4 parts by weight, 0.89 parts by weight of bis (3-trimethoxysilylpropyl) amine (made by Toray Dow Corning Co., Ltd., trade name: A-1170), titanium diisopropoxide bis (ethylacetoacetate as a curing catalyst ) (Matsumoto Pharmaceutical Co., Ltd., trade name: ORGATICS TC-750) 4 parts by weight was added and kneaded, kneaded in a substantially moisture-free state, and then sealed in a cartridge which is a moisture-proof container A one-component curable composition was obtained.

(Example 2)
Example 1 except that 100 parts by weight of the trimethoxysilyl-terminated polyoxypropylene polymer (A-2) obtained in Synthesis Example 2 was used instead of the polymer (A-1) in Example 1. Similarly, a curable composition was obtained.

(Example 3)
Example 1 except that 1.24 parts by weight of N-ethyl-γ-aminoisobutyltrimethoxysilane (manufactured by GE Silicones Corp., trade name: Silquest A-Link15) was used instead of A-1170 in Example 1. In the same manner as in Example 1, a curable composition was obtained.

Example 4
Instead of A-1170 in Example 1, 1.43 parts by weight of (N-phenyl-γ-aminopropyl) trimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name: Y-9669) was used. Obtained a curable composition in the same manner as in Example 1.

(Example 5)
A curable composition was obtained in the same manner as in Example 1 except that A-1170 in Example 1 was not used.

(Example 6)
80 parts by weight of the trimethoxysilyl group-terminated polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the isomethoxysilyl group-containing acrylic polymer (A-3) obtained in Synthesis Example 3 33.3 parts by weight (20 parts by weight of solid content) of the butanol solution was mixed well, and heated at 120 ° C. and reduced pressure for 2 hours using a rotary evaporator to completely remove isobutanol. A curable composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the mixed polymer was used instead of the polymer (A-1) in Example 5.

(Comparative Example 1)
Example 3 was used in the same manner as in Example 1 except that 3 parts by weight of γ-aminopropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: A-1110) was used instead of A-1170 in Example 1. Thus, a curable composition was obtained.

(Comparative Example 2)
Instead of the polymer (A-1) in Comparative Example 1, 100 parts by weight of the trimethoxysilyl-terminated polyoxypropylene polymer (A-2) obtained in Synthesis Example 2 was used, and the usage amount of A-1110 A curable composition was obtained in the same manner as in Comparative Example 1 except that was changed to 1 part by weight.

(Comparative Example 3)
Instead of using A-187 and A-1170 in Example 1, a reaction product of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane (excess of γ-aminopropyltriethoxysilane) A curable composition was obtained in the same manner as in Example 1 except that 4.4 parts by weight (manufactured by Chisso Corporation, trade name: Sila Ace XS-1104) was used.

(Comparative Example 4)
Example 1 except that 2 parts by weight of isopropyltri (N-amidoethyl / aminoethyl) titanate (manufactured by Ajinomoto Fine-Techno Co., Ltd., trade name: Preneact KR-44) was used instead of A-1170 in Example 1. In the same manner as in Example 1, a curable composition was obtained.

(Comparative Example 5)
A curable composition was obtained in the same manner as in Example 1 except that A-187 and A-1170 in Example 1 were not used.

(Comparative Example 6)
Example 1 except that 4 parts by weight of vinyltrimethoxysilane (trade name: A-171 manufactured by Toray Dow Corning Co., Ltd.) was used instead of using A-187 and A-1170 in Example 1. In the same manner, a curable composition was obtained.

(Comparative Example 7)
Instead of using TC-750 in Comparative Example 1, dibutyltin dilaurate (manufactured by Sansha Co., Ltd., trade name: STANN BL) was used in the same manner as Comparative Example 1, except that 0.2 parts by weight was used. A curable composition was obtained.

(Curable)
23 ° C., 50% R.D. H. Stretch the curable composition to a thickness of about 3 mm under conditions, and occasionally touch the surface of the curable composition with a microspatula until the composition no longer adheres to the microspatula. It was measured. The results are shown in Tables 3 and 4.

(Curability after storage)
In order to evaluate the stability after storage, each one-component curable composition was put in a dryer at 50 ° C. for 28 days, taken out, and taken out at 23 ° C. and 50% R.D. H. After being placed in the conditions for one day or longer, the curability was evaluated in the same manner as described above, and compared with the initial value. The value of curability after storage does not change at all compared to the initial curability, that is, the rate of change is 1.0, the rate of change is 0.7 to 1.3, and the rate of change is 0. Less than 0.7 or greater than 1.3 was represented by Δ, and those having a rate of change greater than 3.0 were represented by ×.

