JP2011219507A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having good curability and adhesiveness and free of coloring, while using a non-tin catalyst.SOLUTION: The curable composition contains (A) a polyoxyalkylene polymer having a silicon-containing group capable of crosslinking by forming a siloxane bond and (B) an aluminum carboxylate salt in which a carbon atom adjacent to a carbonyl group constituting a carboxylate ion is quaternary carbon. The curable composition may further contain an amine compound as (C) component.

Description

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

  A polyoxyalkylene polymer containing at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have a property that a cured product can be obtained.

  These polyoxyalkylene polymers are disclosed in (Patent Document 1) and the like, have already been industrially produced, and are widely used for applications such as sealing materials, adhesives and paints.

  These curable compositions containing a polyoxyalkylene polymer having a reactive silicon group are cured using a silanol condensation catalyst. In the case of a one-part curable composition, dibutyltin bis (acetylacetate) is used. Organic tin-based catalysts having a carbon-tin bond, such as natto, are widely used. However, in recent years, the toxicity of organotin compounds has been pointed out.

  Techniques using divalent carboxylic acid tin salts are disclosed in (Patent Document 2), (Patent Document 3) and the like as curing catalysts other than organic tin. In addition, as a non-tin-based curing catalyst (Patent Document 4), a technique using various carboxylic acid metal salts is disclosed.

  However, when the nontin-based carboxylic acid metal salt described in (Patent Document 4) is used as a curing catalyst for a curable composition containing a polyoxyalkylene polymer, the curability is not sufficient. Alternatively, there is a problem that the obtained cured product is colored.

JP-A-52-73998 Japanese Patent No. 3062626 JP 2000-345054 A (US6410640) JP 2003-206410 A

  The present invention relates to a curable composition containing a polyoxyalkylene polymer having a reactive silicon group as a main component and having a good curability and a non-coloring cure using a non-tin catalyst. An object is to provide a sex composition.

  As a result of intensive investigations to solve such problems, the present inventors have obtained practical curability by using a carboxylic acid aluminum salt (B) having a specific structure as a silanol condensation catalyst of this polymer. The inventors have found that a curable composition having no color can be obtained, and have completed the present invention.

That is, the present invention
(1).
(A) a polyoxyalkylene polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, and
(B) a carboxylate aluminum salt in which the carbon atom adjacent to the carbonyl group constituting the carboxylate ion is a quaternary carbon;
A curable composition comprising:
(2).
(C) The curable composition according to (1), which further contains an amine compound as a component,
(3).
The curable composition according to (1) or (2), wherein the polyoxyalkylene polymer as the component (A) is a polyoxypropylene polymer,
(4).
(B) The curable composition according to any one of (1) to (3), wherein the aluminum carboxylate salt is aluminum neodecanoate,
(5).
The curable composition according to any one of (1) to (4), further comprising a silane coupling agent;
(6).
The component (A) according to any one of (1) to (5), wherein 0.01 to 20 parts by weight of the carboxylic acid aluminum salt of the component (B) is contained with respect to 100 parts by weight of the polyoxyalkylene polymer of the component. Curable composition,
(7).
(A) 0.01 to 20 parts by weight of the carboxylic acid aluminum salt and (C) the amine compound of 0.01 to 20 parts by weight with respect to 100 parts by weight of the component polyoxyalkylene polymer. Part of the curable composition according to any one of (2) to (5),
About.

  The curable composition of the present invention is excellent in curability without coloring while using a non-tin catalyst.

  The present invention will be described in detail below.

The reactive silicon group contained in the polyoxyalkylene polymer having a reactive silicon group has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and a siloxane bond is formed by a reaction accelerated by a silanol condensation catalyst. It is a group that can be cross-linked by forming. As the reactive silicon group, the general formula (1):
-SiR ¹ _3-a X _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 (R ′) ₃ SiO— (R ′ is Each independently represents a triorganosiloxy group represented by a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and X is independently a hydroxyl group or a hydrolyzable group. And a is any one of 1, 2, and 3).

