JP2009120720A - Composition containing organic polymer having reactive silicone group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cured product exhibiting excellent strength and elongation while maintaining workability of an organic polymer composition having a reactive silicone group. <P>SOLUTION: Provided is the composition comprising an organic polymer (A) having groups represented by general formula (1):-[Si(R<SP>1</SP><SB>2-b</SB>)(X<SP>1</SP><SB>b</SB>)O]<SB>m</SB>Si(R<SP>1</SP><SB>3-a</SB>)X<SP>1</SP><SB>a</SB>(1) and an acid (B). Therein, R<SP>1</SP>is a 1 to 20C alkyl group, a 6 to 20C aryl group, a 7 to 20C aralkyl group, or a triorganosiloxy group represented by formula: (R')<SB>3</SB>SiO-, wherein two or more R<SP>1</SP>groups exist, the R<SP>1</SP>groups may be identical or different from each other; R' is a 1 to 20C monovalent hydrocarbon group, where the three R's may be identical or different from each other; X<SP>1</SP>is OH or a hydrolysable group; (a) and (b) are each 0 or 1; m(b)s may be identical or different from each other, and satisfy a+Σb=1; and (m) is an integer of 0 to 19. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and a silicon group that can be condensed by forming a siloxane bond (hereinafter sometimes referred to as “reactive silicon group”). The present invention relates to a composition containing an organic polymer.

  An organic polymer having at least one reactive silicon group such as a dimethoxymethylsilyl group in the molecule becomes rubbery by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like even at room temperature. It is known to cure.

  Among these organic polymers having a reactive silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer have already been industrially produced and are used as sealing materials, adhesives. And widely used in applications such as paints (for example, Patent Documents 1 and 2).

  Various properties such as curability, adhesiveness, and mechanical properties are required for curable compositions used for sealing materials, adhesives, paints, and the like and rubber-like cured products obtained by curing. For example, in a seal of a joint having a large expansion / contraction width, high followability to strength and strength are required.

Mechanical properties of a cured product obtained from a curable composition containing an organic polymer having a reactive silicon group are greatly influenced by the main chain skeleton of the organic polymer. In general, in a three-dimensional network structure forming a cured product, when the molecular weight between crosslinking points is large, good stretchability tends to be obtained. On the other hand, when the molecular weight of the organic polymer is increased, the viscosity increases, and the workability tends to decrease. In addition, there is a method of reducing the viscosity by diluting with a plasticizer or a solvent and improving the stretchability while maintaining good workability. However, depending on the case, sufficient mechanical strength may not be obtained, There is concern about the influence on various physical properties caused by bleed-out of plasticizer. As a method of obtaining a composition that provides a cured product exhibiting high strength and high stretchability while solving the above-mentioned problems and ensuring workability, the molecular weight between crosslink points of the cured product is determined using a chain extension reaction. A method of increasing the size can be considered. Specifically, by using a polymer having a monofunctional reactive group at both ends, it has a low molecular weight and low viscosity before curing, but has a high molecular A cured product having high elasticity is obtained. However, in the conventional method using an organic tin compound generally used as a curing catalyst for a reactive silicon group-containing organic polymer, the monofunctional silicon group has extremely low reactivity and sufficient physical properties. A cured product could not be obtained. Patent Document 3 discloses a technique that exhibits the above effect by using a carboxylic acid tin salt as a curing catalyst. However, there is still room for improvement. In Patent Document 4, a reactive silicon group-containing polymer having a special terminal structure in which a reactive silicon group is bonded to a polymer main chain via a methylene spacer (—CH ₂ —) by a urethane bond or a urea bond. There has been proposed a method for improving the above-mentioned problem by improving the reactivity of a monofunctional silicon group. However, even in this method, it is difficult to say that the chain extension effect of the monofunctional polymer is sufficient, and there is a concern that the storage stability (viscosity increase, workability decrease) accompanying the high activation of the silicon group may occur. . Further, this is a limited technique that cannot be applied to a conventional polymer having a trimethylene spacer (—CH ₂ CH ₂ CH ₂ —).
JP-A-52-73998 JP-A 63-6041 JP 2001-323151 A JP 2005-514504 Gazette

  The present invention is a composition comprising an organic polymer having a reactive silicon-containing group as a main component, has good workability before the reaction, and has excellent strength and stretchability due to the reaction of the reactive silicon group. It aims at providing the composition which gives the hardened | cured material to show.

  As a result of intensive studies to solve the above problems, the present inventors have completed the following invention.

That is, the present invention
(I)
General formula (1):
-[Si (R ¹ _2-b ) (X ¹ _b ) O] _m Si (R ¹ _3-a ) X ¹ _a (1)
(Wherein R ¹ is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when there are two or more R ^{1 s} , they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, 3 R's may be the same or different, X ¹ represents a hydroxyl group or a hydrolyzable group, a and b are each 0 or 1, and m b's are the same. And an organic polymer (A) having a silicon group and an acid (B) represented by the following formula: m + represents an integer of 0 to 19. Composition,
(II)
The composition according to (I), which contains an amine compound (C),
(III)
The composition according to any one of (I) and (II), wherein X ^{1 in the} general formula (1) is an alkoxy group,
(IV)
The main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylic acid ester polymer (I) to (III) A composition according to any one of
(V)
The composition according to (IV), wherein the main chain skeleton of the organic polymer (A) is polypropylene oxide,
(VI)
The composition according to any one of (I) to (V), wherein the acid (B) is a carboxylic acid,
(VII)
General formula (2):
_{^{- [Si (R 2 2-}} d) (X 2 d) O] n Si (R 2 3-c) X 2 c (2)
(In the formula, R ² is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ² are present, they may be the same or different, where R ′ is the same as above, and X ² represents a hydroxyl group or a hydrolyzable group. C is 0, 1, 2 or 3, d is 0, 1 or 2, and c + Σd ≧ 2 is satisfied, and n is an integer of 0 to 19. The composition according to any one of (I) to (VI), which contains an organic polymer (D) having a group,
(VIII)
The composition according to (VII), wherein X ^{2 in the} general formula (2) is an alkoxy group,
(IX)
(VII) or (VIII), wherein the main chain skeleton of the organic polymer (D) is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylate polymer A composition according to any one of
(X)
The composition according to (IX), wherein the main chain skeleton of the organic polymer (D) is polypropylene oxide,
(XI)
Any one of (VII) to (X) containing 1 to 60 parts by weight of the organic polymer (D) with respect to 100 parts by weight of the total amount of the organic polymer (A) and the organic polymer (D). The composition according to item,
(XII)
A curable composition comprising the composition according to any one of (I) to (XI),
About.

  The composition of the present invention gives a cured product exhibiting excellent strength and elongation while maintaining workability.

  The present invention will be described in detail below.

The organic polymer (A) contained in the composition of the present invention has at least one general formula (1) per molecule:
-[Si (R ¹ _2-b ) (X ¹ _b ) O] _m Si (R ¹ _3-a ) X ¹ _a (1)
(Wherein R ¹ is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when there are two or more R ^{1 s} , they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, 3 R's may be the same or different, X ¹ represents a hydroxyl group or a hydrolyzable group, a and b are each 0 or 1, and m b's are the same. May be different and satisfy a + Σb = 1, m is an integer from 0 to 19, and is hereinafter referred to as “monofunctional reactive silicon group”. In some cases.)

1 functional reactive silicon group in the organic polymer (A), as described in the general formula (1), the hydrolyzable groups X ¹ to one chromatic on silicon.

In particular, the general formula (3):
-SiR ¹ ₂ X ¹ (3)
A reactive silicon group represented by the formula (wherein R ¹ and X ¹ are the same as described above) is preferable because introduction is easy.

The hydrolyzable group described by X ¹ in the general formula (1) or (3) is not particularly limited, and examples thereof include known hydrolyzable groups such as hydrogen atom, halogen atom, alkoxy group, acyloxy Group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. 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, and the alkoxy group is mildly hydrolyzable and easy to handle. More preferred.

  Specific examples of the alkoxy group are not particularly limited, and for example, methoxy group, ethoxy group, 1-propoxy group, 2-propoxy group, 1-butoxy group, 2-butoxy group, tert-butyloxy group, octoxy group, lauryl Examples thereof include an oxy group, a phenoxy group, and a benzyloxy group. Among these, a methoxy group and an ethoxy group are preferable because of easy synthesis, and a methoxy group is more preferable because of good reactivity in a hydrolysis reaction and the like.

R ¹ in the general formula (1) or (3) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. Examples thereof include a hydrocarbon group such as an aralkyl group, or a triorganosiloxy group described by a general formula: R ′ ₃ SiO—, wherein R ′ is a methyl group, a phenyl group, or the like. In these, a methyl group is preferable from the ease of introduction | transduction.

