JP5295544B2 - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition securing practical stability and exhibiting high elongation with low stress without reducing adhesiveness of a cured product. <P>SOLUTION: The curable composition comprises a polyether-based polymer A having a cross-linkable reactive silicon group, a carboxylic acid alkali metal salt B containing at least one kind of metal selected among lithium and sodium, and a curing catalyst C mixed if necessary. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a polyether-based polymer 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 comprising a coalescence (A) and an alkali metal carboxylate (B).

  An organic polymer containing at least one reactive silicon group in the molecule can form a rubber-like cured product by crosslinking the reactive silicon group through hydrolysis and siloxane bond formation at room temperature due to moisture or the like. It is known to have an interesting property.

  Among these polymers having reactive silicon groups, polyether polymers and polyisobutylene polymers are disclosed in Patent Documents 1 to 7, and in particular, polyether polymers and polyisobutylene polymers are Already industrially produced, it is widely used in applications such as sealing materials, adhesives and paints.

  Among these, for example, a curable composition using a main chain of polypropylene oxide is liquid at room temperature, and has a characteristic of becoming a rubber elastic body when cured, and is widely used as a sealing material for buildings. ing.

  When the rubber elastic body as described above is used for a building application, it is necessary to follow the movement of the joint. Therefore, a rubber elastic body that generally has a low elongation and a high elongation is desired. As a method of reducing the stress, a method of reducing the content of reactive silicon groups is known, but it often causes the rubber surface to become sticky (called residual tack). This is believed to be due to the remaining molecular chains that are not involved in crosslinking.

  Further, as described in Patent Document 8, as a technique for reducing the stress and increasing the elongation of a rubber elastic body, a compound having an α, β diol structure or an α, γ diol structure in the molecule is added to the composition. Methods for doing this are known.

On the other hand, what was described in patent document 9 is mentioned as invention regarding the curable composition using the polymer which has a reactive silicon group powder, and a carboxylic acid compound. Most of the techniques described in Patent Document 9 relate to the metal atoms of Group 2 to Group 10 of the periodic table.
JP-A-52-73998 JP 05-125272 A Japanese Patent Laid-Open No. 03-72527 Japanese Patent Laid-Open No. 63-6003 JP-A 63-6041 Japanese Patent Publication No. 01-38407 Japanese Patent Laid-Open No. 08-231758 Japanese Patent Laid-Open No. 11-80533 JP 2003-206410 A

  However, the method of reducing the content of reactive silicon groups has a problem that the resilience of rubber is greatly reduced.

  The present invention provides a curable composition characterized by low stress and high elongation without deteriorating the adhesiveness of a cured product while ensuring practical restoration properties.

  As a result of examination in view of the above-mentioned present situation, among the polyether polymer (A) having a crosslinkable reactive silicon group and an alkali metal carboxylate, at least one metal selected from lithium and sodium is used. It has been found that the above problems can be solved by containing the salt (B) and, if necessary, the curing catalyst (C), and the present invention has been completed.

  The curable composition of the present invention has the effect that the cured product exhibits the physical properties of low stress and high elongation, and also exhibits physical properties that are sufficiently practical for the restorability and adhesiveness.

  The component (A) has at least one reactive silicon group on average in one molecule of the polymer. When the number of reactive silicon groups contained in one molecule is 1 or more, practically sufficient curability can be obtained. However, if the amount is too large, the crosslink density becomes too high, and there is a possibility that good mechanical properties may not be exhibited. Therefore, the number is preferably 1.1 to 5.

The main chain skeleton of the polyether polymer having at least one reactive silicon group in one molecule of the component (A) has a repeating unit represented by the following general formula (1).
—R ¹ —O— (1)
(In the formula, R ¹ represents a divalent organic group.)
R ¹ is not particularly limited as long as it is a divalent organic group, but a linear or branched alkylene group having 1 to 14 carbon atoms is preferable. More preferably, it is a C2-C4 linear or branched alkylene group.

The repeating unit represented by the general formula (1) is not particularly limited, for _{example, -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- and the like.

  The main chain skeleton of the polyether polymer may be composed of one type of repeating units represented by the general formula (1), or may be composed of two or more types of repeating units. When used for a sealing material or the like, a polymer containing propylene oxide as a main component is particularly preferable.

  The main chain skeleton of the polyether polymer may have other bonding components such as a urethane bond as long as the characteristics of the polyether polymer are not significantly impaired. Other examples of such bonding modes include ester bonds, urea bonds, carbamate bonds, sulfide bonds, disulfide bonds, and the like.