(Viscosity change before and after storage)
Similarly to the above, for each of the curable compositions at the initial stage and after storage, a BM viscometer (manufactured by Tokyo Keiki Co., Ltd.), rotor No. 7 was used to measure the 2 rpm viscosity at 23 ° C. The value obtained by dividing the viscosity value after storage by the initial value is calculated as the viscosity increase rate after storage, and the viscosity increase rate from 1.0 to 1.4 is ○, greater than 1.4 and less than 2.0 Were marked with Δ, 2.0 or more were marked with x, and those that could not be measured due to gelation were marked with xx.

(Adhesiveness of cured product)
After placing the curable composition on four types of adherends (anodized aluminum, stainless steel plate, glass, acrylic plate) in close contact with each other and curing for 7 days under a constant temperature and humidity condition of 23 ° C. and 50% RH After cutting with a razor blade at the interface between the cured product and the substrate and pulling in the direction of 90 degrees, the fractured state of the cured product was observed, and the cohesive failure rate (CF rate) was measured.

The results are shown in Tables 3 and 4. In the table, a CF ratio of 100% is indicated as ◯, 50% or more and less than 100% as Δ, and less than 50% as ×. As a comprehensive evaluation of adhesiveness, the total of x of the adhesion to four types of substrates is 0, the total of x is 1 to 2, the total of x is 3 to 4 X.

(Environmental compatibility)
Those not using an organic tin compound are indicated as ◯, and those using an organic tin compound are indicated as ×.

As shown in Examples 1 to 6, using (A) an organic polymer having a reactive silicon group, (B) a titanium catalyst, and (C) an epoxysilane, curing without a compound having a primary amino group The composition is environmentally friendly because it has fast curability, little change in viscosity before and after storage, good stability, good adhesion to the substrate, and no organotin compound. It is a thing. On the other hand, Comparative Examples 1 to 4 to which a compound having a primary amino group has been added have increased viscosity after storage and lack stability. In Comparative Example 5, which does not contain any silane coupling agent, the initial curability is fast, but the adhesion to the substrate is poor, and it is cured in the cartridge after storage, resulting in poor physical property stability. In Comparative Example 6 using vinylsilane instead of epoxysilane, the stability of physical properties before and after storage is good, but the adhesion to the substrate is poor. Comparative Example 7 using an organotin compound has good curability and stability after storage, but has insufficient adhesion, has an environmental burden, and has poor environmental compatibility.

The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. Can be used for etc. Since the hardened | cured material obtained by hardening | curing the curable composition of this invention is excellent in a softness | flexibility and adhesiveness, it is more preferable to use as a sealing material or an adhesive agent among these.

Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, adhesives for vehicle panels, adhesives for electrical / electronic / precision equipment assembly, sealing materials for direct glazing, sealing materials for multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, Can also be used.

Claims (7)

(A) an organic polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond;
(B) a titanium catalyst,
(C) a silane compound having an epoxy group and an alkoxy group,
A curable composition containing, and an organic tin compound in the composition, in a primary substantially one-component curable composition characterized by containing no compound having an amino group There,
A curable composition wherein the main chain skeleton of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer and a (meth) acrylic ester polymer . The curable composition according to claim 1, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer. The titanium catalyst (B) has the general formula (1):
Ti (OR ¹ ) ₄ (1)
The curability according to claim 1 or 2 , wherein R ¹ is an organic group, and four R ^{1 s} may be the same or different from each other. Composition. The compound represented by the general formula (1) is represented by the general formula (2):

[Wherein, n R ^{2 s} are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. (4-n) pieces of R ³ are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. (4-n) A ¹ and (4-n) A ² are each independently —R ⁴ or —OR ⁴ (wherein R ⁴ is substituted or unsubstituted having 1 to 8 carbon atoms) Of the monovalent hydrocarbon group). n is 0, 1, 2, or 3. ] A titanium chelate represented by the general formula (3):

(Wherein R ³ , A ¹ , and A ² are the same as described above. R ⁵ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.) The curable composition according to claim 3 . The curable composition according to any one of claims 1 to 4 , wherein the silane compound having an epoxy group (C) and having an alkoxy group is γ-glycidoxypropyltrimethoxysilane. The sealing material which uses the curable composition in any one of Claims 1-5 . The adhesive agent using the curable composition in any one of Claims 1-5 .