  More specific examples of the monofunctional reactive silicon group of the organic polymer (A) include methoxydimethylsilyl group, ethoxydimethylsilyl group, isopropoxydimethylsilyl group, methoxydiethylsilyl group, ethoxydiethylsilyl group, methoxydiphenyl. Examples include silyl group, phenoxydimethylsilyl group, chlorodimethylsilyl group, acetoxydimethylsilyl group, hydroxydimethylsilyl group, methoxydimethylsilyloxydimethylsilyl group, and ethoxydimethylsilyloxydimethylsilyl group. From the viewpoint of high reactivity, a methoxydimethylsilyl group, an ethoxydimethylsilyl group, a phenoxydimethylsilyl group, a chlorodimethylsilyl group, and a hydroxydimethylsilyl group are preferable. From the viewpoint of stability, a methoxydimethylsilyl group and an ethoxydimethylsilyl group are more preferable. The ethoxydimethylsilyl group is particularly preferred because the alcohol produced in the hydrolysis reaction of the reactive silicon group is ethanol and has higher safety.

  The organic polymer (A) has an average of at least one monofunctional reactive silicon group in one molecule of the polymer, but only the organic polymer (A) is used as the reactive silicon group-containing polymer. When preparing the composition, the average number of monofunctional reactive silicon groups is preferably 1.2 to 5, more preferably 1.4 to 4, more preferably 1.6 to 3 per molecule. .5 is more preferable, and 1.8 to 3 is particularly preferable. If the number of reactive silicon groups is less than this, there is a risk that the molecular weight will hardly increase even if they react. On the other hand, if the amount is too large, a cured product having a high elastic modulus tends to be obtained, and the effects of the present invention may not be obtained.

  Examples of the method for introducing the reactive silicon group in the organic polymer (A) include known methods, and examples thereof include the following methods (a) to (c).

  (A) A method in which a hydrosilane having a reactive silicon group is reacted with a polymer having an unsaturated group to cause hydrosilylation.

  (B) A method of reacting a polymer having an unsaturated group with a compound having a mercapto group and a reactive silicon group.

  (C) A method in which a 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 methods (a) to (c), among the methods (c), 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, or (a) The method is preferable because a high conversion rate can be obtained in a relatively short reaction time. Among them, the polymer having a reactive silicon group obtained by the method (a) is more preferable than the polymer obtained by the method (c). However, the method (b) is particularly preferred because the polymer obtained by the method (b) has a strong odor based on mercaptosilane.

  (I) The hydrosilane compound used in the method is not particularly limited. For example, halogenated silanes such as chlorodimethylsilane and chlorodiethylsilane; alkoxysilanes such as methoxydimethylsilane, ethoxydimethylsilane and phenoxydimethylsilane; Examples include acyloxysilanes such as acetoxydimethylsilane and acetoxydiphenylsilane. Among these, halogenated silanes and alkoxysilanes are preferable because of their high efficiency of silylation reaction, and more preferable because the hydrolyzability of the composition from which the alkoxysilanes are obtained is mild and easy to handle. Among the alkoxysilanes, ethoxydimethylsilane, an organic polymer from which methoxydimethylsilane is obtained, and a composition containing the same are preferable because of good storage stability, and the reactivity of the organic polymer from which methoxydimethylsilane is obtained. Is particularly preferable because of its high value.

(A) In the method, the general formula (4):
—O—R ³ —CR ⁴ ═CH ₂ (4)
(In the formula, R ³ is a divalent hydrocarbon group having 10 or less carbon atoms, and R ⁴ is an organic group having 1 to 20 carbon atoms.) An organic polymer having an unsaturated group at its terminal is used. Thus, the introduction rate of silicon groups can be increased. In particular, when producing a composition using the linear organic polymer (A), it is preferable to increase the introduction rate of silicon groups because the molecular chain length can be efficiently extended.

R ³ in the general formula (4) is not particularly limited, and is preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms from the viewpoint of ease of synthesis. Specifically, R ³ is most preferably a methylene group. R ⁴ in the general formula (4) is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable because of easy synthesis.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is introduced into an unsaturated bond site of a polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. There are no particular limitations on the method. The compound having a mercapto group and a reactive silicon group is not particularly limited, and examples thereof include γ-mercaptopropylmethoxydimethylsilane and γ-mercaptopropylethoxydimethylsilane.

  As a method of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method disclosed in JP-A-3-47825 can be mentioned. However, it is not particularly limited. The compound having an isocyanate group and a reactive silicon group is not particularly limited, and examples thereof include γ-isocyanatopropylmethoxydimethylsilane, γ-isocyanatopropylethoxydimethylsilane, isocyanatemethylmethoxydimethylsilane, and isocyanatemethylethoxydimethylsilane. can give.

  The number average molecular weight of the organic polymer (A) is about 3,000 to 100,000, more preferably 3,000 to 50,000, particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC. . When the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced is increased, which may be inconvenient in terms of production cost. Tend to be inconvenient.

  The main chain skeleton of the organic polymer (A) is not particularly limited, and those having various main chain skeletons can be used. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene , Polyoxyalkylene polymers such as polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, etc. Copolymers, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or copolymers of butadiene and acrylonitrile and styrene, and hydrogenating these polyolefin polymers Hydrocarbon polymer such as hydrogenated polyolefin polymer obtained by polyester; polyester polymer obtained by condensation of dibasic acid such as adipic acid and glycol, or ring-opening polymerization of lactones; ethyl (meth) (Meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as acrylate and butyl (meth) acrylate; radical polymerization of monomers such as (meth) acrylic acid ester monomers, vinyl acetate, acrylonitrile and styrene Obtained vinyl polymer; graft polymer obtained by polymerizing vinyl monomer in the polymer; polysulfide polymer; polycondensation of polyamide 6, hexamethylenediamine and adipic acid by ring-opening polymerization of ε-caprolactam Polyamide 6,6, hexamethylenediamine and sebacic acid Polyamide 6 · 10 by polycondensation of γ-polyamide, Polyamide 11 by polycondensation of ε-aminoundecanoic acid, Polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, Copolyamide having two or more components among the above polyamides, etc. For example, organic polymers such as polycarbonate polymers and diallyl phthalate polymers produced by condensation polymerization from bisphenol A and carbonyl chloride. Among these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature. The resulting cured product is preferred because of its excellent cold resistance.

  The glass transition temperature of the organic polymer (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. When the glass transition temperature exceeds 20 ° C., the viscosity in winter or in a cold region may become high and handling may be difficult, and the flexibility of the cured product may be reduced and elongation may be reduced. The glass transition temperature can be determined by DSC measurement according to the measurement method defined in JISK7121.

  In addition, polyoxyalkylene polymers and (meth) acrylic acid ester polymers are preferred because they have high moisture permeability and are excellent in deep part curability and further in adhesion when made into one-component compositions. An oxyalkylene polymer is particularly preferable.

The polyoxyalkylene polymer essentially has the general formula (5):
—R ⁵ —O— (5)
(Wherein R ⁵ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁵ in the general formula (5) is a carbon atom. A linear or branched alkylene group having 1 to 14 or 2 to 4 is preferable. Specific examples of the repeating unit represented by the general formula (5) include

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, it is preferable that a polymer composed mainly of a propylene oxide polymer is amorphous or has a relatively low viscosity.

  The saturated hydrocarbon polymer is a polymer that has substantially no carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton is (1) ethylene, propylene, 1-butene, isobutylene, etc. (2) A homopolymerization of a diene compound such as butadiene or isoprene, or a copolymerization with the olefin compound. Thereafter, it can be obtained by a method of hydrogenation. Among these, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because they are easy to introduce functional groups at the terminals, easily control the molecular weight, and can increase the number of terminal functional groups. A polymer is more preferable. Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene polymer, all of the repeating units may be formed from isobutylene units or may be a copolymer with other repeating units. However, the repeating unit derived from isobutylene is 50% by weight from the viewpoint of rubber properties. Those having the above are preferable, those having 80% by weight or more are more preferable, and those having 90 to 99% by weight are particularly preferable.

  It does not specifically limit as a (meth) acrylic acid ester type monomer which comprises the principal chain of the said (meth) acrylic acid ester type polymer, A well-known thing can be used, for example, (meth) acrylic acid, ( Methyl) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic acid tert-butyl, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (Meth) acrylic acid phenyl, (meth) acrylic acid toluyl, (meth) acrylic acid benzyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxybutyl, (meth) acrylic acid 2-hydroxyethyl, (Meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, γ- (methacryloyloxypropyl) methoxydimethylsilane, γ- (methacryloyloxypropyl) ethoxydimethylsilane, γ- (methacryloyl) (Oxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethyl ester of (meth) acrylic acid Chill, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, Bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2- (meth) acrylic acid 2- Examples include (meth) acrylic acid ester monomers such as perfluorodecylethyl and 2-perfluorohexadecylethyl (meth) acrylate. These may be used alone or may be used by copolymerizing a plurality thereof. Is possible.

  As the (meth) acrylic acid ester polymer, a polymer obtained by copolymerizing a (meth) acrylic acid ester monomer and a vinyl monomer copolymerizable therewith can also be used. The vinyl monomer is not particularly limited, and examples thereof include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid And dialkyl esters; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenol Maleimide monomers such as lumaleimide and cyclohexylmaleimide; Vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; Vinyl monomers containing amide groups such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, benzoic acid Vinyl ester monomers such as vinyl and vinyl cinnamate; alkenyl monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. Can also be used as a copolymerization component.

  Among the (meth) acrylic acid ester polymers obtained from the above monomers, a copolymer composed of a styrene monomer and a (meth) acrylic acid monomer is preferable because of its excellent physical properties. A (meth) acrylic acid ester polymer composed of an acid ester monomer is more preferred, and an acrylic acid ester polymer composed of an acrylic acid ester monomer is particularly preferred.