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  Hydrolyzable groups and hydroxyl groups can be bonded to one silicon atom in the range of 1 to 3, and 2 or 3 is preferable from the viewpoint of curability. When two or more hydrolyzable groups or hydroxyl groups are bonded to the silicon atom, they may be the same or different. A reactive silicon group having three hydroxyl groups or hydrolyzable groups on a silicon atom has high activity and good curability, and is excellent in resilience, durability and creep resistance of the resulting cured product. Therefore, it is preferable. On the other hand, a reactive silicon group having two hydroxyl groups or hydrolyzable groups on a silicon atom is preferable because it is excellent in storage stability and the obtained cured product has high elongation and high strength.

Specific examples of R ¹ in the general formula (1) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.

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

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

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

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

  (C) A polyoxyalkylene 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 functional group reactive to this functional group and a reactive silicon group. .

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

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. , Methyldimethoxysilane, phenyldimethoxysilane, alkoxysilanes such as 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyldiacetoxysilane Examples thereof include, but are not limited to, acyloxysilanes such as: ketoximate silanes such as bis (dimethylketoximate) methylsilane and bis (cyclohexylketoximate) methylsilane. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the resulting polyoxyalkylene polymer has high curability, storage stability, elongation characteristics, and tensile strength. . Trimethoxysilane is particularly preferable from the viewpoints of curability and restorability of the resulting curable composition.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is subjected to a radical addition reaction in the presence of a radical initiator and / or a radical generating source, and the polyoxyalkylene polymer is unsaturated. Although the method etc. which introduce | transduce into a binding site are mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropylmethyldiethoxy. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropylmethyldiethoxy. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, 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, fairly dangerous compounds such as dimethoxysilane and tetrahydrosilane are produced. However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. Therefore, when a group in which three hydrolyzable groups such as trimethoxysilyl group are bonded to one silicon atom is used as the silicon-containing group, the synthesis method (b) or (c) may be used. preferable.

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

  The polyoxyalkylene polymer having a reactive silicon group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably 1,000 to It is 50,000, and particularly preferably 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, an average of at least one reactive silicon group contained in the polyoxyalkylene polymer per molecule of the polymer, Preferably 1.1 to 5 are present. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. The reactive silicon group may be at the end of the main chain of the polyoxyalkylene polymer molecular chain, at the end of the side chain, or at both. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network chain length of the polyoxyalkylene polymer component contained in the finally formed cured product is increased, so that high strength, A rubber-like cured product having a high elongation and a low elastic modulus is easily obtained.

The polyoxyalkylene polymer essentially has the general formula (3):
-R ⁴ -O- (3)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ⁴ in the general formula (3) 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 (3) include
_{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3) 2 O-, _{-CH 2 CH 2 CH 2 CH 2} O-
Etc. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or has a relatively low viscosity.

  Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

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

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

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

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

The amide segment has the general formula (4):
—NR ⁵ —C (═O) — (4)
(R ⁵ is a hydrogen atom or a monovalent organic group, preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 8 carbon atoms. An unsubstituted monovalent hydrocarbon group).

  Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (4).

An example of an industrially easy production method of a polyoxyalkylene polymer having an amide segment and a reactive silicon group is illustrated by reacting an excess polyisocyanate compound with a polyoxyalkylene polymer having an active hydrogen-containing group at the terminal. To form a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or a part of the isocyanate group has the general formula (5)
W-R ⁶ -SiR ¹ _3-a X _a (5)
(In the formula, R ¹ , X and a are the same as described above. R ⁶ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. W is produced by a method in which a W group of a silicon compound represented by a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary) is reacted. Can be mentioned. Examples of known production methods for organic polymers related 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 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21879 (US) (Japanese Patent No. 5364955), Japanese Patent Laid-Open No. 10-53637 (US Pat. No. 5,757,751), Japanese Patent Laid-Open No. 11-100197, Japanese Patent Laid-Open No. 2000-169544, Japanese Patent Laid-Open No. 2000-169415, Japanese Patent Laid-Open No. 2002-212415, and Japanese Patent No. 3313360. , US Pat. No. 4,067,844, US Pat. No. 37 No. 1445, JP 2001-323040, and the like.

