JP4864421B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition containing an organic titanium compound, and more specifically, contains an organic titanium compound that exhibits curing performance even in the presence of a nitrogen compound and a polymer having a crosslinkable silicon group at the terminal. The present invention relates to a curable composition.

  Conventionally, it is well known that a polymer having a crosslinkable silicon group is cured by moisture in the air at room temperature to give a rubber elastic body, such as polyorganosiloxane. Since these hardened | cured material is excellent in water resistance, a weather resistance, etc., it is utilized for sealing materials. For curing these compositions, organotin compounds and organotitanium compounds are often used as catalysts.

  A composition containing these polymers having a crosslinkable silicon group has an amino acid such as γ-aminopropyltrimethoxysilane or γ- (2-aminoethyl) aminopropyltrimethoxysilane for the purpose of imparting adhesiveness. Although a group-containing alkoxysilane is blended, when an organic titanium compound is used as a curing catalyst, nitrogen acts as a catalyst poison of titanium, and thus has a problem that it cannot be cured. Therefore, an organic tin compound or an amine compound has been used as a catalyst for curing a composition containing a nitrogen compound.

  However, when an organotin compound is used as a catalyst, since the catalytic function remains after curing, there is a problem that curing proceeds further and the cured product becomes harder, and when a large amount of moisture exists, the cured product becomes softer. It was. Furthermore, in recent years, organotin compounds are suspected as endocrine disrupting chemicals, and there is concern about their effects.

Among these, a method of using an organic titanium compound having a β-diketone as a ligand as a catalyst for curing a composition containing a nitrogen compound (see Patent Document 1), or an organic titanium compound having an acid as a ligand. A method to be used (see Patent Document 2) has been proposed. However, these methods have a problem that the curing rate is not sufficient or the storage stability is inferior when mixed with a polymer having a crosslinkable silicon group.
Japanese Patent Laid-Open No. 2002-249672 JP 2003-147220 A

  The present invention provides a curable composition that is stable even in the presence of a nitrogen compound, has high reactivity, can be cured at room temperature, and has excellent storage stability when mixed with a polymer having a crosslinkable silicon group. There is.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable composition that can solve the above problems can be obtained by containing a specific organic titanium compound, and have reached the present invention.

［一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、相互に同一又は異なって、アルコキシル基又はβ−ジケトナート基を示す。］

［一般式（２）中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、相互に同一又は異なって、水素原子、アルキル基又はアルコキシル基を示す。］
（Ｃ）少なくとも１個のアミノ基を有するアルコキシシランである接着性付与剤 ０．０５〜２０重量部
を含有することを特徴とする硬化性組成物を提供するものである。 That is, the first form of the present invention is at least the components (A), (B) and (C).
(A) Polymer material having at least one hydroxyl group or hydrolyzable functional group bonded to silicon 100 parts by weight (B) Represented by compound represented by general formula (1) and general formula (2) 0.1 to 20 parts by weight of a compound obtained by reacting a compound

[In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different from each other and each represents an alkoxyl group or a β-diketonate group. ]

[In General Formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other and each represents a hydrogen atom, an alkyl group or an alkoxyl group. ]
(C) Provided is a curable composition characterized by containing 0.05 to 20 parts by weight of an adhesion-imparting agent that is an alkoxysilane having at least one amino group .

［一般式（３）中、１種以上のＲ^９は、相互に同一又は異なって、アルキル基を示し、１種以上のＲ^１０は、相互に同一又は異なって、β−ジケトナート基を示し、ｐ及びｑは、０≦ｐ＜４、０＜ｑ≦４、ｐ＋ｑ＝４、ｐ≠２、ｑ≠２なる実数である。］
（Ｃ）少なくとも１個のアミノ基を有するアルコキシシランである接着性付与剤 ０．０５〜２０重量部
を含有することを特徴とする硬化性組成物を提供するものである。 In addition, the second embodiment of the present invention includes at least components (A), (B ′) and (C).
(A) Polymer material having at least one hydroxyl group or hydrolyzable functional group bonded to silicon 100 parts by weight (B ′) Compound represented by formula (3) 0.1 to 20 parts by weight

[In General Formula (3), one or more types of R ⁹ are the same or different from each other and represent an alkyl group, and one or more types of R ¹⁰ are the same or different from each other and represent a β-diketonate group, p and q are real numbers such that 0 ≦ p <4, 0 <q ≦ 4, p + q = 4, p ≠ 2, and q ≠ 2. ]
(C) Provided is a curable composition characterized by containing 0.05 to 20 parts by weight of an adhesion-imparting agent that is an alkoxysilane having at least one amino group .