  In particular, when the organic polymer (A) is used for applications such as general construction, butyl acrylate is required because physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required. A butyl acrylate polymer composed of a monomer is preferred. Moreover, when using for the use as which oil resistance etc. are requested | required, such as a motor vehicle use, the copolymer which has ethyl acrylate as a main component is preferable. Polymers made of ethyl acrylate are excellent in oil resistance but may be slightly inferior in low-temperature properties (cold resistance). To improve low-temperature properties, it is possible to replace a part of ethyl acrylate with butyl acrylate. Is possible. However, since the good oil resistance is impaired as the proportion of butyl acrylate is increased, the proportion is preferably 40 mol% or less, more preferably 30 mol% for applications requiring oil resistance. More preferably, it is as follows. It is also preferable to use 2-methoxyethyl acrylate or 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve low-temperature characteristics 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, the ratio is preferably 40 mol% or less when heat resistance is required. In accordance with various uses and required purposes, it is possible to obtain a suitable polymer by changing the ratio in consideration of required physical properties such as oil resistance, heat resistance and low temperature characteristics. For example, although not particularly 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 (molar ratio of 40 to 50 / 20-30 / 30-20). In the present invention, these preferable monomers may be copolymerized with other monomers and further block-copolymerized. In this case, it is preferable that these preferable monomers are 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.

  Although it does not specifically limit as a manufacturing method of the principal chain of an organic polymer (A), The following method is mentioned.

  The method for synthesizing the polyoxyalkylene polymer is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623 can be used. Polymerization method using transition metal compound-porphyrin complex catalyst such as complex obtained by reaction, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Polymerization method using double metal cyanide complex catalyst shown in each publication such as Japanese Patent No. 3427256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, and polymerization method using a catalyst comprising a polyphosphazene salt shown in JP-A-10-273512 , Japanese Patent Laid-Open No. 11060722 A polymerization method using a catalyst comprising a phosphazene compound and the like.

  The method for synthesizing the saturated hydrocarbon polymer is not particularly limited, and various conventionally reported polymerization methods can be mentioned, but the living polymerization method that has been reported in many recent years is particularly preferable. Among these, in the case of a saturated hydrocarbon polymer, particularly an isobutylene polymer, inifer polymerization discovered by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, page 2843), and can be polymerized with a molecular weight of about 500 to 100,000 with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends. It has been.

  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, a peroxide or the like as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. 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 halogen, which is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a high 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 Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  These organic polymers (A) comprising various main chain skeletons may be used alone or in combination of two or more.

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

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

The amide segment has the general formula (6):
—NR ⁶ C (═O) — (6)
(R ⁶ is 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. Urethane groups can be listed. 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 (6).

An example of an industrially easy method for producing a polymer containing an amide segment and a reactive silicon group is as follows. An excess polyisocyanate compound is reacted with a polymer having an active hydrogen-containing group at a terminal to form a polyurethane main chain. Or a polymer having an isocyanate group at the terminal thereof, or at the same time, all or part of the isocyanate group is represented by the general formula (7):
U-R ⁷ -SiR ¹ ₂ Y (7)
(In the formula, R ¹ is the same as described above. R ⁷ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. U is a hydroxyl group, An active hydrogen-containing group selected from a carboxyl group, a mercapto group, and an unsubstituted or monosubstituted amino group, wherein Y is independently a hydroxyl group or a hydrolyzable group. What is manufactured by the method of reacting can be mentioned.

Further, the polymer having an active hydrogen-containing group at the terminal is represented by the general formula (8):
O = C = N—R ⁷ —SiR ¹ ₂ Y (8)
(Wherein R ¹ , R ⁷ , and Y are the same as described above) can be produced by reacting the reactive silicon group-containing isocyanate compound.

  Examples of the polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxyl group at the terminal (polyolefin polyol). , Polythiol compound, polyamine compound, polyalkyleneimine, polysiloxane and the like. Among these, polyether polyol, polyacryl polyol, polyolefin polyol, and polysiloxane are preferable because the obtained polymer has a relatively low glass transition temperature and the obtained cured product is excellent in cold resistance. In particular, polyether polyol is particularly preferred because the resulting polymer has a low viscosity and good workability and good deep curability. Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the cured products of the resulting polymers have 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 preferable. 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 has a lower degree of unsaturation, a smaller Mw / Mn, a lower viscosity, a high acid resistance, and a high weather resistance oxyalkylene heavy. It is preferable because a coalescence 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. Specific examples include UH-2000 manufactured by Toagosei Co., Ltd.

  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 (7), when it illustrates specifically, (gamma) -aminopropyl methoxydimethylsilane, N-((beta) -aminoethyl) -gamma-aminopropyl methoxydimethylsilane, (gamma)-( Contains amino groups such as N-phenyl) aminopropylmethoxydimethylsilane, N-ethylaminoisobutylmethoxydimethylsilane, N-cyclohexylaminomethylethoxydimethylsilane, N-cyclohexylaminomethylethoxydimethylsilane, N-phenylaminomethylmethoxydimethylsilane Silanes; hydroxy group-containing silanes such as γ-hydroxypropylmethoxydimethylsilane; mercapto group-containing silanes such as γ-mercaptopropylmethoxydimethylsilane; Further, Michael addition reaction products of various α, β-unsaturated carbonyl compounds and amino group-containing silanes, or Michael addition reaction products of various (meth) acryloyl group-containing silanes and amino group-containing compounds are also generally used. It can be used as a silicon compound of formula (7).

  The reactive silicon group-containing isocyanate compound of the general formula (8) is not particularly limited, but specific examples include γ-methoxydimethylsilylpropyl isocyanate, γ-ethoxydimethylsilylpropyl isocyanate, methoxydimethylsilylmethyl isocyanate, and the like. Can be mentioned. Moreover, the compound obtained by making the silicon compound of General formula (7) react with the excess said polyisocyanate compound can also be used as a reactive silicon group containing isocyanate compound of General formula (8).

  When there are many amide segments in the main chain skeleton of the organic polymer (A), the viscosity of the polymer tends to increase. Moreover, a viscosity may rise after storage, and workability | operativity of the composition obtained may fall. Furthermore, the amide segment may be cleaved by heat or the like. Therefore, in order to obtain a composition having excellent storage stability and workability, it is preferable that the amide segment is not substantially contained. On the other hand, the reactivity tends to be improved by the amide segment in the main chain skeleton of the organic polymer (A). Therefore, when the main chain skeleton of the organic polymer (A) contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and more preferably 2 to 3 Is particularly preferred.

  The main chain structure of the organic polymer (A) may be a straight chain without branching or a branched chain having three or more terminals. In the organic polymer (A) having a silicon group of the general formula (1) at each end, the linear organic polymer (A) plays a role of chain extension reaction, and the branched organic polymer (A) is Can serve as a cross-linking point. For example, for the purpose of increasing the molecular weight by a chain extension reaction, it is preferable to use a linear organic polymer (A). On the other hand, it is preferable to use a branched organic polymer (A) for the purpose of obtaining a cured product imparted with elasticity by reacting the composition of the present invention. Moreover, the organic polymer which has 3 or more of silicon groups of General formula (1) in 1 molecule as a crosslinkable organic polymer (A) can also be used. The linear organic polymer (A) and the branched organic polymer (A) can be mixed and used at an arbitrary ratio, but only the organic polymer (A) is used as a polymer component. For the purpose of obtaining a cured product, the weight ratio of linear organic polymer (A) / branched organic polymer (A) is preferably 0/100 to 75/25. To 50/50 is more preferable. If the weight ratio of the linear organic polymer (A) is larger than this, a cured product may not be obtained.

  In the present invention, acid (B) is used as the silanol condensation catalyst. The silanol condensation catalyst plays a role of promoting the siloxane formation reaction by the reactive silicon group and moisture of the organic polymer (A) and the organic polymer (D) described later.

  As the acid (B) as the silanol condensation catalyst, various kinds of inorganic acids such as hydrochloric acid, odorous acid, phosphoric acid and boronic acid; carboxylic acids; organic sulfonic acids such as trifluoromethanesulfonic acid; and organic acidic phosphates are used. However, carboxylic acids are preferred from the viewpoint of ease of handling.