Further, the polyoxyalkylene polymer having an active hydrogen-containing group at the terminal is represented by the general formula (6).
O = C = N—R ⁶ —SiR ¹ _3−a X _a (6)
(However, in the formula, R ¹ , R ⁶ , X, and a are the same as those mentioned above.) Those produced by reacting with a reactive silicon group-containing isocyanate compound can be mentioned. Examples of known production methods of organic polymers related to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6,046,270), JP-A 58- No. 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.

  Examples of the polyoxyalkylene polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer (polyether polyol) having a hydroxyl group at the terminal.

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

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex 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.

  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 (5), when it illustrates concretely, (gamma) -aminopropyl trimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyl trimethoxysilane, (gamma)-( Amino such as N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; and the like. 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 products of various α, β-unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds, The Michael addition reaction product of can also be used as the silicon compound of general formula (5).

  The reactive silicon group-containing isocyanate compound represented by the general formula (6) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triexylsilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl 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 (5) 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 (6).

  When there are many amide segments in the main chain skeleton of the polyoxyalkylene polymer which is the component (A) of the present invention, the viscosity of the polyoxyalkylene polymer is increased and the composition may have poor workability. . On the other hand, the amide segment in the main chain skeleton of the component (A) tends to improve the curability of the composition of the present invention. Therefore, when the main chain skeleton of the component (A) includes an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 7, and particularly preferably 2 to 5 preferable. When the number is less than 1, the curability may not be sufficient, and when the number is more than 10, the polyoxyalkylene polymer may have a high viscosity, resulting in a poor workability composition.

  In the curable composition of the present invention, as the component (B), a carboxylic acid aluminum salt in which the carbon atom adjacent to the carbonyl group constituting the carboxylic acid ion is a quaternary carbon is used. The component (B) acts as a so-called silanol condensation catalyst capable of forming a siloxane bond from a hydroxyl group or hydrolyzable group bonded to a silicon atom contained in the polyoxyalkylene polymer as the component (A). is there.

  The component (B) of the present invention exhibits particularly good catalytic activity when combined with the polyoxyalkylene polymer as the component (A). Moreover, it is a non-tin catalyst and a curing catalyst with a small environmental load. Furthermore, the hardened | cured material obtained by hardening the curable composition of this invention does not have coloring based on (B) component. That is, it is a non-tin catalyst that achieves both curing catalyst activity and non-coloring properties.

  Moreover, (B) component of this invention is a salt of carboxylic acid and aluminum whose carbon atom adjacent to the carbonyl group which comprises carboxylate ion is a quaternary carbon. The component (B) of the present invention is excellent in curing as compared with a carboxylic acid aluminum salt in which the carbon atom adjacent to the carbonyl group constituting the carboxylic acid ion is tertiary carbon, secondary carbon, or primary carbon. Showing gender. Here, the tertiary carbon indicates a carbon atom bonded to three carbon atoms, and the quaternary carbon indicates a carbon atom bonded to four carbon atoms.

  The carboxylic acid in which the carbon atom adjacent to the carbonyl group constituting the carboxylate ion of the component (B) is a quaternary carbon is represented by the general formula (7):

(Wherein R ⁷ , R ⁸ and R ⁹ are each independently a substituted or unsubstituted monovalent organic group which may contain a carboxyl group), or a general fatty acid ion represented by Formula (8):

(Wherein R ¹⁰ is a substituted or unsubstituted monovalent organic group, R ¹¹ is a substituted or unsubstituted divalent organic group, each of which may contain a carboxyl group) and the general formula (9 ):