The reactive silicon group contained in the component (A) is represented by the following general formula (2).
^{_{- [Si (R 2) 2}} -a (X) a O] p -Si (R 3) 3-b (X) b (2)
(In the formula, R ² and R ³ are the same or different and are each 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 ⁴ ) _3. SiO- (R ⁴ is R ⁴ .3 pieces of a monovalent hydrocarbon group having 1 to 20 carbon atoms may be the same or different) shows a triorganosiloxy group represented by When ^two or more of R ² or R ³ are present, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more of X are present, They may be the same or different, a represents an integer of 0 to 2, b represents an integer of 0 to 3, p represents an integer of 0 to 19. p is 2 or more. in some cases, the p number _{^{- [Si (R 2) 2}} -a (X) a O] p - a in group, the In the reactive silicon group represented by the general formula (2), there is at least one hydrolyzable group or hydroxyl group represented by X. Suppose)
The alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and a cyclohexyl group.

  The aryl group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a pyrenyl group.

  The aralkyl group having 7 to 20 carbon atoms is not particularly limited, and examples thereof include a benzyl group and a phenethyl group.

  The monovalent hydrocarbon group having 1 to 20 carbon atoms is not particularly limited. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, ethynyl group, 1- Examples include propenyl group, vinyl group, allyl group, 1-methylbutyl group, 2-ethylbutyl group, cyclohexyl group, and phenyl group.

  It does not specifically limit as a hydrolysable group represented by said X, A conventionally well-known thing can be used. For example, hydrogen atom, halogen atom, alkoxy group, aryloxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group, isocyanide group, isocyanate group, And isothiocyanate groups. 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.

  The hydroxyl group or hydrolyzable group represented by X can be bonded to one silicon atom in the range of 1 to 3. Moreover, the sum total of the hydroxyl group and hydrolyzable group in the reactive silicon group represented by the general formula (2) is preferably in the range of 1 to 5. The number of silicon atoms forming the reactive silicon group may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, up to 20 silicon atoms may be used.

In the present invention, among the reactive silicon groups represented by the general formula (2), the following general formula (3)
-Si (R ³ ) _3-b (X) _b (3)
A reactive silicon group represented by the formula (wherein R ³ , X and b are the same as above) is preferably used because it is easily available.

In the component (A), the method for introducing the reactive silicon group is not particularly limited, and a known method can be used. For example, it can be introduced by the following method.
(A) A polyether 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 which are reactive with the functional group, and contains an unsaturated group. A polyether polymer is obtained, or a polyether polymer containing an unsaturated group is obtained by copolymerization with an unsaturated group-containing epoxy compound, and then the obtained polyether group containing an unsaturated group A method of hydrosilylating a polymer by reacting a hydrosilane having a reactive silicon group.
(B) A method in which a polyether 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 method in which a polyether polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group. .

  Among the 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 preferred.

  The component (A) may be linear or branched, and the molecular weight is preferably about 500 to 50,000. More preferably, it is 1000-30000.

  Specific examples of the component (A) are not particularly limited. For example, JP-B No. 45-36319, JP-B No. 46-12154, JP-A No. 50-156599, JP-A No. 54-6096 are disclosed. JP, 55-13767, JP 55-13468, JP 57-164123, JP 3-2450, U.S. Pat. No. 3,632,557, U.S. Pat. 345,053, U.S. Pat. No. 4,366,307, U.S. Pat. No. 4,960,844, etc., and JP-A 61-197631, JP-A 61-215622. A polymer having a number average molecular weight of 6000 or more and Mw / Mn of 1.6 or less disclosed in each publication such as JP-A-61-215623 and JP-A-61-218632. In and molecular weight distribution can be given a narrow polyether polymer or the like.

  The polyether polymer containing the reactive silicon group may be used alone or in combination of two or more. In addition, a polyether polymer obtained by using a vinyl polymer having a reactive silicon group in combination can also be used.

  The method for producing a polyether polymer obtained by blending the vinyl polymer containing the reactive silicon group is not particularly limited. For example, JP 59-122541 A and JP 63-112642 A1. The thing etc. which are indicated by gazette, JP, 6-172631, A, etc. can be mentioned.

  Moreover, the method of superposing | polymerizing a (meth) acrylic-ester type monomer in presence of the oxyalkylene type polymer containing the said reactive silicon group can also be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-59-168014, JP-A-60-228516, JP-A-60-228517, and the like. However, it is not limited to these.