  The curable composition of the present invention is excellent in storage stability and has good curability even at room temperature without any practical problems even in the presence of a nitrogen compound.

  The first embodiment of the present invention will be described below. The component (A) contained in the curable composition of the present invention is a polymer material having at least one hydroxyl group or hydrolyzable functional group bonded to silicon, but has the general formula: XYX It is preferable that it is a polymeric material represented by these. In the formula, Y represents an organic molecular chain or a siloxane molecular chain, and X represents an organic group having a hydroxyl group or a hydrolyzable functional group bonded to silicon.

  The organic molecular chain is not particularly limited, but a polyoxyalkylene chain, a urethane bond-containing polyoxyalkylene chain, and the like are preferable in terms of a good balance of elasticity after curing, strength, flexibility, and the like. An ethylene chain and a polyoxypropylene chain are particularly preferable.

  As the siloxane molecular chain, a dimethylsiloxane chain, a methylphenylsiloxane chain, and the like are preferable from the viewpoint of versatility.

X is an organic group having a hydroxyl group or a hydrolyzable functional group. The hydrolyzable functional group is not particularly limited, and examples thereof include an alkoxyl group and a ketoxime group. Of these, an alkoxyl group is particularly preferred. X includes —R ¹¹ ₂ SiOH, —R ¹¹ ₂ SiOR ¹² , —R ¹¹ Si (OR ¹² ) ₂ , —Si (OR ¹² ) ₃ , —SiR ¹¹ ₂ —R ¹³ —SiR ¹¹ _z (OR ¹² ). _3-z [wherein R ¹¹ represents a methyl group, R ¹² represents an alkyl group or an oxyalkyl group having up to 6 carbon atoms, and R ¹³ represents one of siloxane spacers having up to 6 silicon atoms. 2 represents a divalent hydrocarbon group which may be interrupted by one or more, and z represents 0 or 1. ] Is preferable from the viewpoint of curability.

  Component (A) is in the curable composition of the present invention and is blended as the main polymer.

  The component (B) contained in the curable composition of the present invention is a compound obtained by reacting the compound represented by the general formula (1) with the compound represented by the general formula (2).

［一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、相互に同一又は異なって、アルコキシル基又はβ−ジケトナート基を示す。］

[In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different from each other and each represents an alkoxyl group or a β-diketonate group. ]

［一般式（２）中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、相互に同一又は異なって、水素原子、アルキル基又はアルコキシル基を示す。］

[In General Formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other and each represents a hydrogen atom, an alkyl group or an alkoxyl group. ]

  The component (B) used in the present invention is used as a curing catalyst, and one or more of each of an organic titanium compound represented by the general formula (1) and a compound represented by the general formula (2) It is obtained by reacting. Therefore, the component (B) may be a single substance or a mixture. Further, the reaction may be completed or in the middle. Furthermore, reaction by-products such as alcohol may be included, and unreacted substances may be included. In addition, the component (B) may be obtained by separating a reaction product represented by, for example, the formula (3) from the product obtained by the reaction, or the product obtained by the reaction. It may be as it is. It is preferable that the component (B) is the product obtained by the reaction as it is, from the standpoint of reducing coloring and keeping the viscosity low.

In the general formula (1), the substituent represented by R ¹ , R ² , R ³ , R ⁴ is not particularly limited as long as it is an alkoxyl group or a β-diketonate group, but a linear chain having 1 to 8 carbon atoms. Or a branched alkoxyl group; a β-diketonate group such as an acetylacetonate group or an ethylacetoacetate group is preferred. R ¹ , R ² , R ³ and R ⁴ in the general formula (1) may be the same as or different from each other.

  Specifically, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, tert-amyloxy group, octyloxy group, acetylacetonate group Alternatively, an ethyl acetoacetate group is particularly preferable.

  Specific examples of the compound represented by the general formula (1) include tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisobutyl titanate, tetra-sec-butyl titanate, tetra-tert- Examples include butyl titanate, tetra-tert-amyl titanate, di-tert-amyl-diisopropyl titanate, tetra-2-ethylhexyl titanate, titanium diisopropoxybis (acetylacetonate), titanium diisopropoxybis (ethylacetoacetate), and the like. .