(Wherein, R ¹² is a substituted or unsubstituted trivalent organic group, which may contain a carboxyl group), and a cyclic fatty acid ion containing a structure represented by:

  Specific examples of the carboxylic acid in which the carbon atom adjacent to the carbonyl group constituting the carboxylate ion is a quaternary carbon include pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2 -Diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2- Linear monocarboxylic acids such as dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid, 2,2-dimethyl-3-hydroxypropionic acid, dimethylmalonic acid, ethylmethylmalonic acid, Linear dicarboxylic acids such as diethyl malonic acid, 2,2-dimethyl succinic acid, 2,2-diethyl succinic acid, 2,2-dimethyl glutaric acid, 3-methyl isoqueste Acid, chain tricarboxylic acid such as 4,4-dimethylaconitic acid, 1-methylcyclopentanecarboxylic acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2- Methylbicyclo [2.2.1] -5-heptene-2-carboxylic acid, 2-methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, And cyclic carboxylic acids such as bicyclo [2.2.1] heptane-1-carboxylic acid and bicyclo [2.2.2] octane-1-carboxylic acid. Many compounds containing such structures exist in natural products, but of course they can also be used.

  In particular, from the viewpoint of good compatibility with the component (A), an aluminum salt of a monocarboxylic acid is more preferable, and an aluminum salt of a chain monocarboxylic acid is more preferable. In addition, aluminum pivalate, aluminum neodecanoate, aluminum versatic acid, aluminum 2,2-dimethyloctanoate, aluminum 2-ethyl-2,5-dimethylhexanoate and the like are particularly preferred because they are easily available.

  Moreover, it is preferable that carbon number of the acid group part of the carboxylic acid aluminum salt of (B) component is 5-20, It is more preferable that it is 6-18, It is still more preferable that it is 7-16, 8- 12 is particularly preferred. If the number of carbons exceeds this range, it tends to become solid and is difficult to be compatible with the component (A), and the activity cannot be obtained, which is not preferable. On the other hand, a small number of carbon atoms is not preferable from the viewpoint of volatility and odor. From these points, the component (B) is particularly preferably aluminum neodecanoate, aluminum versatic acid, aluminum 2,2-dimethyloctanoate or aluminum 2-ethyl-2,5-dimethylhexanoate.

  The amount of component (B) used is preferably about 0.01 to 20 parts by weight, more preferably about 0.5 to 10 parts by weight, based on 100 parts by weight of component (A). If the blending amount of component (B) is below this range, the curing rate may be slow, and the curing reaction may not proceed sufficiently, which is not preferable. On the other hand, if the blending amount of component (B) exceeds this range, the pot life may be too short, resulting in poor workability, and is not preferable from the viewpoint of storage stability.

  Moreover, each said carboxylic acid aluminum salt can be used in combination of 2 or more types besides using it individually.

  On the other hand, when the carboxylic acid aluminum salt as the component (B) is low in activity and an appropriate curability cannot be obtained, an amine compound as the component (C) can be added as a promoter.

  Specific examples of the component (C) amine compound include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, laurylamine, pentadecylamine, Aliphatic primary amines such as cetylamine, stearylamine, cyclohexylamine; dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, Aliphatic secondary amines such as dilaurylamine, dicetylamine, distearylamine, methylstearylamine, ethylstearylamine, butylstearylamine, etc. Aliphatic tertiary amines such as triamylamine, trihexylamine and trioctylamine; aliphatic unsaturated amines such as triallylamine and oleylamine; aromatics such as laurylaniline, stearylaniline and triphenylamine And other amines such as monoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine, diethylenetriamine, triethylenetetramine, benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2 4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU), 1,5 -Diazabicyclo (4, 3, 0) nonene-5 (DBN) etc. are mentioned, However, It is not limited to these.

