JP2002105265A - One-component curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an curable composition which mainly consists of a saturated hydrocarbon polymer with a reactive silicone group, used as an one- component sealing material which has an excellent adhesive property and storage stability while improving a curing property. SOLUTION: The one-component curable composition contains (A) a saturated hydrocarbon polymer having at least one reactive silicone group, (B) an ester plasticizer, (C) a condensation curing catalyst, and (D) a silane coupling agent having (D-1) a reactive silicone group and (D-2) at least one group selected from a group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond (hereinafter referred to as a "silicon-containing group").
Curable composition containing a saturated hydrocarbon polymer having a "reactive silicon group") as a main component.

[0002]

2. Description of the Related Art Saturated hydrocarbon-based polymers containing at least one reactive silicon group in the molecule can form a siloxane bond at room temperature by a reaction such as a hydrolysis reaction of the reactive silicon group by moisture or the like. It is known that it has an interesting property of being cross-linked to give a rubber-like cured product. Since this polymer is excellent in heat resistance, water resistance, weather resistance, etc., it is used as a sealing material for construction, a sealing material for vehicles, an adhesive, a waterproof material, a sealing material for electricity, a sealing material for double glazing, and the like. And is effective.

[0003] However, this saturated hydrocarbon-based polymer is characterized by low water vapor and gas permeability due to its main chain structure, and when used as a one-pack type sealing material (particularly in a deep part). )) Has a slightly poor curability,
There has been a problem that only the two-liquid type has been practically used. Also, conventionally, it has been desired to reduce the viscosity of the curable composition to improve the workability.

[0004]

DISCLOSURE OF THE INVENTION In view of the above-mentioned circumstances, the present invention has improved the curability of a curable composition containing a saturated hydrocarbon polymer having a reactive silicon group as a main component, and in particular, has improved the curability of a deep part. Another object of the present invention is to provide a curable composition which can be favorably used as a one-pack type sealing material having adhesiveness and storage stability.

Further, the present invention provides a curable composition containing a saturated hydrocarbon polymer having a reactive silicon group as a main component, the curable composition having low viscosity and excellent workability. It is intended for.

[0006]

Means for Solving the Problems The present inventors have studied to solve such a problem, and as a result, by adding an ester plasticizer to this polymer, the curability, particularly the deep curability, has been improved. It has been found that the adhesiveness is improved while securing storage stability by adding a silane coupling agent having a specific structure as an adhesiveness-imparting agent. Further, the above problems have been solved by the composition of the present invention, and the present invention has been completed.

That is, the present invention relates to a saturated hydrocarbon polymer (A) having at least one silicon-containing group which has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can be crosslinked by forming a siloxane bond. ), An ester-based plasticizer (B), a condensation curing catalyst (C), and a silicon-containing group (a) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond, And a one-part curable composition containing a silane coupling agent (D) having at least one group (b) selected from the group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate group. . Further, the present invention is also a one-pack type sealing material composition for a building produced by dehydrating the one-pack type curable composition. Hereinafter, the present invention will be described in detail.

The saturated hydrocarbon polymer having a reactive silicon group (A) according to the present invention has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by forming a siloxane bond. Group, that is, a saturated hydrocarbon polymer having at least one reactive silicon group.

The saturated hydrocarbon polymer having a reactive silicon group is a polymer substantially containing no carbon-carbon unsaturated bond other than the aromatic ring, and is, for example, polyethylene, polypropylene, polyisobutylene, hydrogenated polybutadiene. And hydrogenated polyisoprene. As the reactive silicon group, general formula (1):

[0010]

Embedded image

Wherein R ¹ and R ² are each independently 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 independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms) and is a triorganosiloxy group. X is each independently a hydroxyl group or a hydrolyzable group. a is 0,
1, 2, or 3, b is 0, 1, or 2, and a and b do not become 0 at the same time. m is 0 or an integer of 1 to 19].

The hydrolyzable group representing X includes, for example,
Examples thereof include commonly used groups such as 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. Among these, an alkoxy group,
An amide group and an aminooxy group are preferred, but an alkoxy group is particularly preferred because of its mild hydrolyzability and easy handling. Among them, those having 1 to 10 carbon atoms are preferable, those having 1 to 5 carbon atoms are more preferable, and those having 1 to
Three are particularly preferred.