In the general formula (2), the substituent represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ is not particularly limited as long as it is a hydrogen atom, an alkyl group, or an alkoxyl group. It is preferably one having 1 to 4 carbon atoms, specifically hydrogen atom; alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group; methoxy group Alkoxyl groups such as ethoxy group, isopropoxy group and tert-butoxy group are particularly preferable. R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formula (2) may be the same as or different from each other. R ⁶ and R ⁷ are preferably a hydrogen atom or an alkyl group.

  Specific examples of the compound represented by the general formula (2) include acetylacetone, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2,2,6,6-tetramethyl-3. , 5-heptanedione, 3-methyl-2,4-pentanedione, methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, ethyl benzoyl acetate, ethyl butyryl acetate, ethyl isobutyryl acetate, ethyl 2-methyl Examples include acetoacetate, ethyl 2-benzylacetoacetate, dimethyl malonate, diisopropyl malonate, and the like.

  The reaction ratio is not particularly limited. In the compound represented by the general formula (1), when β-diketonate is not added, the reaction ratio is generally 1 mol part of the compound represented by the general formula (1). The compound represented by the formula (2) is preferably reacted in the range of 0.2 to 1.5 mol parts, particularly preferably in the range of 0.2 to 1 mol parts. Moreover, it is also preferable to react the compound represented by General formula (2) in the range of 2.5-4 mol part with respect to 1 mol part of compound represented by General formula (1), 3-4 mol It is also particularly preferable to carry out the reaction in the range.

  In the compound represented by the general formula (1), when 1 mol of β-diketonate is added, it is represented by the general formula (2) with respect to 1 mol part of the compound represented by the general formula (1). It is preferable to make it react in 0.1-0.5 mol part of the compound. Moreover, it is also preferable to make the compound represented by General formula (2) react in the range of 1.5 mol part-3 mol part with respect to 1 mol part of compound represented by General formula (1), It is also particularly preferable to react in the range of 3 mol.

  In the compound represented by the general formula (1), when 2 mol of β-diketonate is added, it is represented by the general formula (2) with respect to 1 mol part of the compound represented by the general formula (1). It is preferable to make it react in the range of 0.5 mol part-2 mol part, and it is especially preferable to make it react in the range of 1-2 mol.

  When there are too many compounds represented by General formula (2), it may color, and when there are too few, a balance of sclerosis | hardenability and storage stability may not be taken. Further, when the reaction ratio of the compound represented by the general formula (2) is out of the above range, the produced titanium compound may be a monoamine compound or a diamine compound as an adhesion promoter. Only curable compositions that are inferior in curability and storage stability may be provided, and therefore may not be used in combination with aminoalkoxysilanes that are excellent in general-purpose adhesion.

  About the reaction conditions of the compound represented by General formula (1) and the compound represented by General formula (2), it is not necessary to perform strong heating, long-time reaction, solvent distillation, etc. The desired component (B) can be synthesized by stirring at 70 ° C. for 1 to 60 minutes.

  As content of a component (B), it is 0.1-20 weight part with respect to 100 weight part of polymeric materials (A). When there is too little content of a component (B), a cure rate will become slow and hardening reaction may not fully advance. On the other hand, if the content of the component (B) is too large, local heat generation and foaming occur during curing, and coloring becomes strong, so that it may be difficult to obtain a good cured product. Preferably, it is 0.5-10 weight part, Most preferably, it is 1-5 weight part.

  The adhesion-imparting agent (C) contained in the curable composition of the present invention refers to an organofunctional alkoxysilane and is contained to improve the adhesion of the curable composition to the substrate. Although there is no particular limitation as long as it is an organic functional alkoxysilane, in the present invention, the adhesion imparting agent (C) is preferably an alkoxysilane containing at least one amino group in the molecule. Adhesive expression at normal temperature with respect to various adherends is favorable and preferable. Further, the curable composition of the present invention has a feature that even if the adhesion-imparting agent (C) has an amino group in the molecule, the curable composition can be cured without being inhibited. Such titanium compounds are particularly preferably combined with various adherends with amino group-containing alkoxysilanes having good room temperature adhesion.

  The adhesiveness-imparting agent (C) is not particularly limited as long as the above conditions are satisfied. Specific examples include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ -Aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, Examples thereof include γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, partial hydrolysis products thereof, and the like.