  As these (C) components, the cocatalyst ability varies greatly depending on the structure of the (C) component itself and the compatibility with the (A) component. Therefore, in the present invention, octylamine, lauryl are used because of their high cocatalyst ability. Primary amines such as amines are preferred, and amine compounds having a hydrocarbon group having at least one heteroatom are preferred. Examples of heteroatoms include N, O, S and the like, but are not limited thereto. Examples of such amine compounds include those exemplified for the above-mentioned other amines. Among these, an amine compound having a hydrocarbon group having a hetero atom on any one of the 2nd to 4th carbon atoms is more preferable. Examples of such amine compounds include ethylenediamine, ethanolamine, dimethylaminoethylamine, diethylaminoethylamine, 3-hydroxypropylamine, diethylenetriamine, 3-methoxypropylamine, 3-lauryloxypropylamine, N-methyl-1,3-propane. Examples include diamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3- (1-piperazinyl) propylamine, and 3-morpholinopropylamine. Of these, 3-diethylaminopropylamine and 3-morpholinopropylamine are more preferable because of their high promoter ability. 3-Diethylaminopropylamine is particularly preferred because it provides a curable composition with good adhesion, workability, and storage stability.

  The compounding amount of the amine compound as the component (C) is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the component (A). If the compounding amount of the amine compound is less than 0.01 parts by weight, the curing rate may be slow, and the curing reaction may not proceed sufficiently. On the other hand, when the compounding amount of the amine compound exceeds 20 parts by weight, the pot life becomes too short, and the workability tends to deteriorate. On the contrary, the curing speed may be slow.

  On the other hand, when the carboxylic acid aluminum salt as the component (B) is low in activity and an appropriate curability cannot be obtained, a carboxylic acid can be added as a promoter.

  The carboxylic acid is not particularly limited, and various carboxylic acids can be used. A carboxylic acid in which the carbon atom adjacent to the carbonyl group is a tertiary carbon (such as 2-ethylhexanoic acid) or a carboxylic acid having a quaternary carbon ( Neodecanoic acid, pivalic acid, etc.) are more preferable because of their high curing rate, and carboxylic acids in which the carbon atom adjacent to the carbonyl group is a quaternary carbon are particularly preferable. Moreover, the carboxylic acid whose carbon atom adjacent to a carbonyl group is a quaternary carbon is excellent also in adhesiveness compared with other carboxylic acid.

  Other curing catalysts can be used in combination to such an extent that the effects of the present invention are not reduced. Specific examples include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); dibutyltin dilaurate , Dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate) ), Dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), dioctyl Bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), dibutyltin oxide And tetrasilicates such as a reaction product of silicate compound and dibutyltin oxide and phthalate; aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetate Examples include organoaluminum compounds such as acetate; zirconium alkoxides such as zirconium tetrakis (acetylacetonate). However, when adding an organic tin compound, depending on the amount added, the toxicity or environmental burden may increase, so the amount of the organic tin compound used is 100 parts by weight of component (A). 0.5 parts by weight or less is preferable, 0.1 parts by weight or less is more preferable, 0.01 parts by weight or less is more preferable, and it is most preferable that the substance is not substantially contained.

  Moreover, a silicate can be used for the composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the resilience, durability and creep resistance of the polyoxyalkylene polymer (A) of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When using a silicate, the usage-amount is 0.1-20 weight part with respect to 100 weight part of (A) component, Preferably it is 0.5-10 weight part.

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

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

  Examples of the partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

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

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

  Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A No. 2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to 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 organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol group present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

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

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

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

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

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

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

  As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall. A preferable finishing method and the like are described in JP-A-9-53063.

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

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

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

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

  Specific examples of balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.

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

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

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

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

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

  The number average molecular weight of the polymer plasticizer is preferably 500 to 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, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a GPC method in the case of a vinyl polymer, and by a terminal group analysis method in the case of a polyether polymer. Moreover, it is measured by molecular weight distribution (Mw / Mn) GPC method (polystyrene conversion).

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

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

  The amount of the plasticizer used is 5 to 150 parts by weight, preferably 10 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of component (A). If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.

