JP2007091929A - Organosiloxane-modified polyoxyalkylene polymer and/or (meth)acrylic ester polymer and curable composition containing the polymers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyoxyalkylene polymer and/or a (meth)acrylic ester polymer excellent in curability and tensile properties and useful for sealants and adhesives and to provide a curable composition containing the polymers. <P>SOLUTION: Disclosed is a polyoxyalkylene polymer and/or a (meth)acrylic ester polymer having a group represented by formula (1): -(SiR<SP>1</SP><SB>2</SB>O)<SB>n</SB>SiR<SP>1</SP><SB>2</SB>-R<SP>2</SP>-SiX<SB>3</SB>(wherein R<SP>1</SP>is a hydrocarbon group or a triorganosiloxy group; R<SP>2</SP>is a divalent 3 to 20C linear alkylene group; X is a hydroxy group or a hydrolyzable group; and n is an integer of 0 to 100). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a polyoxyalkylene having a silicon-containing group (hereinafter also referred to as “reactive silicon group”) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond. The present invention relates to a polymer and / or a (meth) acrylic acid ester polymer (hereinafter also referred to as “organic polymer”), and a curable composition containing the organic polymer.

An organic polymer having a reactive silicon group in the molecule has a characteristic that it reacts with moisture in the air even at room temperature and cures into a rubber-like shape, and is disclosed in Patent Document 1 and the like. These organic polymers have already been industrially produced and are widely used for applications such as sealing materials and adhesives.

Sealing materials and adhesives may be required to have a rubber-curing property in a shorter time (hereinafter also referred to as “fast curing” for short). Moreover, it may be desired that the obtained cured product has higher tensile strength.

As a technique for obtaining a fast-curing curable composition, Patent Document 2 discloses a curable composition using an organic polymer containing a silicon-containing functional group having three hydrolyzable groups on silicon. ing. Patent Document 3 discloses a cured product obtained by curing the curable composition by using an organic polymer containing a silicon-containing functional group having three or more hydrolyzable groups on silicon. Techniques for improving creep resistance, durability and resilience are disclosed. On the other hand, a typical industrial product of an organic polymer having a reactive silicon group is formed by bonding two hydrolyzable groups per silicon atom in order to obtain a cured product having excellent elongation and flexibility. It has a reactive silicon group at the end of the polymer.

Various methods for producing an organic polymer having a reactive silicon group have been disclosed. Among them, a production method in which hydrosilane having a reactive silicon group is allowed to act on an organic polymer having an unsaturated group is a production method in which a high conversion can be obtained in a relatively short reaction time. The polymer is characterized by low viscosity and good workability.

However, in order to introduce a reactive silicon group in which three hydroxyl groups or hydrolyzable groups are bonded per silicon atom by using the above-described production method in which hydrosilane is allowed to act, trimethoxysilane or the like However, the silane compound may be difficult to obtain from the viewpoint of safety.

On the other hand, Patent Literature 4, Patent Literature 5, and Patent Literature 6 disclose polyoxyalkylene polymers in which reactive silicon groups are introduced using organosiloxane-modified hydrosilane compounds having reactive silicon groups. Yes. The hydrosilane compound is highly safe.

As a method for obtaining an organosiloxane-modified hydrosilane compound containing a reactive silicon group formed by bonding three hydroxyl groups or hydrolyzable groups per silicon atom, as described in Patent Document 4, Patent Document 5, etc. And general formula (3):
_{^{H- (SiR 1 2 O) n}} SiR 1 2 -H (3)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group or (R ′) ₃ SiO— (R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 × n + 2 R ^{1 s} may be the same or different from each other, and n represents an integer of 0 to 100). It can be obtained by a hydrosilylation reaction between dihydroorganosiloxane and a silane compound having a silicon-containing functional group having three hydroxyl groups or hydrolyzable groups on silicon and an unsaturated group.
JP-A-52-73998 International Publication No. 98/047939 Pamphlet International Publication No. 04/039892 Pamphlet JP-A-6-166810 US Pat. No. 5,403,881 Japanese Patent Laid-Open No. 9-12709

However, when a polymer in which a reactive silicon group is introduced using an organosiloxane-modified hydrosilane compound specifically disclosed in Patent Document 4, Patent Document 5 and Patent Document 6, curing of the resulting curable composition is performed. It has been found that there is a problem that the properties and the strength of the cured product are not sufficient.
An object of the present invention is to provide an organosiloxane-modified polyoxyalkylene polymer having improved curability and cured product strength, and a curable composition containing the polymer.