A hydrolyzable group or a hydroxyl group can be bonded to one silicon atom in the range of 1 to 3 (a + m
b) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms forming the reactive silicon group is one or more. In the case of silicon atoms linked by a siloxane bond or the like, the number is preferably 20 or less. In particular, the general formula (2)

[0014]

Embedded image

(Wherein R ² , X, and a are the same as those described above) are preferred because the raw material can be easily obtained. The number of reactive silicon groups in one molecule of the saturated hydrocarbon-based polymer is one or more, preferably 1.1 to 5. If the number of reactive silicon groups contained in the molecule is less than one, the curability may be insufficient and good rubber elasticity may not be obtained.

The reactive silicon group may be present at the terminal or inside the molecular chain of the saturated hydrocarbon polymer, or may be present at both. In particular, when the reactive silicon group is located at the molecular end, the amount of the effective network chain of the saturated hydrocarbon-based polymer component contained in the finally formed cured product is increased, so that a high-strength, high-elongation rubber-like It is preferable in that a cured product is easily obtained. These saturated hydrocarbon polymers having a reactive silicon group can be used alone or in combination of two or more.

The polymer constituting the skeleton of the saturated hydrocarbon polymer having a reactive silicon group (A) used in the present invention is as follows:
(1) an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene or the like is polymerized as a main monomer, or (2) a diene-based compound such as butadiene or isoprene is homopolymerized, or Can be obtained by copolymerizing the above-mentioned olefin-based compound, followed by hydrogenation.However, an isobutylene-based polymer or a hydrogenated polybutadiene-based polymer can easily introduce a functional group into a terminal and have a molecular weight of It is preferable because it can be easily controlled and the number of terminal functional groups can be increased.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units,
The monomer unit having copolymerizability with isobutylene is contained in the isobutylene-based polymer in an amount of preferably 50% or less (% by weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 10% or less. Is also good. That is, those having a total amount of 50% of repeating units derived from isobutylene are preferable, and those having 70% are more preferable.
% Is more preferable.

Examples of such a monomer component include, for example,
Examples thereof include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Specifically, 1-butene, 2-butene, 2
-Methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochloro Styrene, dichlorostyrene, β-pinene, indene, vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl -1,1,3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethyl Examples include ruchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylmethyldimethoxysilane. Further, when vinylsilanes or allylsilanes are used as a monomer having copolymerizability with isobutylene, the silicon content increases and the number of groups that can act as a silane coupling agent increases, and the adhesiveness of the obtained composition is increased. improves.

In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the above-mentioned isobutylene-based polymer, other monomer units in addition to the main monomer unit are used. You may make it contain. Saturated hydrocarbon polymer having a reactive silicon group in the curable composition of the present invention (A)
Is preferably 30% or more, more preferably 20% or more, and particularly preferably 10% or more.

In the curable composition of the present invention, the curability of the one-pack type curable composition is increased, the viscosity is reduced to facilitate handling, and the extrudability and workability at low temperatures are improved. Therefore, an ester plasticizer is used as the component (B). By adding an ester plasticizer as a component (B), the curability, the extrudability at low temperatures and the workability are improved, and depending on the base material, the adhesiveness is improved, and the paintability and stainability are affected. And a curable composition having a small amount of water can be obtained. Further, when an ester-based plasticizer is added, the tensile properties of the cured product become higher elongation and higher strength, and may become more desirable properties as an elastic sealant for construction.

Specific examples of the ester plasticizer include dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butylbenzyl phthalate,
Di-n-octyl phthalate, diisononyl phthalate,
Phthalates such as diisodecyl phthalate and diundecyl phthalate; non-aromatic dibasic esters such as di (2-ethylhexyl) adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate and di (2-ethylhexyl) sebacate; Aromatic esters such as di-2-ethylhexyl tetrahydrophthalate, tri-2-ethylhexyl trimellitate and triisodecyl trimellitate; esters of polyalkylene glycols such as diethylene glycol benzoate and triethylene glycol dibenzoate; tricresyl phosphate And phosphate esters such as tributyl phosphate. Among them, non-aromatic dibasic acid esters are preferable because they have particularly good low-temperature fluidity and curability (particularly, deep curability). These may be used alone or in combination of two or more.