  To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, isocyanatemethyltrimethoxysilane, isocyanate. Isocyanate group-containing silanes such as methyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, isocyanatemethyldiethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyl Limethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- ( 2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N -Ethylamino) -2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ-ureido Propyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxy Amino group-containing silanes such as silane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyl Mercapto group-containing silanes such as triethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- Epoxy group-containing silanes such as 3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2 -Methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane and other carboxysilanes; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ -Vinyl type unsaturated group-containing silanes such as acryloyloxypropyltriethoxysilane and methacryloyloxymethyltrimethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; Tris (3-trime Silyl propyl) isocyanurate silanes such as isocyanurate and the like. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . Examples of the reaction product of the silane coupling agent include the reaction product of aminosilane and epoxysilane, the reaction product of aminosilane and isocyanate silane, and partial condensates of various silane coupling agents. The silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of (A) component. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  The effects of the silane coupling agent added to the curable composition of the present invention are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.

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

  A tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclohexane. Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9) Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

  The tackifier resin is used in an amount of 5 to 1,000 parts by mass, preferably 10 to 100 parts by mass, per 100 parts by mass of the component (A).

  A solvent or 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. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher 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.

  You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; 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 break elongation. 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 described in 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 silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029 Examples thereof include a compound of a polyhydric alcohol having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol or sorbitol, which generates a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis.

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

  The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of component (A).

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. Further, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight per 100 parts by weight of component (A).

  In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight per 100 parts by weight of component (A).

  A photocurable material can be used in the composition of the present invention. When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved. A photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups The compound which contains 3 or more same functional groups on average in 1 molecule is preferable. (All Aronix is a product of 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 used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of component (A). When the amount is 20 parts by weight or more, the cured product tends to be too hard and tends to crack.

  An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene and 1,3-pentadiene Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. The amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (A). If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An antioxidant (antiaging agent) can be used in the composition of the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by Adeka Argus Chemical Co., Ltd.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Co., Ltd.) A hindered amine light stabilizer 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 preferably in the range of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of component (A).

  A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (A). Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan); MARK LA-57, LA-62, LA-67, LA-63 (all above Adeka) 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).

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

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

  When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

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

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

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

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

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

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

  Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, and anti-anticides. And fungicides. These various additives may be used alone or in combination of two or more. Specific examples other than the specific examples of the additives listed in the present specification include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-62-2904, It is described in Japanese Laid-Open Patent Publication No. 2001-72854.

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

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl By adding an alkoxysilane compound such as methyldiethoxysilane or γ-glycidoxypropyltrimethoxysilane, the storage stability is further improved.

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

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

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

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

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

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

(Synthesis Example 1)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. A polypropylene oxide having a number average molecular weight of about 19,000 (polystyrene equivalent molecular weight measured using Tosoh's HLC-8120GPC as the liquid feeding system, TOS-GEL H type as the column, and THF as the solvent). It was. Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. As a result, a polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained.

After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain a purified allyl group-terminated polypropylene oxide (hereinafter, allyl polymer). 100 parts by weight of the resulting allyl polymer was reacted with 1.35 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst. Polypropylene oxide (A-1) was obtained. ^{As a} result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal methyldimethoxysilyl groups was about 1.7 on average per molecule.

(Synthesis Example 2)
Under a nitrogen atmosphere at 23 ° C., 77.4 g (450 mmol) of neodecanoic acid was added dropwise to the reaction vessel containing 36.9 g (150 mmol) of aluminum tributoxide over 10 minutes. During the addition, the reaction proceeded exothermically. After completion of dropping, the mixture was heated to 50 ° C. and further stirred for 5 hours, and then generated butanol was devolatilized under reduced pressure to obtain aluminum neodecanoate (B-1).