As a result of diligent studies to solve such problems, the present inventors have a reactive silicon group formed by bonding three hydroxyl groups or hydrolyzable groups per silicon atom, and further, Organosiloxane-modified polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer in which the alkylene group bonded to the reactive silicon group (R ^{2 in the following} general formula (1)) is an alkylene group having a specific structure As a result, it was found that a curable composition having fast curability and high cured product strength can be obtained, and the present invention was completed.

That is, the present invention provides a general formula (1) as a silicon-containing group that can be crosslinked by forming a siloxane bond:
^{_{- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group or (R ′) ₃ SiO— (R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 × n + 2 R ^{1 s} may be the same or different from each other, and R ² may be a divalent group having 3 to 20 carbon atoms. Represents a linear alkylene group, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different from each other, and n represents an integer of 0 to 100). The present invention relates to a polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer having a group represented by:

The polyoxyalkylene polymer of the present invention preferably contains a polyoxyalkylene polymer polymerized using a double metal cyanide complex catalyst as a main chain skeleton.

The polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer of the present invention is preferably a polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer having an unsaturated group introduced at the terminal. Polymer and general formula (2):
^{_{H- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (2)
(Wherein R ¹ , R ² , X and n are the same as above) represented by a polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer obtained by addition reaction with a hydrosilane compound is there.

R ² is preferably (CH ₂ ) _m (wherein m represents an integer of 3 to 20).

X is preferably a methoxy group.

Furthermore, the present invention provides a curable composition characterized by containing the polyoxyalkylene polymer and / or the (meth) acrylic acid ester polymer.

The present invention will be described in detail below.
In the following description, the polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer (hereinafter also referred to as “organic polymer”) of the present invention is distinguished from other organic polymers. Therefore, it may be referred to as an organic polymer (A).

The polyoxyalkylene polymer and the (meth) acrylic acid ester polymer, which are the main chain skeleton of the component (A) of the present invention, have high moisture permeability and excellent deep part curability when made into a one-component composition. The polyoxyalkylene polymer is more preferable.

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.

The reactive silicon group contained in the organic polymer of the component (A) used in the present invention has the general formula (1):
^{_{- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group or (R ′) ₃ SiO— (R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 × n + 2 R ^{1 s} may be the same or different from each other, and R ² may be a divalent group having 3 to 20 carbon atoms. Represents a linear alkylene group, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different from each other, and n represents an integer of 0 to 100). expressed.

R ¹ in the general formula (1) is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms and more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms from the viewpoint of availability and cost. A monovalent hydrocarbon group having 1 to 4 carbon atoms is particularly preferred.

Specific examples of R ¹ in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group, a halogenated alkyl group such as a 3,3,3-trifluoropropyl 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, or R ′ is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms such as a methyl group or a phenyl group (R ′) _3. And triorganosiloxy group represented by SiO-. Among these, a methyl group is particularly preferable from the viewpoint of availability and cost.

R ² in the general formula (1) is essentially a divalent linear alkylene group having 3 to 20 carbon atoms from the viewpoint of availability, curability, and tensile strength of the cured product. From the viewpoint of cost, a divalent linear alkylene group having 3 to 12 carbon atoms is preferable, a divalent linear alkylene group having 3 to 8 carbon atoms is more preferable, and 2 having 3 or 6 carbon atoms. Divalent hydrocarbon groups are particularly preferred. When the number of carbon atoms of R ² is less than 3, the curability and the tensile strength of the cured product tend to be low, and when the number of carbon atoms is greater than 20, the organic weight increases with the crystallinity of the alkylene group. The workability of coalescence tends to decrease. Further, when the branched chain R ² is present, the tensile strength of the curable and the cured product tends to be low.