  The alkali metal salt of the carboxylic acid component (B) contained in the curable composition of the present invention is not known in detail, but it acts as a crosslink by acting on the reactive silicon group in the polyether polymer. It is considered that the internal stress of the cured product is reduced and high elongation is exhibited by reducing the density or the carboxylic acid alkali metal salt itself acting as a plasticizer.

  Therefore, as the carboxylic acid alkali metal salt used as the component (B), those having a large number of carbon atoms in the carboxylic acid moiety, that is, carboxylic acids generally called higher fatty acids are preferred. This is because a large plasticizing effect can be expected from the long chain higher fatty acid moiety. In addition, when the carbon number of the carboxylic acid moiety is large, the entanglement between the component (B) itself and the polyether polymer acts strongly, so that bleeding to the cured product surface is inhibited and the effect lasts for a long time. .

  In the present invention, the number of carbon atoms in the carboxylic acid moiety is not limited when the plasticizing effect by the moiety itself is not particularly required, and may be 2 or more, but preferably 8 or more when the plasticizing effect is desired, 10 or more are more preferable, and 12 or more are more preferable. On the other hand, 18 or less is preferable from the viewpoint of handling and solubility in the composition.

  Moreover, it is preferable that (B) component of this invention is an alkali metal salt. In general, it is known that an alkaline earth metal salt has a lower solubility in various media because the bond between a metal ion and an anion is stronger than that of an alkali metal. Therefore, when an alkaline earth metal salt of carboxylic acid is used in the present invention, it is difficult to dissolve or disperse in the curable composition, and the desired effect may not be obtained.

  Furthermore, in the case of group 3 or later metal ions, it may be undesirable from the standpoint of availability, toxicity and cost of the metal itself.

  Further, among alkali metals, rubidium, cesium, and francium are rare metals that are present in a small amount on the earth, and thus are difficult to put into practical use from the viewpoint of cost. In general, potassium is used less industrially than sodium, and it is difficult to put it to practical use in this respect. Accordingly, lithium or sodium is preferably used as the alkali metal used in the carboxylic acid alkali metal salt of the component (B) of the present invention.

  Examples of the alkali metal carboxylate include lithium octylate, sodium octylate, lithium 2-ethylhexanoate, sodium 2-ethylhexanoate, lithium caprate, sodium caprate, lithium neodecanoate, and sodium neodecanoate. Lithium laurate, sodium urinate, lithium myristate, sodium myristate, lithium palmitate, sodium palmitate, lithium oleate, sodium oleate, lithium stearate, and sodium stearate are preferred.

  The compound (B) may be used alone or in combination of two or more. The amount of the compound (B) used is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the polyether polymer as the component (A). If the amount is less than 0.1 parts by weight, it is difficult to obtain the intended effect. If the amount exceeds 100 parts by weight, the strength and altitude of the cured product may not be practical, which is not preferable. It is more preferable to use in the range of 1 to 20 parts by weight.

  The curing catalyst for the component (C) contained in the curable composition of the present invention is not particularly limited, and a generally used silanol condensation catalyst can be used. Examples include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, dibutyltin oxide and phthalic acid Reaction products with esters, organotin compounds such as dibutyltin diacetylacetonate; organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; bismuth-tris (2- Reaction products of bismuth salts such as ethylhexoate) and bismuth-tris (neodecanoate) and organic carboxylic acids, etc .; zirconium tetraacetylacetonate, titanium tetraacetyl Chelate compounds such as setnerate; organic lead compounds such as lead octylate; organic vanadium compounds; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzyl Amine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1, Amine compounds such as 8-diazabicyclo (5,4,0) undecene-7 (DBU); or salts thereof with carboxylic acids; excess polyamines and polybasic acids And the like the reaction product of an excess polyamine and epoxy compound; et low molecular weight polyamide resin obtained. These may be used alone or in combination of two or more. Among the silanol condensation catalysts, organometallic compounds, and a combined system of an organometallic compound and an amine compound are preferable from the viewpoint of curability.

  The amount of the silanol condensation catalyst used is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyether polymer as the component (A) having the reactive silicon group. If it is less than 0.01 part by weight, the curing rate is slow, and the curing reaction does not proceed sufficiently. If it exceeds 20 parts by weight, local heat generation and foaming occur during curing, and a good cured product is obtained. Is difficult to obtain. More preferably, it is 0.1 to 10 parts by weight.