(Examples 1-3, Comparative Examples 1-3)
As the component (A), 100 parts by weight of the polymer (A-1) obtained in Synthesis Example 1, 55 parts by weight of diisodecyl phthalate (manufactured by Shin Nippon Rika, Sanso Sizer DIDP), surface-treated colloidal calcium carbonate (manufactured by Shiraishi Kogyo, 120 parts by weight of white glossy CCR) or 120 parts by weight of surface-treated colloidal calcium carbonate (manufactured by Maruo Calcium, Calfine 200M), 20 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, Taipaque R-820), thixotropic agent (manufactured by Enomoto Kasei) 2 parts by weight of Disparon 6500), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals, Tinuvin 327), 1 part by weight of a light stabilizer (Sankyo, Sanol LS770), vinyltrimethoxysilane (manufactured by Momentive, A-171) 2 parts by weight or 1.6 parts by weight of methyl silicate 51 (manufactured by Colcoat), and 3 parts by weight of N- (beta-aminoethyl) -γ-aminopropyltrimethoxysilane (manufactured by Momentive, A-1120) was kneaded under dehydrating conditions. Finally, aluminum neodecanoate (B-1) obtained in Synthesis Example 2 or iron (III) 2-ethylhexanoate (Nihon Kagaku Sangyo, Nikka Octix Iron 6% (T)), 2-ethyl Tin (II) hexanoate (Nitto Kasei, Neostan U-28), Tin (II) neodecanoate (Nitto Kasei, Neostan U-50), 3-diethylaminopropylamine (Wako Pure Chemical Industries), 4-Pipecoline (Wako Pure Chemical Industries, Ltd.) was added according to the formulation shown in Table 1 and then mixed and sealed in a moisture-proof container to obtain a one-component curable composition. Using the prepared one-component curable composition, the curability (skinning time), coloring of the cured product, and adhesiveness were evaluated in the following manner.

(Curing test)
Each curable composition was extruded from the cartridge, filled into a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat surface. This time was set as the curing start time, the surface was touched with a spatula, and the time when the composition did not adhere to the spatula was measured as the skinning time. The skinning time was measured under conditions of 23 ° C. and 50% RH. The results are shown in Table 1.

(Coloring of cured product)
Each curable composition was extruded from the cartridge, filled into a mold having a thickness of about 5 mm using a spatula, and the surface was adjusted to a flat surface. The film was cured for 7 days under conditions of 23 ° C. and 50% RH, and the color of the obtained cured product was visually evaluated. The results are shown in Table 1.

(Adhesion test)
As a result of the above-described evaluation of the color of the cured product, the adhesion was evaluated for the uncolored product. Each curable composition was extruded from the cartridge so as to be in close contact with the steel sheet, thereby preparing a sample. After the prepared sample was cured at 23 ° C. for 7 days, the adhesion was evaluated by a 90-degree hand peel test. Cohesive fracture was marked with ○, and interface fracture was marked with ×. The results are shown in Table 1.

  As shown in Table 1, when the component (B) was used as a curing catalyst, a cured product having good curability, no coloring, and good adhesion was obtained.

(Synthesis Example 3)
Synthesis example using hydroxyl-terminated polypropylene oxide having a number average molecular weight of about 26,000 obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using polyoxypropylene triol having a molecular weight of about 3,000 as an initiator Allyl-terminated trifunctional polypropylene oxide was obtained by the same procedure as in 1. This allyl-terminated polypropylene oxide is reacted with 1.1 parts by weight of methyldimethoxysilane in the same procedure as in Synthesis Example 1, and an average of 1.9 methyldimethoxysilyl group-terminated polyoxypropylene polymers (A -2) was obtained.

(Example 4, Comparative Examples 4-8)
(A) As a component, with respect to 95 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer (A-2) obtained in Synthesis Example 3, colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name Hakujyuka) CCR) 60 parts by weight, colloidal calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name Viscolite R) 60 parts by weight, heavy calcium carbonate (Shiraishi Calcium Co., Ltd., trade name Whiten SB) 20 parts by weight, PPG 3000 (Mitsui Chemicals Co., Ltd., Actol P-23) 60 parts by weight, thixotropic agent (Enomoto Kasei Co., Ltd., Disparon # 305) 3 parts by weight, photocurable resin (manufactured by Toagosei Co., Ltd.) Product name Aronix M-309) 3 parts by weight, benzotriazole UV absorber (Ciba Specialty Chemicals Co., Ltd., product name Tinuvin 327) 1 part by weight, hindered phenol Antioxidant (Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1010), 1 part by weight, respectively weighed, well kneaded with a three-roll paint was a base material.