  Specific examples of carboxylic acids used as a silanol condensation catalyst include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid Linear saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and laccelic acid; undecylenic acid, Linderic acid, Tzuic acid, Fizeteric acid, Myristoleic acid, 2-Hexadecenoic acid, 6-Hexadecenoic acid, 7-Hexadecenoic acid, Palmitoleic acid, Petroceric acid, Oleic acid, Elaidic acid, Asclepic acid, Vaxenoic acid, Gadelic acid, Gondoic acid, cetreic acid, ethanol Monoene unsaturated fatty acids such as carboxylic acid, brassic acid, ceracoleic acid, ximenoic acid, rumecic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10 , 12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid Polyunsaturated fatty acids such as sardine acid, herring acid, docosahexaenoic acid; 2-methylbutyric acid, isobutyric acid, 2-e Rubutyric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2-phenylbutyric acid, isovaleric acid, 2,2-dimethylvaleric acid, 2-ethyl- 2-methylvaleric acid, 2,2-diethylvaleric acid, 2-ethylhexanoic acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2, Branched fatty acids such as 5-dimethylhexanoic acid, versatic acid, neodecanoic acid, and tuberculostearic acid; having triple bonds such as propiolic acid, talylic acid, stearoleic acid, crepenic acid, xymenic acid, 7-hexadesinic acid Fatty acids: naphthenic acid, malvalic acid, sterlic acid, hynocarpsic acid, shawl moulinic acid, gorulinic acid, 1-methylcyclopentanecarboxylic acid , 1-methylcyclohexanecarboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.2] octane-1-carboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, etc. Acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettlic acid, aleurit acid, 2 -Hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, 2,2-dimethyl-3-hydroxypropionic acid, ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid, cereblon Oxygenated fatty acids such as acids A halogen-substituted product of a monocarboxylic acid such as chloroacetic acid, 2-chloroacrylic acid and chlorobenzoic acid. Aliphatic dicarboxylic acids include adipic acid, azelaic acid, pimelic acid, suberic acid, sebacic acid, glutaric acid, oxalic acid, malonic acid, ethylmalonic acid, dimethylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, succinic acid 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, chain dicarboxylic acids such as 2,2-dimethylglutaric acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, Saturated dicarboxylic acids such as acetic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include chain tricarboxylic acids such as aconitic acid, citric acid, isocitric acid, 3-methylisocitric acid, and 4,4-dimethylaconitic acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl Examples thereof include aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. In addition, amino acids such as alanine, leucine, threonine, aspartic acid, glutamic acid, arginine, cysteine, methionine, phenylalanine, tryptophan, histidine and the like can be mentioned. Moreover, the carboxylic acid derivative etc. which produce carboxylic acid by hydrolysis of carboxylic anhydride, ester, amide, nitrile, acyl chloride, etc. can also be used. Among them, 2-ethylhexanoic acid, octylic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, versatic acid, neodecanoic acid, oleic acid, or naphthenic acid can be easily obtained. It is preferable because it is inexpensive and has good compatibility with the organic polymer (A). 2-ethylhexanoic acid, octylic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5- Dimethylhexanoic acid, versatic acid, and neodecanoic acid are more preferable because they have good activity, and 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, versatic acid, and neodecanoic acid are particularly preferable.

  An acid (B) may be used independently and may use 2 or more types together.

  The amount of the acid (B) used is 100 parts by weight of the organic polymer (A) or, when the following organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D). 0.1 to 30 parts by weight is preferable with respect to 100 parts by weight, and 1 to 10 parts by weight is more preferable. When the compounding amount of the acid (B) is below this range, the reaction rate may be slow, and the catalyst activity may decrease after storage. On the other hand, if the blending amount of the acid (B) exceeds this range, the pot life may be too short and the workability may deteriorate.

  Furthermore, in order to further increase the activity of the acid (B), an amine compound (C) can be used in combination as a promoter.

  The amine compound (C) is not particularly limited. For example, aliphatics such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, cyclohexylamine Primary amines: dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, di (2-ethylhexyl) amine, didecylamine, dilaurylamine, dicetylamine, distearylamine, methyl Aliphatic secondary amines such as stearylamine, ethylstearylamine, butylstearylamine; triethylamine, tria Aliphatic tertiary amines such as ruamine, trihexylamine and trioctylamine; Aliphatic unsaturated amines such as triallylamine and oleylamine; Pyridine, 2-aminopyridine, 2- (dimethylamino) pyridine, 4- (dimethylamino) pyridine, 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine, 2- Piperidinemethanol, 2- (2-piperidino) ethanol, piperidone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) , 6- (Dibutylamino) -1,8- Azabicyclo [5,4,0] -7-undecene (DBA-DBU), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), 1,4-diazabicyclo [2,2,2] Nitrogen-containing heterocyclic compounds such as octane (DABCO) and aziridine, and other amines include monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N- Methyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2- (2-aminoethylamino) ethanol, benzylamine, 3-methoxypropylamine, 3 -Lauryloxypropylamine, 3-dimethyl Ruaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2- (1-piperazinyl) ethylamine, xylylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol And the like; guanidines such as guanidine, phenylguanidine and diphenylguanidine; and biguanides such as butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide.

  Among these, octylamine, 2-ethylhexylamine, laurylamine, and 3-diethylaminopropylamine are preferable because they exhibit high promoter activity and are easily available.

  The amount of the amine compound (C) used is preferably 0.001 to 20 parts by weight, more preferably 0 to 100 parts by weight of the total amount of the organic polymer (A) and the following organic polymer (D). 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable. When the compounding amount of the amine compound (C) is less than 0.001 part by weight, the reaction rate becomes slow and the effect as a promoter may not be obtained. On the other hand, even if the compounding amount of the amine compound (C) exceeds 20 parts by weight, the effect as a co-catalyst cannot be obtained sufficiently, and conversely, the reactivity may decrease.

  A known silanol condensation catalyst other than the acid (B) can be used to the extent that the effects of the present invention are not impaired.

  Specific examples include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, carboxyl Carboxylic acid metal salts such as iron oxide, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diiso Titanium compounds such as propoxy titanium bis (ethyl acetocetate); dibutyl tin dilaurate, dibutyl tin maleate, dibutyl tin phthalate, dibutyl tin dioctanoate, dibutyl tin bis (2-ethyl Sanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyl Tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl tin bis (octyl maleate), dibutyl tin dimethoxide, dibutyl tin bis (nonyl phenoxide), dibutenyl tin oxide, dibutyl tin Organic tin compounds such as oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester; aluminum Aluminum compounds such as squirrel (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); various metal alkoxides such as tetrabutoxyhafnium Etc. However, since the organic tin compound has a concern about the influence on the environment, the organic tin compound is used in an amount of 100 parts by weight of the organic polymer (A) or the organic weight when the following organic polymer (D) is contained. It is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, still more preferably 0.05 parts by weight or less, based on 100 parts by weight of the total amount of the union (A) and the organic polymer (D). It is particularly preferred that

  The silanol condensation catalyst contained in the composition of the present invention may be used in combination with the above various types.

The composition of the present invention, together with the organic polymer (A), has the general formula (2):
^{_{- [Si (R 2 2-}} d) (X 2 d) O] n Si (R 2 3-c) X 2 c (2)
(In the formula, R ² is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ² are present, they may be the same or different, where R ′ is the same as above, and X ² represents a hydroxyl group or a hydrolyzable group. C is 0, 1, 2 or 3, d is 0, 1 or 2, and c + Σd ≧ 2 is satisfied, and n is an integer of 0 to 19. An organic polymer (D) having a group (hereinafter sometimes referred to as “polyfunctional reactive silicon group”) can be contained. When the organic polymer (A) containing a monofunctional reactive silicon group and the organic polymer (D) containing a polyfunctional reactive silicon group are used together in the case of preparing a curable composition in the present invention, It is particularly useful.

  The hydrolyzable group described in the general formula (2) is not particularly limited, and examples thereof include known hydrolyzable groups such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, Examples thereof include 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. More preferred.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and (c + Σd) is preferably in the range of 2 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.

In particular, the general formula (9):
-SiR ² _3-e X ² _e (9)
(In the formula, R ² and X ² are the same as described above. E represents 2 or 3.) The reactive silicon group represented by

R ² described in the general formula (2) or (9) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. And a hydrocarbon group such as an aralkyl group, or a triorganosiloxy group described by a general formula: R ′ ₃ SiO—, where R ′ is a methyl group, a phenyl group, or the like. In these, a methyl group is preferable from the ease of introduction | transduction.

  The organic polymer (D) having a silicon group described in the general formula (2) or (9) is not particularly limited, and examples thereof include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxy Examples thereof include a methylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a dimethoxymethylsilyloxydimethylsilyl group, and a diethoxymethylsilyloxydimethylsilyl group. Among these, a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable because of high activity and good curability can be obtained, and a dimethoxymethylsilyl group is particularly preferable because of excellent storage stability.

  As a method for introducing the reactive silicon group of the organic polymer (D), the same method as the method (b), (b), (c) for introducing the reactive silicon group into the organic polymer (A) is used. Can be used.

  (I) The hydrosilane compound used when producing the organic polymer (D) by the method is not particularly limited. For example, halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane; Alkoxysilanes such as triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, dimethoxyethylsilane; acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; bis (dimethylketoximate) methylsilane And ketoximate silanes such as bis (cyclohexyl ketoximate) methyl silane. Of these, halogenated silanes and alkoxysilanes are particularly preferred. Furthermore, the hydrolyzability of the curable composition from which alkoxysilanes can be obtained is more preferable because it is gentle and easy to handle. Among alkoxysilanes, dimethoxymethylsilane is a curable composition containing an organic polymer that can be easily obtained. The composition is particularly preferred because it has high curability, storage stability, elongation characteristics and tensile strength.

  Examples of silicon compounds used in the production of the organic polymer (D) by the (b) method include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, and γ-mercapto. Examples thereof include propyldiethoxymethylsilane and mercaptomethyltriethoxysilane.