  The curable composition of the present invention may further include a dehydrating agent, a compatibilizing agent, an adhesion improving agent, a physical property adjusting agent, a storage stability improving agent, a filler, a plasticizer, an anti-aging agent, an ultraviolet ray, if necessary. Various additives such as absorbers, metal deactivators, ozone degradation inhibitors, light stabilizers, amine radical chain inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, flame retardants, antistatic agents, etc. An agent can be added as appropriate.

  The filler is not particularly limited. For example, wood powder, walnut shell powder, rice husk powder, pulp, cotton chips, mica, graphite, diatomaceous earth, white clay, kaolin, clay, talc, fumed silica, sedimentation property. Examples thereof include silica, silicic anhydride, quartz powder, glass beads, calcium carbonate, magnesium carbonate, titanium oxide, carbon black, glass balloon, aluminum powder, zinc powder, asbestos, glass fiber, and carbon fiber. These may be used alone or in combination of two or more.

  It does not specifically limit as a preparation method of the curable composition of this invention, For example, a carboxylic-acid alkali metal salt compound (B) is added to a polyether polymer (A), and heating stirring etc. are carried out as needed. It can be applied and uniformly dispersed. However, it is not necessary to make it completely uniform and transparent, and even if it is in an opaque state, a sufficient effect can be obtained if it is dispersed.

  As the above-mentioned mixing method, a mixer, three rolls, a kneader, or the like can be used. Moreover, you may use a dispersibility improving agent together as needed.

  The curable composition obtained as described above can be applied to a one-component curable composition as well as a two-component curable composition. In the case of the one-pack type, it is obtained by preparing the curable composition of the present invention in a substantially moisture-free state, and can be stored for a long time if stored in a sealed state, and quickly if exposed to the atmosphere. Curing is started from the surface.

  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 coating materials, casting materials, medical rubber materials, medical adhesives, medical equipment seal materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, coating materials, primers, electromagnetic shielding Conductive materials, heat conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and sealing materials for anticorrosion and waterproofing of 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. .

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

  In the following synthesis examples, examples and comparative examples, “part” and “%” represent “part by weight” and “% by weight”, respectively.

In the following synthesis examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (TSO-GEL H type manufactured by Tosoh Corporation) and tetrahydrofuran (THF) as a GPC solvent were used.
(Synthesis Example 1) Synthesis Example of Polyether Polymer (A-1) Having Crosslinkable Silyl Group Propylene oxide using polyoxypropylene diol having a molecular weight of about 2,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst To obtain polypropylene oxide having a number average molecular weight of about 25,500. 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. Unreacted allyl chloride was removed by vacuum devolatilization. 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 vacuum devolatilization. As a result, a bifunctional polypropylene oxide (P-1) having a number average molecular weight of about 25,500 having an allyl group at the end was obtained.

With respect to 100 parts by weight of the obtained allyl group-terminated polypropylene oxide (P-1), 1.1 parts by weight of methyldimethoxysilane and 90 ° C. for 5 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst Reaction was performed to obtain a methyldimethoxysilyl group-terminated polypropylene oxide (A-1). ^{As a} result of measurement by ¹ H-NMR, the average number of terminal methyldimethoxysilyl groups was about 1.2 per molecule.
(Synthesis example 2) Synthesis example of poly (n-butyl acrylate) polymer (A-2) having a crosslinkable silyl group In a nitrogen atmosphere, a 250 L reactor was charged with CuBr (1.09 kg), acetonitrile (11.4 kg). ), N-butyl acrylate (26.0 kg) and diethyl 2,5-dibromoadipate (2.28 kg) were added, and the mixture was stirred at 70 to 80 ° C. for about 30 minutes. To this was added pentamethyldiethylenetriamine to initiate the reaction. 30 minutes after the start of the reaction, n-butyl acrylate (104 kg) was continuously added over 2 hours. During the reaction, pentamethyldiethylenetriamine was appropriately added so that the internal temperature became 70 ° C to 90 ° C. The total amount of pentamethyldiethylenetriamine used so far was 220 g. Four hours after the start of the reaction, volatile components were removed by heating and stirring at 80 ° C. under reduced pressure. Acetonitrile (45.7 kg), 1,7-octadiene (14.0 kg) and pentamethyldiethylenetriamine (439 g) were added thereto, and stirring was continued for 8 hours. The mixture was heated and stirred at 80 ° C. under reduced pressure to remove volatile components.