R ² in the general formula (1) is preferably (CH ₂ ) _m (wherein m represents an integer of 3 to 20) from the viewpoints of curability and tensile strength of the cured product.
As a specific example of R ² in the general formula (1),
_{-CH 2 CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -,
Etc. Among these, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH _2- is preferable from the viewpoint of availability, curability, and tensile strength of the cured product,
_{-CH 2 CH 2 CH 2 -,} - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 - are more preferable,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 CH 2 - is particularly preferred.

The reactive silicon group represented by the general formula (1) has three hydroxyl groups or hydrolyzable groups X on the silicon atom, and cures the curable composition containing the organic polymer as the component (A). The hardened | cured material obtained shows high restoring property.

The hydrolyzable group is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

More specific examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. A methoxy group and an ethoxy group are more preferable, and a methoxy group is particularly preferable because of high activity and good curability.
N in the general formula (1) is an integer of 0 to 100. Preferably it is an integer of 1 to 5, particularly preferably 1.

The method for introducing the reactive silicon group is not particularly limited, and examples thereof include the following methods.
First, a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer containing an unsaturated group is obtained by the following method. The polyoxyalkylene polymer containing an unsaturated group has a polyoxyalkylene polymer having a functional group such as a hydroxyl group in the molecule, and an active group and an unsaturated group that are reactive with the functional group. It can be obtained by reaction with an organic compound or copolymerization with an unsaturated group-containing epoxy compound. The (meth) acrylic acid ester polymer containing an unsaturated group is a (meth) acrylic acid ester polymer having a functional group such as halogen obtained by the living radical polymerization method described later, and this functional group. It can be obtained by a reaction with an organic compound having an active group and an unsaturated group, or a radical polymerization of a monomer having an unsaturated group and a (meth) acrylate monomer.

Next, an organic polymer having an unsaturated group introduced at the terminal and the general formula (2):
^{_{H- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (2)
(Wherein R ¹ , R ² , X, and n are the same as described above) are reacted with a hydrosilane compound in the presence of a platinum group metal catalyst to react as a component (A) of the present invention. An organic polymer having a silicon group is obtained.

The above method is preferable because a high conversion can be obtained in a relatively short reaction time. Furthermore, the organic polymer having a reactive silicon group obtained by the above method is preferable because it becomes a curable composition having a low viscosity and good workability.

Specific examples of the hydrosilane compound represented by the general formula (2) include, for example,
_{H-Si (CH 3) 2} OSi (CH 3) 2 -CH 2 CH 2 CH 2 -Si (OCH 3) 3
_{H-Si (CH 3) 2} OSi (CH 3) 2 -CH 2 CH 2 CH 2 -Si (OC 2 H 5) 3
_{H-Si (CH 3) 2} OSi (CH 3) 2 -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -Si (OCH 3) 3
_{H-Si (CH 3) 2} OSi (CH 3) 2 -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -Si (OC 2 H 5) 3
Etc.

Although the manufacturing method of the hydrosilane compound represented by General formula (2) is not specifically limited, For example, General formula (3):
_{^{H- (SiR 1 2 O) n}} SiR 1 2 -H (3)
(Wherein R ¹ and n are as defined above), and the general formula (4):
^{_{H 2 C = CH-R 3}} -SiX 3 (4)
(Wherein X is the same as above, R ³ represents a divalent linear alkylene group having 1 to 18 carbon atoms) and a vinyl group-containing silane represented by a platinum group metal catalyst. Can be obtained by hydrosilylation reaction.

Specific examples of the platinum group metal catalyst include, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972), a complex of chloroplatinic acid and an olefin (US Pat. No. 3). 159,601, 3,159,662, and 3,775,452), platinum black, palladium or the like is supported on a support such as alumina, silica, or carbon. And rhodium-olefin complexes, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. Of these, the complex type is preferably used by dissolving in an organic solvent such as alcohol, ketone or ether.

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, particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

In order to obtain a rubber-like cured product having high strength, high elongation and low elastic modulus, the average number of 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 (5):
-R ⁴ -O- (5)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ in the general formula (5) 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 (5) 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 in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or has a relatively low viscosity.