The ester plasticizer is used in place of a solvent for the purpose of adjusting the reaction temperature and adjusting the viscosity of the reaction system when introducing a reactive silicon group into the saturated hydrocarbon polymer. There may be. The ester plasticizer (B)
The curability of a curable composition containing a saturated hydrocarbon polymer having a reactive silicon group, particularly deep curability, is greatly improved, and furthermore, the mechanical properties of the cured product, adhesion, heat resistance,
It does not adversely affect various properties such as weather resistance.

The number-average molecular weight of the ester plasticizer as the component (B) is not particularly limited, but is preferably in the range of 200 to 1,000, and particularly preferably in the range of 300 to 500. When the number average molecular weight is less than 200, the mechanical properties of the cured product may change significantly with time due to large heat loss, and if it exceeds 1000, the plasticizing effect may be insufficient, The workability of the composition may deteriorate.

The amount of the component (B) is 100 parts.
The amount is preferably 10 to 150 parts with respect to parts (parts by weight, hereinafter the same), but particularly preferably 30 to 100 parts. If the amount is less than 10 parts, the effect of lowering the viscosity may not be sufficient, and if it exceeds 150 parts, the mechanical properties and adhesiveness of the composition may be reduced.

Further, a plasticizer other than the ester plasticizer may be used in combination. The plasticizer other than the ester plasticizer is not particularly limited, but generally used saturated hydrocarbon, paraffin, and aromatic plasticizers can be used.

The condensation curing catalyst which is the component (C) of the present invention is a conventionally known one. As a specific example, for example,
Titanate such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diethylhexanolate, dibutyltin dioctate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate , Dibutyltin diisooctyl malate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin maleate, dibutyltin diacetate, tin octylate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethylmalate, Tin carboxylates such as dioctyltin diisooctylmalate, dioctyltin diversate, tin naphthenate; dibutyltin dimethoxide, dibutyltin diphenoxide, dibutyltin Tin alkoxides such as sopropoxide; tin oxides such as dibutyltin oxide and dioctyltin oxide; reactants of dibutyltin oxide with phthalic acid esters; dibutyltin bisacetylacetonate; aluminum trisacetylacetonate; aluminum trisethylacetoacetate And organic aluminum compounds such as diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine , Diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylurea Benzylamine, diethylaminopropylamine, xylylenediamine, 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)
And the like, or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines with epoxy compounds; Condensation curing catalysts such as silane coupling agents having an amino group such as aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane; and other known acid catalysts and basic catalysts. Examples include condensation curing catalysts.

When rapid curing at room temperature is required among these catalysts, it is preferable to use a tetravalent tin compound, particularly dialkoxy tin dialkoxide, and particularly dibutyl tin bisacetylacetonate, dibutyl tin dimethoxide, Dibutyltin dipropoxide is preferred. The effect of the present invention is remarkably exhibited when a tetravalent tin compound such as dialkyltin dialkoxide is used as a curing catalyst because the curing rate does not decrease even after storage. These catalysts may be used alone or in combination of two or more.

The amount of the component (C) is 0.1 to 20 parts by weight based on 100 parts of the saturated hydrocarbon polymer in the component (A).
Parts is preferable, and 1 to 10 parts is more preferable. If the amount of the silanol curing catalyst falls below this range, the curing rate may be slow, and the curing reaction may not be sufficiently advanced. On the other hand, if the amount of the silanol curing catalyst exceeds this range, local heat generation and foaming may occur during curing, making it difficult to obtain a good cured product. Is also not preferred.

The silane coupling agent, which is the component (D) in the present invention, has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by forming a siloxane bond. And at least one group selected from the group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate group (b)
And imparts adhesiveness to the one-part curable composition of the present invention.

Here, examples of the reactive silicon group (a) include groups represented by the above general formula (1), preferably the above general formula (2). Examples of the hydrolyzable group include the groups already exemplified, but a methoxy group,
Ethoxy groups and the like are preferred because of their high hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly preferably 3 or more.

The silane coupling agent as the component (D) includes, in addition to the reactive silicon group (a), at least one selected from the group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate group. It has one group.

These silane coupling agents are selected from the viewpoints of imparting adhesion to the one-part curable composition and not impairing the storage stability of the composition itself. For example, γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane, which is a silane coupling agent having a primary amino group often used for the purpose of imparting adhesiveness, is used as the one-part curable composition. In particular, when a non-aromatic dibasic acid ester is used as the component (B), a problem arises in that the curability during storage is greatly reduced.