  (C) As an example of the silicon compound used when producing the organic polymer (D) by the method, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyldimethoxymethylsilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanate Examples thereof include propyldiethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  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, dangerous compounds such as dimethoxysilane are formed. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. For this reason, when a group in which three hydrolyzable groups such as a trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, it is preferable to use the method (b) or (c). .

  The organic polymer (D) may be linear or branched, and its number average molecular weight is about 3,000 to 100,000, more preferably 3,000 to 50,000 in terms of polystyrene in GPC. Particularly preferably from 3,000 to 30,000. If the number average molecular weight is less than 3,000, the cured product tends to be disadvantageous in terms of elongation characteristics.

  There is no restriction | limiting in particular also in the principal chain skeleton of an organic polymer (D), The structure, a physical property, and a manufacturing method can be demonstrated similarly to said organic polymer (A).

  The main chain skeleton of the organic polymer (D) may have a single structure or a plurality of structures.

  The method for producing the organic polymer (D) and the compound whose main chain skeleton is a polyoxyalkylene polymer is not particularly limited. For example, JP-B Nos. 45-36319, 46-12154, and JP-A-50 No. 156599, No. 54-6096, No. 55-13767, No. 55-13468, No. 57-164123, No. 3-2450, US Pat. No. 3,362,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, U.S. Pat. No. 4,960,844 or the like, or JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-61-218632, JP-A-3-72527 , Number average molecular weight 6,000 or more shown in each publication such as JP-A-3-47825, JP-A-8-231707, etc. w / Mn is a molecular weight distribution in high molecular weight 1.6 is narrow manufacturing method of the polyoxyalkylene polymer may be mentioned.

  There are no particular limitations on the method for producing the organic polymer (D) and the main chain skeleton is a saturated hydrocarbon polymer. For example, JP-B-4-69659, JP-B-7-1088928, 63-254149, JP-A 64-22904, JP-A-1-197509, JP-A-2539445, JP-A-2873395, JP-A-7-53882 and the like. can give.

  The method for producing the organic polymer (D) and the main chain skeleton being a (meth) acrylic acid ester polymer is not particularly limited, and examples thereof include Japanese Patent Publication No. 3-14068 and Japanese Patent Publication No. 4-55444. , A production method using a free radical polymerization method using a chain transfer agent shown in each publication such as JP-A-6-221922, or an atom transfer radical shown in JP-A-9-272714 A production method using a polymerization method is exemplified.

When producing an organic polymer (D) containing an amide segment, a polymer having an isocyanate group at the terminal and the general formula (10):
^{_{U-R 7 -SiR 2 3-}} f Y f (10)
(Wherein, R ² , R ⁷ , U and Y are the same as described above. F is any one of 2 and 3). Examples of known production methods for polymers relating to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), Japanese Patent Application Laid-Open No. Sho 62- 13430 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21879 (US Pat. No. 5364955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-11-100197, JP-A-2000-169544, JP-A-2000-169545, JP-A-2002-212415, JP-A-3313360, US Pat. No. 4,067,844, US Pat. No. 3711 No. 45, such as JP-A-2001-323040, and the like.

Further, the polymer having an active hydrogen-containing group at the terminal is represented by the general formula (11):
O = C = N—R ⁷ —SiR ² _3-f Y _f (11)
(Wherein, R ² , R ⁷ , Y, and f are the same as described above) can be produced by reacting the reactive silicon group-containing isocyanate compound. Examples of known production methods for polymers relating to this production method include JP-A Nos. 11-279249 (US Pat. No. 5,990,257), JP-A No. 2000-119365 (US Pat. No. 6,046,270) and JP-A No. 58-29818. (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981, etc. Can be given.

  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)-( Amino groups such as N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Containing silanes; 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 (EP0831108), JP-A 2000-169544, JP-A 2000-169545. As described in the above, Michael addition reaction product of various α, β-unsaturated carbonyl compounds and amino group-containing silanes, or Michael of various (meth) acryloyl group-containing silanes and amino group-containing compounds. Addition reactants can also be used as silicon compounds of general formula (10).

  The reactive silicon group-containing isocyanate compound of the general formula (11) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiethoxysilylpropyl 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 a silicon compound of the general formula (10) with an excess of the polyisocyanate compound is also represented by the general formula: It can be used as the reactive silicon group-containing isocyanate compound (11).

  The organic polymer (A) containing a monofunctional reactive silicon group and the organic polymer (D) containing a polyfunctional reactive silicon group can be used by mixing at an arbitrary ratio. The content of (D) is the weight ratio of organic polymer (D) / organic polymer (A), and the upper limit is preferably 90/10 or less, more preferably 80/20 or less, and even more preferably 60/40 or less. . When the ratio of the organic polymer (A) is smaller than this, the molecular weight between crosslink points of the cured product is not sufficiently increased, and mechanical strength such as strength and elongation tends not to be improved. On the other hand, the lower limit of the organic polymer (D) / organic polymer (A) is preferably greater than 0/100, more preferably greater than 10/90, and even more preferably greater than 25/75 in weight ratio. . When the ratio of the organic polymer (D) is smaller than this, a cured product may not be obtained.

  When the composition of the present invention contains both the organic polymer (A) and the organic polymer (D), the main chain skeletons of the organic polymer (A) and the organic polymer (D) are the same or different. Each of them may be a single main chain skeleton or a mixture of two or more main chain skeletons, but they are preferably compatible with each other.

  In the production of the organic polymer (A) containing a monofunctional reactive silicon group, both a monofunctional reactive silicon group and a polyfunctional reactive silicon group may be introduced. For example, when a reactive silicon group is introduced by hydrosilylation, both monofunctional reactive silicon group and polyfunctional reactive silicon group are contained by simultaneously reacting ethoxydimethylsilane and dimethoxymethylsilane as a hydrosilane compound. Although an organic polymer may be obtained, this is synonymous with the combined use of the organic polymer (A) and the organic polymer (D).

  In the composition of this invention, adhesiveness imparting agents, such as a silane coupling agent, can be added as needed. Here, the silane coupling agent is a compound having a hydrolyzable silicon group and other functional groups in the molecule. By using silane coupling agents, various substrates such as inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic resin, polyester, polyethylene, polypropylene, and polycarbonate are used. The effect of significantly improving the adhesion between the adherend and the curable composition can be obtained under non-primer conditions or primer treatment conditions.

  When the silane coupling agent is used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly significant. Can function as such.

Examples of the hydrolyzable silicon group in the silane coupling agent include those in which X ² described in the general formula (2) is a hydrolyzable group. For example, the organic polymer (A) and the organic polymer ( Examples of the hydrolyzable group exemplified in the section D) include methoxy group, ethoxy group and the like from the viewpoint of hydrolysis rate. The number of hydrolyzable groups in the silane coupling agent is preferably 2 or more, particularly 3 or more.

  Examples of functional groups other than hydrolyzable silicon groups contained in the silane coupling agent include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, and the like. . Among these, a substituted or unsubstituted amino group, epoxy group, isocyanate group, isocyanurate and the like are preferable due to their high effect of improving adhesiveness, and an amino group is particularly preferable.

  The silane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxy. Silane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-Aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl -Γ-aminopropyltrimethoxy Sisilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylamino Aminosilanes such as methyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; γ-isocyanatopropyltrimethoxysilane, γ-isocyanate Propyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) di Isocyanate silanes such as methoxymethylsilane; ketimine silanes such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-mercaptopropyltrimethoxysilane, γ- Mercaptosilanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Epoxy compounds such as triethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Carboxysilanes such as β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyl Vinyl-type unsaturated group-containing silanes such as trimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane And isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate; vinyltrimethoxysilane and the like. The reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, the reaction product of aminosilane and (meth) acryloyloxy group-containing silane, and the like can also be used. Condensates obtained by partially condensing the silanes can also be used. Further, 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. .

  In the composition of the present invention, only one type of the silane coupling agent may be added to the composition, or two or more types may be used in combination.

  In the present invention, the silane coupling agent may act as a crosslinking agent.

  The amount of the silane coupling agent used in the present invention is 100 parts by weight of the organic polymer (A) or, when the organic polymer (D) is contained, the organic polymer (A) and the organic polymer (D). Is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 1 to 7 parts by weight with respect to 100 parts by weight of the total amount. If the blending amount is less than 0.01 parts by weight, the adhesiveness may not be sufficiently obtained. On the other hand, if the blending amount exceeds 20 parts by weight, the curing rate for practical use may not be obtained, and the reaction may not proceed sufficiently.

  As the adhesion-imparting agent, it is possible to use compounds other than the silane coupling agent, and specific examples thereof are not particularly limited. Isocyanates can be used. These adhesiveness imparting agents may be used alone or in combination of two or more.

  In the composition of the present invention, a filler can be added depending on the application. Fillers are used to ensure workability by adjusting the viscosity and thixotropy of the curable composition, adjust the strength of the cured product, improve adhesion, improve various physical properties such as imparting chemical resistance, and cure such as coloring and design It can be used to modify the surface of an object and reduce the cost per weight. There is no particular limitation on the filler, and reinforcing fillers such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; 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, and PMMA powder, and fibrous fillers such as glass fibers and filaments. When the filler is used, the amount used is 100 parts by weight of the organic polymer (A), or the total amount of the organic polymer (A) and the organic polymer (D) when the organic polymer (D) is contained. 1 to 250 parts by weight is preferable with respect to 100 parts by weight, and 10 to 200 parts by weight is more preferable.