As a polymerization method of the polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, or a complex obtained by reacting an organoaluminum compound and a porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent 3,278,457, US Patent 3,278,458, US Patent 3,278,459, US Patent 3,427,256, US Patent 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited. Among these, a polymerization method using a double metal cyanide complex catalyst is preferable because a polymer having a large number average molecular weight and a small molecular weight distribution (Mw / Mn) can be obtained.

A method for producing a polyoxyalkylene polymer having a reactive silicon group is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, JP-A-57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Killen polymer can be exemplified, but not particularly limited thereto.

The above polyoxyalkylene polymers having a reactive silicon group may be used alone or in combination of two or more.
The main chain skeleton of the polyoxyalkylene polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

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, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl), 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid. 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 rumaleimide; 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 from the physical property of a product etc. is preferable. 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 Application 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.

The curable composition of this invention contains the organic polymer (A) which has the reactive silicon group of this invention mentioned above.
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 curing catalyst can be added to the curable composition of the present invention. Specific examples include carboxylic acid metal salts such as tin 2-ethylhexanoate, tin versatate, and bismuth 2-ethylhexanoate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2 -Ethylhexanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate) Acid), dibutyltin bis (benzyl maleate), dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin Oxide, di Dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetate), reaction product of dibutyltin oxide and silicate compound, reaction product of dialkyltin dicarboxylate and silicate compound such as dibutyltin dilaurate, dibutyltin oxide Organic compounds such as tetraisopropoxytitanium, tetra-n-butoxytitanium, diisopropoxytitanium bis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), etc. Titanates; organoaluminum compounds such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium tet Zirconium compounds such as tetrakis (acetylacetonate) and the like.

A curing catalyst is used in 0.001-10 weight part with respect to 100 weight part of (A) component, Preferably it is 0.01-3 weight part, More preferably, it is used in 0.05-1 weight part.

A silane coupling agent can be added to the curable composition of the present invention. Specific examples include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, and (isocyanatemethyl). Isocyanate group-containing silanes such as dimethoxymethylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriiso Propoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrime Xysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2- Aminoethyl) aminopropyltriisopropoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltri Ethoxysilane N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, etc. Amino group-containing silanes; Ketimine type silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltri Mercapto group-containing silanes such as ethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. Epoxy group-containing silanes; carboxy such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane Silanes; vinyl type unsaturated such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane Group-containing silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate; In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . Examples of the reaction product of the silane coupling agent include the reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, and partial condensates of various silane coupling agents.

The silane coupling agent is preferably about 0.1 to 15 parts by weight, more preferably about 1 to 10 parts by weight, and particularly preferably about 3 to 7 parts by weight with respect to 100 parts by weight of the component (A). If the blending amount is below this range, the adhesion and storage stability may not be sufficient. On the other hand, if the blending amount exceeds this range, the deep curability may not be sufficient.

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, phenolic 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, storage stability can be improved particularly when a one-component composition is used.

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. Obtainable. 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 with respect to 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%.

When using a balloon, the anti-slip agent as described in JP-A-2000-154368 and the surface of a cured product as described in JP-A-2001-164237 are matted to give an uneven state. An amine compound for obtaining a state, particularly a primary and / or secondary amine having a melting point of 35 ° C. or higher can be added.

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-7-113073, JP-A-9-53063, JP-A-10-10. -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 bonding 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 the bonding interface is 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; 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.

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 is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

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, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).

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 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer of component (A). If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be 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 mention | raise | lifted. 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, and trimethylol described in JP-A-11-241029 Examples thereof include 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.

Further, there may be mentioned also compounds which 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.

In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the 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 photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a very short time by 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. Typical 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, 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 Toa Gosei Chemical 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 increasing the weather resistance, and when the amount is more than 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, zirconium octylate, and amine compounds. 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.

An antioxidant (antiaging agent) can be used 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. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (All from Asahi Denka Kogyo Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all from Sankyo Co., Ltd.) It is also possible to use hindered amine light stabilizers shown in (1). Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant 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.

A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer is used in an amount of 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. Specific examples of the light stabilizer are also described in JP-A-9-194731.

When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (and above) Examples thereof include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Corporation).