Specific examples of the silane coupling agent (D) in the present invention include secondary amino such as γ-phenylaminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine and γ-anilinopropyltrimethoxysilane. Group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. Isocyanate group-containing silanes; isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane; 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate and the like Containing isocyanurate group Silanes and the like can be mentioned.

Also, derivatives of these modified derivatives, 2
Amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, blocked isocyanate silanes, phenylamino long-chain alkylsilanes, aminosilylated silicones, etc. containing a tertiary amine can also be used as the silane coupling agent. Such a silane coupling agent is easily decomposed in the presence of moisture, but can be stably present when added to the component (A) of the composition of the present invention.

The silane coupling agent used in the present invention is
Usually, a reactive silicon group-containing saturated hydrocarbon polymer 100
Parts are used in the range of 0.01 to 20 parts. In particular, it is preferable to use it in the range of 0.1 to 10 parts. The above-mentioned adhesiveness-imparting agent may be used alone or in combination of two or more.

In the curable composition of the present invention, various fillers are used as needed. Specific examples of the filler include, for example, wood flour, pulp, cotton chips, asbestos,
Glass fiber, carbon fiber, mica, walnut husk powder, rice husk powder, graphite, diatomaceous earth, clay, fume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, Quartz, aluminum fine powder, flint powder,
Zinc powder and the like. Among these fillers, precipitated silica, fumed silica, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable.

In particular, the use of colloidal calcium carbonate (specifically, Sealets made by Maruo Calcium Co., Ltd.) treated with about 3% by weight of a fatty acid ester as a surface treatment agent is a problem to be solved by the present invention. It is preferable because certain workability can be remarkably improved, and a compound having good thixotropic property and thread breaking property can be obtained. These fillers may be used alone or in combination of two or more.

When the filler is used, it is preferably used in an amount of 1 to 500 parts, more preferably 50 to 20 parts, per 100 parts of the component (A).
0 parts is more preferred.

Further, various additives may be added to the curable composition of the present invention, if necessary, in addition to the filler described above. Examples of such additives include, for example, a curing accelerator that promotes a condensation reaction of an amine or the like, a physical property modifier that adjusts the tensile properties of the resulting cured product, an adhesion improver, an antioxidant, and a radical inhibitor. , UV absorbers, metal deactivators, ozone deterioration inhibitors, light stabilizers, photocurable resins, anti-sagging agents, phosphorus peroxide decomposers, lubricants, pigments, foaming agents,
Examples include an antioxidant and a dehydrating agent. Specific examples of such additives include, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149,
It is described in each specification of JP-A-64-22904.

In preparing the one-part curable composition of the present invention, the viscosity of the composition can be reduced by mixing and dehydrating the components. This is an effect not expected by the present inventors. The dehydration can be performed, for example, by heating under reduced pressure. The conditions at that time are not particularly limited, but are, for example, 100 to 200 ° C. and less than 1 atmosphere. Thereby, the water content of the composition is reduced to 1000 p.
pm, more preferably 800
ppm or less, more preferably 600 ppm or less. It is considered that the reason why the viscosity of the conventional curable composition is high is that water contained in the composition interacts with a filler or the like, thereby imparting thixotropy and acting as a thickener. Therefore, by performing dehydration of the composition, the point that the viscosity, which has conventionally been a problem in the case of the two-pack type, has a slightly lower workability, has been improved, and a curable composition having a low viscosity and excellent workability is obtained. I can do it.

[0042]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Examples 1 to 3 and Comparative Examples 1 and 2 As shown in Table 1, a paraffin-based process oil (Idemitsu Kosan Co., Ltd.) was used as a component (A) for polyisobutylene oligomer EP500S (manufactured by Kaneka Chemical Industry Co., Ltd.). )
(Trade name: PS-32), di-2-ethylhexyl adipate (Nippon Rika Co., Ltd.) as an ester plasticizer (B)
Manufactured by Sansosizer DOA), colloidal calcium carbonate (manufactured by Maruo Calcium Co., Ltd., Nanocoat S25), heavy calcium carbonate (manufactured by Shiraishi Calcium Co., trade name: PO320B10), antioxidant (Trade name MARK AO-50, manufactured by Asahi Denka Co., Ltd.)
The mixture was mixed for about 10 minutes using a twin-screw stirrer (manufactured by Inoue Seisakusho) until the mixture became visually uniform.