  As content of an adhesive provision agent (C), it is 0.05-20 weight part with respect to 100 weight part of polymeric materials (A). When there is too little content of an adhesive provision agent (C), adhesiveness may not express. On the other hand, when there is too much content of an adhesive provision agent (C), sclerosis | hardenability may worsen. Preferably, it is 0.1-10 weight part, Most preferably, it is 0.5-5 weight part.

  The curable composition of the present invention further contains a crosslinking agent as component (D) in an amount of 20 parts by weight or less with respect to 100 parts by weight of component (A). To improve the physical properties and storage stability. The component (D) contained in the curable composition of the present invention is not particularly limited as long as it reacts with the polymer material of the component (A) to form a siloxane bond, but is an organofunctional alkoxysilane. Preferably there is. In the present invention, the component (D) is particularly preferably a silane or siloxane compound having at least two hydrolyzable functional groups from the viewpoints of versatility and crosslinking performance.

  The crosslinking agent (D) is not particularly limited as long as the above conditions are satisfied. Specific examples include, for example, methyltri (methylethylketoximo) silane, vinyltri (methylethylketoximo) silane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyl Examples include triacetoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, and partial hydrolysis products thereof.

  The content of the crosslinking agent (D) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer material (A) when the main skeleton of the polymer material (A) is a siloxane molecular chain. When there is too little content of a crosslinking agent (D), bridge | crosslinking may become inadequate. On the other hand, when there is too much content of a crosslinking agent (D), hardening time may become late. Preferably, it is 0.5-10 weight part, Most preferably, it is 1-5 weight part. When the main skeleton of the polymer material (A) is a polyoxyalkylene chain, the crosslinking agent may or may not be blended.

  Hereinafter, a second embodiment of the present invention will be described. The 2nd form in this invention is a curable composition characterized by containing a component (A), (B '), and (C) at least. In the second embodiment, the component (A) and the component (C) are the same as those used in the first embodiment described above, and the same is true for preferable ones, specific examples, effects of inclusion, and the like.

［一般式（３）中、１種以上のＲ^９は、相互に同一又は異なって、アルキル基を示し、１種以上のＲ^１０は、相互に同一又は異なって、β−ジケトナート基を示し、ｐ及びｑは、０≦ｐ＜４、０＜ｑ≦４、ｐ＋ｑ＝４、ｐ≠２、ｑ≠２なる実数である。］ Therefore, regarding the second embodiment, the component (B ′) will be described. The component (B ′) is a compound represented by the general formula (3). The component (B ′) does not need to be a single substance, and may be a mixture of two or more compounds represented by the general formula (3). In that case, p and q are also average values of two or more compounds, and are not necessarily integers.

[In General Formula (3), one or more types of R ⁹ are the same or different from each other and represent an alkyl group, and one or more types of R ¹⁰ are the same or different from each other and represent a β-diketonate group, p and q are real numbers such that 0 ≦ p <4, 0 <q ≦ 4, p + q = 4, p ≠ 2, and q ≠ 2. ]

In General Formula (3), R ⁹ may be one type or two or more different types. R ⁹ is the same or different from each other, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, tert-amyl group or octyl group. It is preferable that

In the general formula (3), R ¹⁰ may be one type or two or more different types. R ¹⁰ is the same or different from each other, and is preferably an acetylacetonate group or an ethylacetoacetate group.

When the alkoxysilane having one amino group is used as the adhesion promoter (C), the organotitanium compound represented by the general formula (3) is 2 <p and q <2, From the viewpoint of storage stability, it is particularly preferable that 3 ≦ p and q ≦ 1.

  On the other hand, when an alkoxysilane having two or more amino groups is used as the adhesion-imparting agent (C), p <2 and 2 <q are preferable in terms of curability and storage stability, and p ≦ It is particularly preferable that 1 and 3 ≦ q.

  When p = q = 2, even when an alkoxysilane having one amino group was used as the adhesion promoter (C), an alkoxysilane having two amino groups was used as the adhesion promoter (C). Even in this case, both curability and storage stability are inferior.

  The synthesis method of the component (B ′) represented by the general formula (3) is not particularly limited, but by reacting the compound represented by the general formula (1) with the compound represented by the general formula (2). Easy to synthesize. When synthesizing the organotitanium compound of component (B ′), it is not necessary to perform strong heating, long-time reaction, distilling off the solvent, etc., and stirring at 10 to 70 ° C. for 1 to 60 minutes. Thus, a desired compound can be synthesized.