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 tetrabromobisphenol A glycidyl ether, 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 preferred are 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, the effect of improving the impact strength and toughness of the cured epoxy resin is difficult to obtain, 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. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. 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 stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyethylamines such as ethyl) amine and tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyl Triethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyl aminosilane such as methyldimethoxysilane; and may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. 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, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides. 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 the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. 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 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 is 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.

According to the present invention, a curable composition useful as a sealant or adhesive having improved curability and tensile strength, including an organosiloxane-modified polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer. Can provide things.

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 with 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 (using Tosoh's HLC-8120GPC as the liquid feeding system) The column used a Tosoh TSK-GEL H type, and the solvent obtained was a polystyrene oxide (polystyrene equivalent molecular weight measured using THF). Subsequently, a methanol solution of NaOMe equivalent to 1.2 times equivalent to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As a result, a polypropylene oxide having a number average molecular weight of about 25,500 having an allyl group at the end was obtained.

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 devolatilization under reduced pressure to obtain a purified allyl group-terminated polypropylene oxide (hereinafter, allyl polymer). With respect to 100 parts by weight of the obtained allyl polymer, 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst, the following chemical formula:
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
And dimethyldisiloxane-modified trimethoxysilyl group-terminated poly (R) in which R ^{2 in the} general formula (1) is —CH ₂ CH ₂ CH ₂ —. Oxypropylene (A-1) was obtained. ^{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 1.3 on average per molecule.

(Synthesis Example 2)
For the allyl-terminated polypropylene oxide obtained in Synthesis Example 1, the following chemical formula was used in the same procedure as in Synthesis Example 1.
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
Is reacted with 2.8 parts by weight of the silane compound represented by formula (1), the terminal has an average of 1.3 trimethoxysilyl groups, and R ^{2 in the} general formula (1) is —CH ₂ CH ₂ CH ₂ CH. Dimethyldisiloxane-modified polyoxypropylene (A-2) which was ₂ CH ₂ CH ₂ — was obtained.

(Comparative Synthesis Example 1)
For the allyl-terminated polypropylene oxide obtained in Synthesis Example 1, the following chemical formula was used in the same procedure as in Synthesis Example 1.
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
A silane compound represented by the following chemical formula,
HSi (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH (CH ₃ ) Si (OCH ₃ ) ₃
The reaction is carried out using 2.3 parts by weight of a 62/38 (mol ratio) mixed solution with the silane compound represented by formula (1), having an average of 1.3 trimethoxysilyl groups at the ends, A dimethyldisiloxane-modified polyoxypropylene (A-3) in which R ² of —CH ₂ —CH ₂ — or —CH (CH ₃ ) — was obtained.

(Examples 1-2, Comparative Example 1)
(Curable)
Dibutyltin bis (acetylacetonate) (manufactured by Nitto Kasei, Neostan U-220) with respect to 100 parts by weight of the polymers (A-1 to A-3) obtained in Synthesis Examples 1-2 and Comparative Synthesis Example 1. 0.15 part by weight was added, kneaded well with a spatula for 2 minutes, and allowed to stand under constant temperature and humidity conditions of 23 ° C and 50%. The curing time was measured by setting this time as the curing start time and touching the surface of the composition with the tip of the spatula, and setting the time when the composition no longer adhered to the spatula as the skinning time. The results are shown in Table 1.

(Tensile property of cured product)
To 100 parts by weight of the polymers (A-1 to A-3) obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1, 1.5 parts of tin octylate (manufactured by Nitto Kasei, Neostan U-28), After adding 0.25 parts by weight of laurylamine (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.6 parts by weight of pure water and mixing well, the defoamed mixture is carefully taken so that bubbles do not enter the polyethylene mold. Cast from No. 3 dumbbell according to JISK6251 from a cured sheet of 3 mm thickness obtained by pouring and curing at 23 ° C. for 1 hour and further at 70 ° C. for 20 hours, and tensile test (tensile at 23 ° C. and 50% RH) Tb: strength at break (MPa) was measured. The results are shown in Table 1.
Table 1 shows the evaluation results of curability and tensile properties of the cured product.