About 1 g of the blend obtained by the above operation was extracted, and the initial water content was measured with a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd.).
It was confirmed that it was not less than ppm.

Next, the above composition was devolatilized under reduced pressure for 1 hour.
After continuing stirring at 20 ° C. for 2 hours, the mixture was cooled to room temperature.
At this time, the water content of the composition was measured in the same manner as the previous time. As a result, it was confirmed that the composition was dehydrated to about 500 ppm, and that the viscosity of the composition was significantly lowered after the dehydration.

The dehydrated composition was treated with an ultraviolet absorber (Sumisorb 400, trade name, manufactured by Sumitomo Chemical Co., Ltd.), a light stabilizer (Sanol LS-765, trade name, manufactured by Sankyo Co., Ltd.), and a dehydrating agent (Nihon Unicar Co., Ltd. Co., Ltd., trade name A-171) was added and stirred for 10 minutes. Further, an isocyanate silane coupling agent (Y-518, manufactured by Nippon Unicar Co., Ltd.)
7) and an epoxysilane coupling agent (A-187, manufactured by Nippon Unicar Co., Ltd.), and after stirring for 10 minutes, a condensation curing catalyst (trade name: U-220, manufactured by Nitto Kasei Co., Ltd.) was added. After performing a defoaming operation under reduced pressure for about 5 minutes under
A one-part curable composition was obtained by filling a one-part aluminum coated paper cartridge (manufactured by Showa Marutsu). The above procedure is summarized in FIG.

In Example 2, an isocyanurate silane coupling agent (Nihon Unicar Co., Ltd.) was used instead of the isocyanate silane coupling agent and the epoxy silane coupling agent used as the component (D) in Example 1.
Comparative Example 1 was a primary aminosilane coupling agent (manufactured by Nippon Unicar Co., Ltd., A-
1110).

In Example 3, diundecyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., trade name: Sanso Co., Ltd.) which is an aromatic ester plasticizer was used instead of the plasticizer as the component (B) used in Example 1. Comparative Example 2 is a paraffin plasticizer (manufactured by Idemitsu Kosan Co., Ltd.).
The product name is Diana Process PS-32). The components used are summarized in Table 1 below.

[0048]

[Table 1]

(1) Adhesion The above one-component curable composition was allowed to stand at room temperature for 24 hours or more, and then subjected to an adhesion test. Specimens used for the adhesion test were prepared as follows. First, using a commercially available gun from a one-liquid cartridge, a substrate was used as an adherend in Example 1
And the one-pack type curable compositions prepared in Comparative Examples 1 and 2. 1 in a constant temperature room at a temperature of 23 ° C and a humidity of 60 ± 5%
After curing for 4 days, a cut was made in the adhesive surface with a cutter knife, a hand peel test was performed, and the surface of the substrate was observed. The case where the cured product itself was broken was referred to as cohesive failure (CF), the case where the cured product was broken while leaving a thin layer at the bonding interface was referred to as thin layer breaking (TCF), and the case where the cured product was broken at the bonding interface was referred to as interface breaking (AF). . The evaluation was made with n = 2, and the ratio of each destruction state was confirmed. Regarding the notation of the result,
For example, in the case of 50% for CF and 50% for AF, it is described as C50A50.

(2) Deep Curability The deep curability is 16.5 mm in inner diameter and 80 m in length.
m in a polyethylene tube filled with the one-pack type curable composition prepared in Examples 1 to 3 and Comparative Examples 1 and 2 at a temperature of 23.
After 7 days in a constant temperature chamber at a temperature of 60 ° C. and a humidity of 60 ± 5%, the hardened portion of the surface layer formed at the tip of the tube was taken out, and the hardened thickness was measured with a vernier caliper.

(3) Storage stability The storage stability of the composition is as follows:
The skinning time was measured as curability after storage for 14 days,
Evaluation was made by the comparison. For skinning time, extrude the sealing material into an ointment can, flatten the surface, lightly press the surface with a microspatula at regular intervals, observe whether the sealing material adheres, and check the tip of the microspatula. The time when the sealing material did not adhere to the sample was determined.皮 indicates that the skinning time after storage was less than 1.5 times the initial skinning time, and x indicates that the skinning time was 1.5 times or more the initial skinning time. Table 2 shows the results.