  As shown in Japanese Patent Application Laid-Open 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.

  In order to obtain a highly transparent composition, as disclosed 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 disclosed in JP 2000-38560 A, 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 its surface, 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 this silanol group with organosilicon halides or alcohols. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, or the like is 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.

  Calcium carbonate is large and is divided into heavy calcium carbonate obtained by pulverizing and classifying natural raw materials and precipitated calcium carbonate (fine calcium carbonate) that is chemically produced. Precipitated calcium carbonate has a smaller primary particle size. It is common. Among the fine calcium carbonates, those having a particle size of 0.1 μm or less are called colloidal calcium carbonate. Most of the fine calcium carbonate is surface-treated with organic substances such as fatty acids and fatty acid esters. Examples of the surface treatment agent include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and other esters and salts thereof; polyoxyethylene Alkyl ether sulfates, long-chain alcohol sulfates, etc., and sulfate ester type anionic surfactants such as sodium salts and potassium salts thereof; alkylbenzene sulfonic acids, alkyl naphthalene sulfonic acids, paraffin sulfonic acids, α-olefin sulfones Examples thereof include acids, alkylsulfosuccinic acids and the like, and sulfonic acid type anionic surfactants such as sodium salts and potassium salts thereof.

  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. When the organic polymer (A) contains 100 parts by weight, or the organic polymer (D), the organic polymer (A) and When the organic polymer (D) is used in an amount of 1 to 200 parts by weight with respect to 100 parts by weight, preferable results are obtained. In addition, when it is desired to obtain a cured product having low strength and large elongation at break, it is mainly selected from titanium oxide, heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. When the filler is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the polymer 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. 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, a fatty acid ester, or a fatty acid salt. The particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and those having no surface treatment can be used.

  Addition of an organic balloon or an inorganic balloon is preferable in order to improve the workability of the composition (such as sharpness) and to make the surface of the cured product matt. 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, it is preferably 5 to 300 μm.

  The composition of the present invention is a sizing board, particularly a ceramic sizing board, such as joints of exterior wall tiles and exterior wall tiles, and exterior wall tile adhesives, because the cured product has good chemical resistance. Although it is suitably used for an adhesive that remains on the joint as it is, it is desirable that the design of the outer wall and the design of the sealing material harmonize. In particular, a high-quality outer wall is used as the outer wall by mixing sputter coating, colored aggregates, and the like. When a flaky or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm is blended in the curable composition of the present invention, the cured product has such a high-class feeling. In harmony with the outer wall and excellent chemical resistance, 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.

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

  The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and those having an appropriate size are 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 scale-like substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 100 mm). The scaly 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 agent 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 according to the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As scale-like or granular substances, natural substances such as silica sand and mica, synthetic rubbers, synthetic resins, and inorganic substances such as alumina are used. In order to enhance the design properties 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 disclosed 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. Preferred diameters, blending amounts, materials, and the like of the balloon are as follows as disclosed in JP-A-10-251618.

  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 may be used. The balloons used can be the same balloon or a mixture of balloons made of different materials. 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 is coated with calcium carbonate, talc, titanium oxide or the like, or an inorganic balloon is 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 with 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 shown in JP-A-2000-154368 and the surface of a cured product as shown in JP-A-2001-164237 are matted to give an uneven state. An amine-based 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 the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A-2000-154368, JP-A-2001-164237, WO97 / 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 vinylidene 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.

  Also when the composition of this invention contains sealing material hardened | cured material particle | grains, hardened | cured material can form an unevenness | corrugation on the surface and can improve the designability. Preferred diameters, blending amounts, materials, etc. of the cured sealant particles are as follows as disclosed 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. The material can be urethane resin, silicone, modified silicone, polysulfide rubber and the like, and is not limited as long as it can be used as a sealing material, but a modified silicone-based sealing material is preferable.

  Moreover, a silicate can be added to the composition of the present invention as necessary. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the composition of the present invention. Furthermore, the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions can be expected. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When the silicate is used, the amount used is 100 parts by weight of the organic polymer (A), or 100 parts by weight of the organic polymer (A) and the organic polymer (D) when the organic polymer (D) is contained. It is preferable that it is 0.1-20 weight part with respect to 0.5-10 weight part.

  The silicate is not particularly limited. For example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n Examples include tetraalkoxysilanes (tetraalkylsilicates) such as butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

  A partially hydrolyzed condensate of tetraalkoxysilane is more preferable because the organic polymer of the present invention has a greater effect of improving the resilience, durability, and creep resistance than tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis using a conventional method. Moreover, the commercially available thing can be used for the partial hydrolysis-condensation product of an organosilicate compound. Examples of such a condensate include methyl silicate 51, ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.) and the like.

  A plasticizer can be added to the composition of the present invention as necessary. By adding the plasticizer, the viscosity and slump property of the composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. The plasticizer is not particularly limited, and examples thereof include phthalates such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, succinic acid Non-aromatic dibasic esters such as isodecyl; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorination Paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  In addition to the plasticizer, a polymer plasticizer may be added for use. 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 called paintability) when an alkyd paint is applied to the cured product can be improved. The polymer plasticizer is not particularly limited. For example, vinyl polymers obtained by polymerizing vinyl monomers by various methods; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Esters of polyesters: Polyester plasticizers 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; molecular weight 500 or more, further 1,000 or more polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like of these polyether polyols Polyethers such as acid ester group, derivatives obtained by converting such an ether group; polystyrenes such as polystyrene and polymethyl -α- methyl styrene; polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, etc. polychloroprene and the like.

  Among these polymer plasticizers, those compatible with the organic polymer (A) and the organic polymer (D) are preferable. From this point, polyethers and vinyl polymers are preferable. Use of polyethers as a plasticizer is preferred because surface curability and deep part curability are improved and curing delay after storage hardly occurs, and 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 preferable, and acrylic polymers such as polyacrylic acid alkyl esters are more preferable. 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. Further, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer shown in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000 to 1,000. 5,000. Most preferably, it is 1,000-3,000. 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, cause contamination due to dust adhesion, etc., 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 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 terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer can be either a compound having a reactive silicon group or a compound having no 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 is preferably lower than that of the organic polymer (A) and the organic polymer (D). When the number average molecular weight of the alkylene polymer is higher than that of the organic polymer (A) and the organic polymer (D), the plasticizing effect may not be obtained.

  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. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.

  The amount of the plasticizer used is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 20 to 100 parts by weight. 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.

  If necessary, a tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifier, Well-known thing can be used regardless of solid and liquid at normal temperature, for example, a styrene-type block copolymer, its hydrogenated substance, a phenol resin, a modified phenol resin (For example, cashew oil-modified phenol resin, tall oil-modified phenol resin, etc.), terpene phenol resin, xylene-phenol resin, cyclopentadiene-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 For example, resin petroleum resin. These may be used alone or in combination of two or more. The styrene block copolymer and its hydrogenated product include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), and styrene-ethylenebutylene-styrene block copolymer. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifier resins may be used alone or in combination of two or more.

  The tackifying resin is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight, It is used in the range of 5 to 1,000 parts by weight, preferably 10 to 100 parts by weight.

  If necessary, a solvent or a diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. are mention | raise | lifted. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

  In the composition of the present invention, a physical property adjusting agent for adjusting the tensile properties of the cured product to be produced can be added as necessary. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Examples thereof include alkoxysilanes having an unsaturated group such as alkylisopropenoxysilane such as silane, vinyltrimethoxysilane and vinyldimethylmethoxysilane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and to improve the elongation at break. The said physical property modifier may be used independently and may be used together 2 or more types.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action 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 shown by Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. Further, compounds that are derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like that generate a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylol disclosed in JP-A-11-241029 Examples thereof include compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol, sorbitol, and the like, which generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis.

Further, a derivative of oxypropylene polymer as shown in JP-A-7-258534, compounds that produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol by hydrolysis can also be mentioned . 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 disclosed in JP-A-6-279893 can also be used.

  The physical property modifier is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, 0% of the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. .1 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

  If necessary, a thixotropic agent (anti-sagging agent) can be added to the composition of the present invention 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 diameter of 10 to 500 μm as disclosed in JP-A-11-349916 or organic fiber as disclosed 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 100 parts by weight of the organic polymer (A) or, when containing the organic polymer (D), 100 parts by weight of the total amount of the organic polymer (A) and the organic polymer (D). In the range of 0.1 to 20 parts by weight.

  If necessary, a compound having an epoxy group in one molecule can be added to the composition of the present invention. When a compound having an epoxy group is used, the restorability of the cured product can be improved. The compound having an epoxy group is not particularly limited, and examples thereof include compounds such as epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. More specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound contains 100 parts by weight of the organic polymer (A), or 0.5% of the total amount of the organic polymer (A) and the organic polymer (D) when the organic polymer (D) is contained. It is good to use in the range of -50 parts by weight.