  Content of a component (B ') is 0.1-20 weight part with respect to 100 weight part of polymeric materials (A). When there is too little content of a component (B '), a cure rate will become slow and hardening reaction may not fully advance. On the other hand, if the amount of component (B) used is too large, local heat generation and foaming will occur during curing, and coloring will become strong, and it may be difficult to obtain a good cured product. Preferably, it is 0.5-10 weight part, Most preferably, it is 1-5 weight part.

  The amount of the adhesion-imparting agent (C) used is 0.05 to 20 parts by weight with respect to 100 parts by weight of the polymer material (A). When there is too little content of an adhesive provision agent (C), adhesiveness may not express. On the other hand, when there is too much content, sclerosis | hardenability may worsen. Preferably, it is 0.1-10 weight part, Most preferably, it is 0.5-5 weight part.

  The content of the crosslinking agent (D) is 20 parts by weight or less with respect to 100 parts by weight of the polymer material (A), but when the main skeleton of the polymer material (A) is a siloxane molecular chain, the polymer material (A) It is preferable that it is 0.1-20 weight part with respect to 100 weight part. When there is too little content of a crosslinking agent (D), bridge | crosslinking may become inadequate. On the other hand, when there is too much content of a crosslinking agent (D), hardening time may become late. Especially preferably, it is 0.5-10 weight part, More preferably, it is 1-5 weight part. When the main skeleton of the polymer material (A) is a polyoxyalkylene chain, the crosslinking agent (D) may or may not be blended.

Further, for both the first form and the second form, the curable composition of the present invention further includes a filler, a colorant, a plasticizer, a curing accelerator, an anti-sagging agent, an anti-aging agent, a solvent, and the like. The substance normally contained in the curable composition may be contained.

  Although the usage method of the curable composition of this invention does not have limitation in particular, It is preferable to use as a sealing material, an adhesive agent, etc. In particular, the curable composition of the present invention is preferably used for the purpose of curing at room temperature from the viewpoint of making the most of the characteristics of the composition of the present invention that absorbs moisture and cures.

  Even if the curable composition containing the component (B) or the component (B ′) uses a nitrogen-containing compound that easily inhibits curability as the (C) adhesiveness-imparting agent, it has excellent curability that can withstand practical use. It is not clear about the action / principle to exert, but by arranging an appropriate number of ligands that balance the coordination ability to titanium according to the type of aminosilane, the activity of the titanium compound is controlled, and the curability and It is considered that the storage stability was balanced.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Synthesis example 1
To a glass reaction vessel equipped with a stirrer, 424 g (1 mol) of titanium diisopropoxybis (acetoacetate) and 200 g (2 mol) of acetylacetone were added, and the mixture was stirred at 60 ° C. for 30 minutes. 624 g was obtained.

Synthesis example 2
To a glass reaction vessel equipped with a stirrer, 487 g (1 mol) of titanium diisopropoxybis (acetylacetonate) and 200 g (2 mol) of acetylacetone were added, and the mixture was stirred at 60 ° C. for 30 minutes. 687 g was obtained.

Synthesis example 3
To a glass reaction vessel equipped with a stirrer, 340 g (1 mol) of tetra-tert-butyl titanate and 26.0 g (0.2 mol) of ethyl acetoacetate were added and stirred at 60 ° C. for 30 minutes. 357 g of compound C was obtained.

Example 1 to Example 3
As component (A), titanium compound A obtained in Synthesis Examples 1, 2 and 3 as component (B) or component (B ′) with respect to 100 parts by weight of hydroxy-terminated dimethylpolysiloxane or alkoxy-terminated dimethylpolysiloxane , B or C, and the component (C) adhesiveness imparting agent and others were blended in parts by weight as shown in Table 1, and kneaded to prepare a curable composition.

  For these, the initial tack-free time after aging at 40 ° C. for 1 day (the time until the surface tack disappears) and the tack-free time after storage deterioration after aging at 40 ° C. for 14 days were measured. The results are shown in Table 2. The tack-free time was measured in a temperature-controlled room with a room temperature of 23 ° C. and a humidity of 50% rh.

Comparative Example 1 to Comparative Example 4
As component (A), titanium diisopropoxy bis (ethyl acetoacetate), titanium diisopropoxy bis (acetylacetonate) or titanium tetra 2-based on 100 parts by weight of hydroxy-terminated dimethylpolysiloxane or alkoxy-terminated dimethylpolysiloxane. Ethyl hexanoate, component (C), and the like were blended in the weight parts shown in Table 1 and kneaded under the same conditions as in Examples 1 to 3 to prepare curable compositions.