[0052]

[Table 2]

From Table 2, it can be seen that in Examples 1 to 3 and Comparative Example 1, the curability at the deep portion was 3 to 6 mm after curing at 23 ° C. for 7 days, whereas in Comparative Example 2, it was about 1 mm. Using an ester plasticizer as the component (B),
Above all, it can be confirmed that the use of a non-aromatic dibasic acid ester significantly improves the deep curability.

In Examples 1 to 3 and Comparative Example 1, except for a part of the base material, it is shown that they have good adhesiveness. In Comparative Example 2, the sample for the adhesion test was
Under the prescribed curing conditions, the inside was not sufficiently cured and the adhesion could not be evaluated.

In Comparative Example 1, the curability was retarded to 1.5 times or more after storage at 50 ° C. for 14 days, whereas Examples 1-3
, The storage stability is good when less than 1.5 times.

As described above, by adding (B) an ester-based plasticizer to (A) a saturated hydrocarbon-based polymer having at least one reactive silicon group in a molecule, curability, particularly, Improving the deep curability, and (D) imparting adhesion while securing storage stability by adding a silane coupling agent having a specific structure as an adhesion-imparting agent. Was confirmed.

[0057]

The curable composition of the present invention can remarkably improve curability, especially deep curability, and has adhesiveness and storage stability. In addition, the curable composition of the present invention is particularly useful as a building sealing material or a sealing material for double glazing because of its low viscosity, and is a workable sealing material when applied in winter.

[Brief description of the drawings]

FIG. 1 is a procedure for preparing a one-part curable composition in Example 1.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09K 3/10 C08K 5/54 F term (Reference) 4H017 AA04 AA31 AB15 AD05 AE03 4J002 AE03X AE05X BB20W CP17W EC077 EH026 EH146 EN027 ER027 EU237 EX038 EX068 EX078 EZ047 FD02X FD026 FD157 FD206 FD208 GJ01 GL00

Claims (7)

[Claims] 1. A saturated hydrocarbon polymer (A) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond, and an ester-based polymer. A plasticizer (B), a condensation curing catalyst (C), a silicon-containing group (a) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of being crosslinked by forming a siloxane bond, and a secondary. A one-part curable composition comprising a silane coupling agent (D) having at least one group (b) selected from the group consisting of an amino group, an epoxy group, an isocyanate group and an isocyanurate group. 2. The saturated hydrocarbon polymer as the component (A),
The number average molecular weight is in the range of 500 to 50,000, and at the terminal of the main chain and / or the terminal of the side chain, a compound represented by the general formula (1): [Wherein, R ¹ and R ² each independently represent a carbon number of 1 to
An alkyl group having 20; an aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms; or (R ′) ₃ SiO—
(R ′ is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms). X is each independently a hydroxyl group or a hydrolyzable group. a is 0, 1, 2, or 3, b is 0, 1, or 2, and a and b do not become 0 at the same time. m is 0 or an integer of 1 to 19].
The one-part curable composition according to claim 1, wherein the one-part curable composition has at least one resin. 3. The one-part curable composition according to claim 2, wherein X is an alkoxy group. 4. The saturated hydrocarbon polymer as component (A),
The one-pack type curable composition according to any one of claims 1 to 3, which has a repeating unit derived from isobutylene in a total amount of 50% by weight or more. 5. The one-part curable composition according to claim 1, wherein the ester plasticizer as the component (B) is a non-aromatic dibasic acid ester. 6. A saturated hydrocarbon polymer (A) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group capable of crosslinking by forming a siloxane bond, 100 parts by weight. 10 to 150 parts by weight of an ester plasticizer (B) and a condensation curing catalyst (C)
0.1 to 20 parts by weight, and a silicon-containing group (a) having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond;
Silane coupling agent (D) having at least one group (b) selected from the group consisting of a secondary amino group, an epoxy group, an isocyanate group and an isocyanurate group (D) 0.01
The one-part curable composition according to any one of claims 1 to 5, wherein the one-part curable composition contains from 20 to 20 parts by weight. 7. A one-pack type sealing material composition for buildings, which is prepared by dehydrating the one-pack type curable composition according to claim 1.