If necessary, a photocurable material can be added to the composition of the present invention. When a photocurable material is used, a film of the photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. Here, the photocurable substance is a substance in which the molecular structure undergoes a chemical change in a considerably short time due to the action of light, resulting in a change in physical properties such as curing. The photocurable substance is not particularly limited, and is a known compound comprising an organic monomer, oligomer, resin or a composition containing them, for example, an unsaturated acrylic compound, polyvinyl cinnamate or an azide resin. Etc. can be used. 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 glycol Examples thereof include monomers such as di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. More specifically, 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 Although such Aronix M-400 multifunctional) and the like, particularly preferably a compound containing an acryl functional group, also a compound containing three or more same functional groups on average in one molecule are preferred. (All of the above are products 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 substance is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, it is 0 with respect to 100 parts by weight of the total amount of the organic polymer (A) and the organic polymer (D). .1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and 0.1 parts by weight or less has no effect of improving weather resistance, and 20 parts by weight or more makes the cured product hard. Too much and tends to crack.

  If necessary, an oxygen curable substance can be added to the composition of the present invention. An oxygen curable substance is an unsaturated compound that can react with oxygen in the air, reacts with oxygen in the air to form a cured film near the surface of the cured product, and sticks to the surface of the cured product. A compound having an action such as prevention of dust and dust adhesion. The oxygen curable substance is not particularly limited, and examples thereof include dry oils typified by drill oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers modified with dry oils. , Epoxy resin, silicon resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene Liquid polymers such as polymers, and liquids 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. Examples thereof include copolymers and various modified products thereof (maleinized modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferred. Moreover, the effect may be enhanced when 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 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. It is good to use in the range of 0.1 to 20 parts by weight, and more preferably 0.5 to 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 may be impaired. As disclosed in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An antioxidant (anti-aging agent) can be added to the composition of the present invention as necessary. When antioxidant is used, the heat resistance of hardened | cured material can be improved. The antioxidant is not particularly limited, and examples thereof include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based antioxidants. Among these, hindered phenol-based antioxidants are preferable. 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 are manufactured by ADEKA Corporation); shown in SANOL LS-770, SANOL LS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114, SANOL LS-744 (all above are manufactured by Sankyo Corporation). Hindered amine light stabilizers can also be used. 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 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. It is good to use in the range of 0.1-10 weight part with respect to it, More preferably, it is 0.2-5 weight part.

  If necessary, a light stabilizer can be added to 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-based, hindered amine-based, and benzoate-based compounds. Among these, hindered amine-based compounds are preferable. The amount of the light stabilizer used is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. It is preferable to use it in the range of 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight. Specific examples of the light stabilizer are also shown 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 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).

  When a light stabilizer and a photocurable material are added in combination to the composition of the present invention, particularly when an unsaturated acrylic compound is used as the photocurable material, a hindered amine is used as disclosed in JP-A-5-70531. A tertiary amine-containing hindered amine light stabilizer is preferably used as the light stabilizer 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) 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 added to the composition of the present invention as necessary. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. The ultraviolet absorber is not particularly limited, and examples thereof include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are preferable. The amount of the ultraviolet absorber used is 100 parts by weight of the organic polymer (A), or when the organic polymer (D) is contained, the total amount of the organic polymer (A) and the organic polymer (D) is 100 parts by weight. It is preferable to use it in the range of 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight. Further, it is preferable to use a phenol-based or hindered phenol-based antioxidant, a hindered amine-based light stabilizer, and a benzotriazole-based ultraviolet absorber in combination.

  An epoxy resin can be added to the composition of this invention as needed. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. The epoxy resin is not particularly limited. For example, a flame retardant epoxy resin such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated resin, etc. Bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A 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 glycerin Glycidyl ethers of polyhydric alcohols such as diglycidyl ether, glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc. Among them, at least two epoxy groups in the molecule What is contained is more preferable in view of high reactivity during curing, and the cured product is easy to form a three-dimensional network, and bisphenol A type epoxy resins or novolac type epoxy resins are particularly preferable. When the epoxy resin and the organic polymer (A) or the organic polymer (A) and the organic polymer (D) are used in combination, the total amount of the organic polymer (A) and the organic polymer (D) The use ratio is preferably ((A) or (A) + (D)) / epoxy resin = 100/1 to 1/100 by weight. When the ratio of ((A) or (A) + (D)) / epoxy resin is less than 1/100, it is difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and ((A) Or when the ratio of (A) + (D)) / epoxy resin exceeds 100/1, the strength of the organic polymer cured product may be insufficient. The preferred use ratio varies depending on the application of the composition, etc., and therefore cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, When the organic polymer (A) or the organic polymer (D) is contained with respect to 100 parts by weight of the resin, the total amount of the organic polymer (A) and the organic polymer (D) is 1 to 100 parts by weight, It is preferable to use 5 to 100 parts by weight. On the other hand, when improving the intensity | strength of hardened | cured material, when it contains 100 weight part of organic polymers (A) or an organic polymer (D), it is the sum total of an organic polymer (A) and an organic polymer (D). It is preferable to use 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of epoxy resin based on 100 parts by weight.

  An epoxy resin and a curing agent that cures the epoxy resin can be used in combination with the composition of the present invention. There is no restriction | limiting in particular as a hardening | curing agent for epoxy resins, A well-known hardening | curing agent for epoxy resins can be used, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine , M-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophorone diamine, amine-terminated polyethers and other primary and secondary amines; 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine and the like Quaternary amines and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride , Anhydrous Alcohols; trimellitic, carboxylic anhydrides, such as anhydrous Kuroren acid phenol; carboxylic acids; compounds such as diketone complex compounds of aluminum or zirconium are exemplified. 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 epoxy resin. Ketimine is present stably in the absence of moisture, and is decomposed into a primary amine and a ketone by moisture, and the resulting primary amine serves as a room temperature curable curing agent for the epoxy resin. When ketimine is used in this way, a one-component composition can be obtained. Ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

  The amine compound and carbonyl compound used for the synthesis of ketimine are not particularly limited and include known compounds. Examples of amine compounds include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, and 1,3. -Diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine and other diamines; 1,2,3-triamino Polyvalent amines such as propane, triaminobenzene, tris (2-aminoethyl) amine, tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; polyoxyalkylene series Polyamine; aminosilanes such as γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and the like. . 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. Aliphatic ketones such as acetone, 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, malon Β-di, such as dimethyl acid, diethyl malonate, methyl ethyl malonate, dibenzoylmethane Carbonyl compounds and the like.

  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.

  In the 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.

  When the flame retardant contains 100 parts by weight of the organic polymer (A) or the organic polymer (D), 5 to 5 parts by weight of the total amount of the organic polymer (A) and the organic polymer (D). It is used in the range of 200 parts by weight, preferably 10 to 100 parts by weight.

  Various additives may be added to the 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 modifiers, 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 shown in Japanese Laid-Open Patent Publication No. 2001-72854.

  The composition of the present invention can be prepared as a one-component type in which all compounding components are preliminarily blended and stored and cured by moisture in the air after construction. A silanol condensation catalyst, a filler, 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 silanol condensation catalyst to the main component containing a polymer having a reactive silicon group, so even if some moisture is contained in the compounding agent, the gel Although there is little concern about conversion, dehydration and drying are preferred when long-term storage stability is required. 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 the dehydrating agent, particularly the silicon compound that can react with water such as vinyltrimethoxysilane, is 100 parts by weight of the organic polymer (A), or the organic polymer (A) when the organic polymer (D) is contained. 0.1-20 weight part is preferable with respect to 100 weight part of total amounts of an organic polymer (D), and the range of 0.5-10 weight part is more preferable.

  The method for preparing the composition of the present invention is not particularly limited. For example, the components described above 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 composition of the present invention forms a three-dimensional network structure by the action of moisture and hardens into a solid having rubbery elasticity.

  The composition of the present invention is used for pressure-sensitive adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, mold preparations, vibration-proof materials, vibration-damping materials, sound-proof materials, foam materials, paints, spray materials Can be used.

  Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.

  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. . Moreover, 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 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.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.

(Synthesis Example 1-1)
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 14,500 having a hydroxyl group at the end (Tosoh's HLC -8120GPC was used, TOS-GEL H type manufactured by Tosoh Corporation was used as the column, and a polystyrene oxide (polystyrene equivalent molecular weight measured using THF) was obtained as the solvent. Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further 1.2 times equivalent of 3-chloro-2-methyl-1- Propene was added to convert the terminal hydroxyl group to a methallyl group. 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 methallyl 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-1) having a number average molecular weight of about 14,500 having a terminal methallyl group was obtained.

(Synthesis Example 1-2)
A platinum complex (Pt / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) having a platinum content of 3 wt% as a catalyst with respect to 100 parts by weight of methallyl-terminated polypropylene oxide (P-1). A propanol solution 150 ppm, 2,5-di-tert-butyl-1,4-benzoquinone 0.3 part by weight was added and reacted with 2.9 parts by weight of ethoxydimethylsilane at 100 ° C. for 4 hours. An oxypropylene polymer (A-1) was obtained.