As shown in Table 1, the polyoxyalkylene system having an organosiloxane-modified reactive silicon group of the present invention in which R ^{2 in the} general formula (1) is a divalent linear alkylene group having 3 to 20 carbon atoms When a polymer was used (Examples 1 and 2), fast curability and high tensile properties were exhibited.

(Examples 3 to 4, Comparative Example 2)
100 parts by weight of the polymers (A-1 to A-3) obtained in Synthesis Examples 1 and 2 and Comparative Synthesis Example 1, 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd., Shiruka Hana CCR), titanium oxide (Ishihara) 20 parts by weight, manufactured by Taipaque R-820), 55 parts by weight of a plasticizer diisodecyl phthalate (manufactured by Shin Nippon Chemical Co., Ltd., Sunsocizer DIDP), 2 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei, Disparon 6500), UV absorber 1 part by weight (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of light stabilizer (manufactured by Sankyo, Sanol LS770), 2 parts by weight of vinyltrimethoxysilane (A-171 manufactured by Toray Dow Corning) as a dehydrating agent N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (A-112 manufactured by Toray Dow Corning, Inc.) 0) 3 parts by weight were kneaded under dehydrating conditions. Finally, 0.15 parts by weight of dibutyltin dilaurate (manufactured by Sansha Co., Ltd., STANN BL) is added as a curing catalyst, mixed well, and then sealed in a moisture-proof container to form a one-component curable composition. Obtained. Using the prepared one-component curable composition, the curability (skinning time) and the tensile properties of the cured product were evaluated in the following manner.

(Curable)
Each curable composition was extruded from the cartridge, filled into a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat surface. This time was set as the curing start time, the surface was touched with a spatula, and the time when the composition did not adhere to the spatula was measured as the skinning time. The skinning time was measured under the condition of 23 ° C./50% RH. The results are shown in Table 2.

(Tensile property of cured product)
Each composition shown in Table 2 was cured at 23 ° C. × 3 days + 50 ° C. × 4 days to prepare a sheet having a thickness of about 3 mm. This sheet was punched into a No. 3 dumbbell mold, and a tensile test was conducted at a pulling speed of 200 mm / min. Tb: strength at break (MPa) was measured. The results are shown in Table 2.
Table 2 shows the composition and the evaluation results of the curability and tensile properties of the cured product.

As shown in Table 2, the polyoxyalkylene system having an organosiloxane-modified reactive silicon group of the present invention in which R ^{2 in the} general formula (1) is a divalent linear alkylene group having 3 to 20 carbon atoms When a polymer was used (Examples 3 and 4), fast curability and high tensile properties were exhibited.

Claims (6)

As a silicon-containing group that can be crosslinked by forming a siloxane bond, the general formula (1):
^{_{- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (1)
(In the formula, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group or (R ′) ₃ SiO— (R ′ is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 2 × n + 2 R ^{1 s} may be the same or different from each other, and R ² may be a divalent group having 3 to 20 carbon atoms. Represents a linear alkylene group, X represents a hydroxyl group or a hydrolyzable group, and three Xs may be the same or different from each other, and n represents an integer of 0 to 100). A polyoxyalkylene polymer and / or a (meth) acrylate polymer having a group represented by The polyoxyalkylene polymer according to claim 1, comprising a polyoxyalkylene polymer polymerized using a double metal cyanide complex catalyst as a main chain skeleton. Polyoxyalkylene polymer and / or (meth) acrylic acid ester polymer in which an unsaturated group is introduced at the terminal and general formula (2):
^{_{H- (SiR 1 2 O) n}} SiR 1 2 -R 2 -SiX 3 (2)
^{(Wherein, R 1, R 2, X} , n are as defined above) polyoxyalkylene-based polymer according to claim 1 or 2, characterized in that it is obtained by addition reaction of a hydrosilane compound represented by And / or (meth) acrylic acid ester polymers. The polyoxyalkylene polymer according to any one of claims 1 to 3, wherein R ² is (CH ₂ ) _m (wherein m represents an integer of 3 to 20). (Meth) acrylic acid ester polymer. The polyoxyalkylene polymer and / or the (meth) acrylic acid ester polymer according to any one of claims 1 to 4, wherein X is a methoxy group. A curable composition comprising the polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer according to any one of claims 1 to 5.