  Toluene is added to this concentrate to dissolve the polymer, diatomaceous earth is added as a filter aid, aluminum silicate and hydrotalcite are added as adsorbents, and an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%) is set to an internal temperature of 100. The mixture was heated and stirred at ° C. The solid content in the mixed solution was removed by filtration, and the filtrate was heated and stirred at an internal temperature of 100 ° C. under reduced pressure to remove volatile components. Furthermore, aluminum silicate, hydrotalcite, and a heat deterioration inhibitor were added as adsorbents to this concentrate, and the mixture was heated and stirred under reduced pressure (average temperature of about 175 ° C., degree of vacuum of 10 Torr or less). Furthermore, aluminum silicate and hydrotalcite were added as adsorbents, an antioxidant was added, and the mixture was heated and stirred at an internal temperature of 150 ° C. in an oxygen-nitrogen mixed gas atmosphere (oxygen concentration 6%). Toluene is added to the concentrate to dissolve the polymer, and then the solid content in the mixed solution is removed by filtration. The filtrate is heated and stirred under reduced pressure to remove volatile matter, and a polymer having an alkenyl group. Got.

Polymer having this alkenyl group, dimethoxymethylsilane (2.0 molar equivalents relative to alkenyl group), methyl orthoformate (1.0 molar equivalents relative to alkenyl group), platinum content of platinum vinylsiloxane complex 3 wt% 150 ppm of isopropanol solution was mixed, and the mixture was heated and stirred at 100 ° C. in a nitrogen atmosphere. The disappearance of the alkenyl group was confirmed by ¹ H-NMR, and the reaction mixture was concentrated to obtain a poly (acrylic acid-n-butyl) polymer (A-2) having a dimethoxysilyl group at the terminal. The number average molecular weight of the obtained polymer (A-2) was about 26000, and the molecular weight distribution was 1.3. When the average number of silyl groups introduced per polymer molecule was determined by ¹ H-NMR analysis, it was about 1.8.

Example 1
Methyldimethoxysilyl-terminated polypropylene oxide (A-1) obtained in Synthesis Example 1, Plasticizer: DIDP (diisodecyl phthalate, manufactured by Kyowa Hakko), Filler: Baiyinhua CCR (grilled calcium carbonate, manufactured by Shiroishi Kogyo), Whiten SB (heavy calcium carbonate, manufactured by Shiroishi Kogyo Co., Ltd.), Colorant: Taipei R-820 (Titanium oxide, manufactured by Ishihara Kogyo Co., Ltd.), Sacrificial inhibitor: Disparon # 6500 (Fatty acid amide wax, manufactured by Enomoto Kasei), UV absorber: Tinuvin -327 (2,4-di-t-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, manufactured by Ciba Specialty Chemicals), light stabilizer: Sanol LS-770 (bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, Sankyo), and sodium stearate (Nacalai) Were mixed by hand according to the formulation shown in Table 1, and then passed through three paint rolls three times to obtain a sufficiently stirred mixture. In these mixtures, vinyl silane: A-171 (vinyl trimethoxysilane, manufactured by GE Toshiba Silicone), aminosilane (A-1120, manufactured by GE Toshiba Silicone), curing catalyst described in Table 1, curing catalyst: dibutyltin diacetylacetate Nart (U-220H, manufactured by Nitto Kasei) was added and thoroughly mixed by hand with a spatula to prepare a curable composition. The physical properties of the cured product are shown in Table 1.
Tensile Properties The obtained curable composition was uniformly stretched to a thickness of about 3 mm, and allowed to cure and cure by leaving still at 23 ° C. and 55% RH for 3 days and then at 50 ° C. for 4 days. The tensile properties of the obtained cured product were evaluated according to JIS K 6301. The results are shown in Table 1.
It was prepared similarly to the resilient above was punched cured product obtained by curing a No. 3 dumbbell-type in conformity with JIS K6301. A marked line with an interval of 20 mm was drawn on the resulting No. 3 dumbbell-shaped cured product, and the No. 3 dumbbell was fixed in a state where the gap between the marked lines was extended to 100 mm, and was allowed to stand at 90 ° C. for 24 hours. . After 24 hours, it was released and allowed to stand at 23 ° C. and 55% RH. The rate at which the marked line was restored after 1 hour had elapsed after release was measured and calculated as the restoration rate.

(Example 2)
In Example 2, U-220H, which is the curing catalyst in Example 1, was changed to a reaction product of dibutyltin oxide and dioctyl phthalate (# 918, manufactured by Sansha Gosei Co., Ltd., hereinafter referred to as # 918). A curable composition was prepared in the same manner as in Example 1 except that 2 parts were used, and the tensile properties and the restoration rate were measured. The results are shown in Table 1.