(Synthesis Example 1-3)
100 parts by weight of the ethoxydimethylsilyl group-terminated polyoxypropylene polymer (A-1) is reacted with 38 parts by weight of methanol at 70 ° C. for 5 hours using 12 ppm of 1 mol / L ethyl ether solution as a catalyst. A base terminal polyoxypropylene polymer (A-2) was obtained. Conversion from an ethoxydimethylsilyl group to a methoxydimethylsilyl group is carried out by a signal (3H: 1.2 ppm) derived from an ethoxy group by ¹ H-NMR spectrum (measured in CDCl ₃ solvent using AMX400 manufactured by BRUKER). Confirmed by disappearance of the vicinity). In addition, a signal corresponding to the exo-methylene proton of the methallyl group at the terminal of the polymer (P-1) (2H: around 4.9 ppm), a signal derived from the methyl proton of the main chain (3H: around 1.1 ppm), heavy The number of methoxydimethylsilyl groups in the polymer (A-2) calculated from the integral ratio of the signal (3H: around 0.1 ppm) derived from the methyl group on the methoxydimethylsilyl group of the union (A-2) is The average was about 2.0 per molecule.

(Synthesis Example 2-1)
A bifunctional polypropylene having a number average molecular weight of about 14,500 and having an allyl group at the end is the same as in Synthesis Example 1-1 except that allyl chloride is used instead of 3-chloro-2-methyl-1-propene. Oxide (P-2) was obtained.

(Synthesis Example 2-2)
100 parts by weight of allyl-terminated polypropylene oxide (P-2) is reacted with 2.3 parts by weight of ethoxydimethylsilane at 100 ° C. for 2 hours using 150 ppm of a 2-propanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Thus, an ethoxydimethylsilyl group-terminated polyoxypropylene polymer (A-3) was obtained.

(Synthesis Example 2-3)
Using the ethoxydimethylsilyl group-terminated polyoxypropylene polymer (A-3), a methoxydimethylsilyl group-terminated polyoxypropylene polymer (A-4) was obtained in the same manner as in Synthesis Example 1-3. Conversion from the ethoxydimethylsilyl group to the methoxydimethylsilyl group was confirmed by the same method as in Synthesis Example 1-3. In addition, a signal corresponding to the exomethylene proton of the allyl group at the terminal of the polymer (P-2) (2H: around 5.2 ppm), a signal derived from the methyl proton of the main chain (3H: around 1.1 ppm), heavy The number of methoxydimethylsilyl groups in the polymer (A-4) calculated from the integral ratio of the signal derived from the methyl group on the union (A-4) methoxydimethylsilyl group (3H: around 0.1 ppm) is 1 The average was about 1.6 per molecule.

(Synthesis Example 3)
Using a methallyl-terminated polypropylene oxide (P-1) and using dimethoxymethylsilane in place of ethoxydimethylsilane, a dimethoxymethylsilyl group-terminated polyoxypropylene-based polymer ( D-1) was obtained. ^{As a} result of measurement by ¹ H-NMR, the number of terminal dimethoxymethylsilyl groups was about 2.0 per molecule on average.

(Synthesis Example 4)
A dimethoxymethylsilyl group-terminated polyoxypropylene polymer (P-2) is used in the same manner as in Synthesis Example 2-2 except that allyl-terminated polypropylene oxide (P-2) is used and dimethoxymethylsilane is used instead of ethoxydimethylsilane. D-2) was obtained. ^{As a} result of measurement by ¹ H-NMR, the number of terminal dimethoxymethylsilyl groups was about 1.6 on average per molecule.

(Synthesis Example 5-1)
A polyoxypropylene diol having a molecular weight of about 2,000 was used as an initiator, and a polypropylene oxide having a number average molecular weight of 28,500 having a terminal hydroxyl group was obtained in the same manner as in Synthesis Example 1-1. A bifunctional polypropylene having a number average molecular weight of about 28,500 and having an allyl group at the end is prepared in the same manner as in Synthesis Example 1-1 except that allyl chloride is used instead of 3-chloro-2-methyl-1-propene. Oxide (P-3) was obtained.

(Synthesis Example 5-2)
A dimethoxymethylsilyl group-terminated polyoxypropylene polymer (P-3) is used in the same manner as in Synthesis Example 2-2 except that allyl-terminated polypropylene oxide (P-3) is used and dimethoxymethylsilane is used instead of ethoxydimethylsilane. D-3) was obtained. ^{As a} result of measurement by ¹ H-NMR, the number of terminal dimethoxymethylsilyl groups was about 1.6 on average per molecule.

(Experimental example)
The following silanol condensation catalyst is added to the organic polymer (A-2), kneaded well, and allowed to stand for 6 days under constant temperature and humidity conditions of 23 ° C. and 50%. The molecular weight of the organic polymer after the reaction (A column made by Shodex was used, and the solvent was a molecular weight in terms of polystyrene measured using chloroform). When 3 parts by weight of acid (B) and 1 part by weight of amine compound (C) are added to 100 parts by weight of organic polymer (A-2), the composition after the reaction has a molecular weight of 100,000 or more. Polymer chains were included. On the other hand, when 2 parts by weight of the organic tin compound is added to 100 parts by weight of the organic polymer (A-2), the GPC chart shows almost no reaction, and the high molecular weight as described above is It was not included. In addition, the silanol condensation catalyst used in this experiment example was Versatic 10 (neodecanoic acid, Japan Epoxy Resin Co., Ltd.) as the acid (B), and 3-diethylaminopropylamine (Wako Pure Chemical Industries, Ltd.) as the amine compound (C). )), Neostan U-220 (dibutyltin (IV) bisacetylacetonate metal (Sn) content = 27.5%, Nitto Kasei Co., Ltd.) as an organic tin compound.

(Examples 1-6, Comparative Examples 1-4)
According to the formulation shown in Table 1, the organic polymer was weighed, a silanol condensation catalyst was added, and the mixture was thoroughly stirred and kneaded with a spatula and defoamed with a centrifuge. Next, the composition is filled into a sheet-like mold having a thickness of about 3 mm, cured for 1 hour under a constant temperature and humidity condition of 23 ° C. and 50%, and then cured for 20 hours in a 70 ° C. dryer to cure the sheet. A product was made. The cured product is punched into a mini dumbbell type test piece (No. 2 (1/3) type small test piece: see JISK7113 Annex 1), and a modulus at 100% elongation (M100) using an autograph (AG-2000A) manufactured by Shimadzu. The strength at break (TB) and the elongation at break (EB) were measured (measuring environment: 23 ° C., tensile speed: 200 mm / min). In Examples 1 to 6 and Comparative Example 4, a mixture of the organic polymer (A) and the organic polymer (D), Comparative Examples 1 and 2, the organic polymer (D), and Comparative Example 3 the organic polymer (D ) And a plasticizer mixture, the viscosity was measured with an E-type viscometer (VISCONIC EHD) manufactured by Tokyo Keiki. The results are shown in Table 1.

  In Table 1, the hardened | cured material obtained from the composition of Examples 1-6 showed the intensity | strength and elongation outstanding compared with the hardened | cured material of the comparative example 1 which does not contain an organic polymer (A). Moreover, when the organic polymer (D) having a large molecular weight was used as in Comparative Example 2, the strength and elongation characteristics tended to improve, but at the same time the viscosity increased. In Comparative Example 3 in which a plasticizer was added for the purpose of reducing the viscosity, the strength of the cured product was reduced. In Comparative Example 4 in which inorganic tin and an amine compound were used as catalyst components, a cured product exhibiting excellent strength and elongation could not be obtained even when the organic polymer (A) and the organic polymer (D) were used in combination. It can be seen that the compositions of the examples have both low viscosity before curing and high strength and high elongation of the cured product.

Claims (12)

General formula (1):
-[Si (R ¹ _2-b ) (X ¹ _b ) O] _m Si (R ¹ _3-a ) X ¹ _a (1)
(Wherein R ¹ is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when there are two or more R ^{1 s} , they may be the same or different, wherein R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, 3 R's may be the same or different, X ¹ represents a hydroxyl group or a hydrolyzable group, a and b are each 0 or 1, and m b's are the same. And an organic polymer (A) having a silicon group and an acid (B) represented by the following formula: m + represents an integer of 0 to 19. Composition.   The composition according to claim 1, comprising an amine compound (C). The composition according to claim ¹ , wherein X ^{1 in the} general formula (1) is an alkoxy group.   The main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylic acid ester polymer. A composition according to claim 1.   The composition according to claim 4, wherein the main chain skeleton of the organic polymer (A) is polypropylene oxide.   The composition according to any one of claims 1 to 5, wherein the acid (B) is a carboxylic acid. General formula (2):
_{^{- [Si (R 2 2-}} d) (X 2 d) O] n Si (R 2 3-c) X 2 c (2)
(In the formula, R ² is 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 a triorganosiloxy group represented by (R ′) ₃ SiO—. And when two or more R ² are present, they may be the same or different, where R ′ is the same as above, and X ² represents a hydroxyl group or a hydrolyzable group. C is 0, 1, 2 or 3, d is 0, 1 or 2, and c + Σd ≧ 2 is satisfied, and n is an integer of 0 to 19. The composition according to any one of claims 1 to 6, comprising an organic polymer (D) having a group. The composition according to claim 7, wherein X ^{2 in the} general formula (2) is an alkoxy group.   The main chain skeleton of the organic polymer (D) is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylic acid ester polymer. A composition according to claim 1.   The composition according to claim 9, wherein the main chain skeleton of the organic polymer (D) is polypropylene oxide.   The organic polymer (D) is contained in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) and the organic polymer (D). Composition.   A curable composition comprising the composition according to claim 1.