  Also for these, the tack free time was measured in the same manner as in Examples 1 to 3. The results are shown in Table 2.

The symbols in Table 1 are as follows.
SZ-6070: Methyltrimethoxysilane (manufactured by Dow Corning Toray)
KBM-603: γ- (2-aminoethyl) aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBM-903: γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

  From the results in Table 2, it is clear that when the room temperature curable composition of the present invention is used, it cures faster than the conventional room temperature curable composition and is also excellent in storage stability. Table 3 summarizes the performance of the results of Examples, Comparative Examples, and others, focusing on the number of amino groups in the component (C) adhesion-imparting agent.

The judgment criteria in Table 3 are as follows.
[Curing property]
○: Initial tack free time is 1 hour or less
Δ: Initial tack free time exceeds 1 hour and 2 hours or less ×: Initial tack free time exceeds 2 hours

[Storage stability]
○: Tack free time after storage deterioration after aging at 40 ° C. for 14 hours or less ×: Similarly, tack free time after storage deterioration exceeds 2 hours

  From Table 3, the titanium compounds according to the present invention (component (B) and component (B ′)) are hardened by selecting the adhesion-imparting agent of component (C) by paying attention to the number of amino groups. It was also found that a curable composition having excellent storage stability (curability after storage deterioration) can be provided. On the other hand, the titanium compound of the comparative example can give only a curable composition that is inferior in curability and storage stability, even if a monoamine compound or a diamine compound is used as an adhesion promoter. It turned out that it cannot use together with the amino alkoxysilane excellent in general purpose adhesiveness.

The curable composition of the present invention is stable even in the presence of a nitrogen compound, is highly reactive even in the presence of a nitrogen compound, can be cured at room temperature, and has a storage stability when mixed with a polymer having a crosslinkable silicon group. Is also excellent, and can be widely used in fields such as sealing materials and adhesives.

Claims (9)

At least components (A), (B) and (C)
(A) Polymer material having at least one hydroxyl group or hydrolyzable functional group bonded to silicon 100 parts by weight (B) Represented by compound represented by general formula (1) and general formula (2) 0.1 to 20 parts by weight of a compound obtained by reacting a compound

[In the general formula (1), R ¹ , R ² , R ³ and R ⁴ are the same or different from each other and each represents an alkoxyl group or a β-diketonate group. ]

[In General Formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other and each represents a hydrogen atom or an alkyl group . ]
(C) A curable composition comprising 0.05 to 20 parts by weight of an adhesion-imparting agent which is an alkoxysilane having at least one amino group. At least components (A), (B ′) and (C)
(A) Polymer material having at least one hydroxyl group or hydrolyzable functional group bonded to silicon 100 parts by weight (B ′) Compound represented by formula (3) 0.1 to 20 parts by weight

[In General Formula (3), one or more types of R ⁹ are the same as or different from each other and represent an alkyl group, and one or more types of R ¹⁰ are the same or different from each other and represent an acetylacetonate group, p and q are real numbers such that 0 ≦ p <4, 0 <q ≦ 4, p + q = 4, p ≠ 2, and q ≠ 2. ]
(C) 0.05-20 weight part of adhesive imparting agents which are the alkoxysilane which has at least 1 amino group, The curable composition of Claim 1 characterized by the above-mentioned . In the general formula (1), R ¹ , R ² , R ³ , R ⁴ are the same or different from each other, and methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, The curable composition according to claim 1 or 2, which is a sec-butoxy group, a tert-butoxy group, a tert-amyloxy group, an octyloxy group, an acetylacetonate group or an ethylacetoacetate group. In the general formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other, and are a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group or tert. The curable composition according to any one of claims 1 to 3, which is a -butyl group . In the general formula (3), one or more kinds of R ⁹ are the same or different from each other, and are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. The curable composition according to any one of claims 2 to 4, which is -butyl group, tert-amyl group or octyl group. The curable composition according to any one of claims 1 to 5 , wherein the component (A) is a polyorganosiloxane. The curable composition according to any one of claims 1 to 6 , further comprising, as component (D), a crosslinking agent in an amount of 20 parts by weight or less based on 100 parts by weight of component (A). object. The curable composition according to any one of claims 1 to 7 , wherein the component (D) is a silane or siloxane compound having at least two hydrolyzable functional groups. The curable composition according to any one of claims 1 to 8 , which is for room temperature curing.