  Next, according to the prescription in Table 2, the above-mentioned main agent was coated with the aluminum neodecanoate (B-1) obtained in Synthesis Example 2 or the aluminum 2-ethylhexanoate (Nikka Chemical, Nikka) as a silanol condensation catalyst. Octix aluminum 8%), bismuth 2-ethylhexanoate (III) (Nippon Chemical Industries, Nikka Octix bismuth 25%), bismuth neodecanoate (III) (Aldrich), tin 2-ethylhexanoate (II) (Nitto Kasei, Neostan U-28), neodecanoic acid tin (II) (Nitto Kasei, Neostan U-50), and laurylamine as component (C) are weighed and mixed for 3 minutes using a spatula did. Here, the number of added parts of the various carboxylic acid metal salts of the component (B) was such that the number of moles of the metal atoms contained was the same. After mixing, a mold having a thickness of about 3 mm was filled with a spatula to prepare a flat surface. This time was set as the curing start time, the surface was touched with a spatula, and the time when the composition did not adhere to the spatula was measured as the skinning time. The skinning time was measured under conditions of 23 ° C. and 50% RH.

  Table 2 shows the composition of the main agent and curing catalyst and the evaluation results of curability (skinning time).

  As shown in Table 2, as a curing catalyst, a carboxylic acid aluminum salt (Nikka Octix Aluminum, Comparative Example 4) in which the carbon atom adjacent to the carbonyl group is a tertiary carbon is a carboxylic acid aluminum salt that is a quaternary carbon. When changed to the component (B) of the present invention (Example 4), a marked improvement in the curing rate was observed. On the other hand, a carboxylic acid tin salt (Neostan U-28, Comparative Example 5) whose carbon atom adjacent to the carbonyl group is tertiary carbon and a carboxylic acid tin salt (Neostan U-50, Comparative Example 6) which is quaternary carbon. When the curability is compared, or bismuth carboxylate (Nikka Octix bismuth, Comparative Example 7) in which the carbon atom adjacent to the carbonyl group is tertiary carbon and bismuth carboxylate (bismuth neodecanoate) in which quaternary carbon is present. When the curability of (III) and Comparative Example 8) were compared, no significant improvement in the curing rate seen with aluminum salts was observed.

Claims (7)

(A) a polyoxyalkylene polymer having a silicon-containing group that can be crosslinked by forming a siloxane bond, and
(B) a carboxylate aluminum salt in which the carbon atom adjacent to the carbonyl group constituting the carboxylate ion is a quaternary carbon;
A curable composition comprising:   The curable composition according to claim 1, further comprising an amine compound as component (C).   The curable composition according to claim 1 or 2, wherein the polyoxyalkylene polymer as the component (A) is a polyoxypropylene polymer.   The curable composition according to any one of claims 1 to 3, wherein the (B) component carboxylic acid aluminum salt is aluminum neodecanoate.   The curable composition according to any one of claims 1 to 4, further comprising a silane coupling agent.   The curability according to any one of claims 1 to 5, comprising 0.01 to 20 parts by weight of the carboxylic acid aluminum salt of the component (B) with respect to 100 parts by weight of the polyoxyalkylene polymer of the component (A). Composition.   (A) 0.01 to 20 parts by weight of the carboxylic acid aluminum salt and (C) the amine compound of 0.01 to 20 parts by weight with respect to 100 parts by weight of the component polyoxyalkylene polymer. The curable composition according to any one of claims 2 to 5, which is contained in a part.