(Example 3)
In Example 3, U-220H, which is the curing catalyst in Example 1, was prepared by using 2.5 parts of neodecanoic acid (Versatic 10, manufactured by Japan Epoxy Resin) and 0.5 parts of N, N-diethyl-1,3-propane. A curable composition was prepared in the same manner as in Example 1 except that the mixture was changed to a mixture composed of diamine (manufactured by Wako Pure Chemical Industries, Ltd.), and the tensile physical properties and the restoration rate were measured. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, it implemented like Example 1 except not having added sodium stearate. The results are shown in Table 1.

(Comparative Example 2)
In Example 2, it implemented like Example 2 except not having added sodium stearate. The results are shown in Table 1.

(Comparative Example 3)
In Example 3, it implemented like Example 3 except not having added sodium stearate. The results are shown in Table 1.

Example 4
Methyldimethoxysilyl group-terminated polypropylene oxide (A-1) obtained in Synthesis Example 1, methyldimethoxysilyl group-terminated poly (n-butyl acrylate) polymer (A-2) obtained in Synthesis Example 2, and filler : UltraPflex (collagen calcium carbonate, manufactured by Specialty Minerals Inc.), Q3T (heavy calcium carbonate, manufactured by JM Huber Corporation), SL-150 (ceramic balloon, manufactured by envirospheres), plasticizer: DIDP (diisodecyl phthalate, Kyowa Hakko), surface modifier (Aronix M-309, manufactured by Toagosei), sagging inhibitor: Disparon # 305 (fatty acid amide wax, manufactured by Enomoto Kasei), light stabilizer: LA63P (Asahi Denka Kogyo), epoxy Resin (Epicoat-828, Bisuf Enol A-type liquid epoxy resin (manufactured by Japan Epoxy Resin) and sodium stearate according to the formulation in Table 2, and after stirring and mixing by hand, the mixture was thoroughly mixed by passing three paint rolls three times. It was. In these mixtures, the number of parts of vinylsilane described in Table 2: A-171 (vinyltrimethoxysilane, manufactured by GE Toshiba Silicones), aminosilane (A-1120, 3- (2-aminoethyl) aminopropyltrimethoxysilane) GE Toshiba Silicone), epoxy silane (A-187, 3-glycidoxypropyltrimethoxysilane, GE Toshiba Silicone), curing catalyst: neodecanoic acid (Versatic 10, Japan Epoxy Resin), laurylamine (Wako Pure) And the mixture was thoroughly mixed by hand with a spatula to prepare a curable composition. The results are shown in Table 2.
The adhesive curable composition was adhered to various adherends (anodized aluminum, SUS304, glass, PVC steel plate, hard PVC, FRP) and cured at 23 ° C. for 7 days. Then, it pulled until the hardened | cured material fractured | ruptured in the 90 degree direction, and the fracture state at that time was observed. A case where the cohesive failure rate (CF rate) was 90% or more was judged as ◎, a case where it was 50% or more and less than 90% was judged as ○, and a case where it was less than 50% was judged as ×.

  Further, the cured product produced in the same manner as described above was cured at 23 ° C. for 7 days, then immersed in pure water and cured at 50 ° C. for 7 days. Then, the water-resistant adhesiveness was evaluated by testing in the same manner as described above. A case where the cohesive failure rate (CF rate) was 90% or more was judged as ◎, a case where it was 50% or more and less than 90% was judged as ○, and a case where it was less than 50% was judged as ×.

(Comparative Example 4)
In Example 4, it implemented like Example 4 except not having added sodium stearate. The results are shown in Table 2.

  From the comparison between Example 1 and Comparative Example 1, it can be seen that when U-220H is used as a curing catalyst, the cured product becomes high elongation with low stress by adding sodium stearate. Furthermore, it can be seen that the recovery rate does not decrease while the stress is low. From the comparison between Example 2 and Comparative Example 2, it is found that the cured product becomes high elongation with low stress by adding sodium stearate even when # 918 is used as the curing catalyst. It can also be seen that the restoration rate does not decrease while the stress is low. Furthermore, from the comparison between Example 3 and Comparative Example 3, it was found that by adding sodium stearate when using a salt composed of neodecanoic acid and N, N-diethyl-1,3-propanediamine as a curing catalyst, It can be seen that the object becomes high elongation with low stress. On the other hand, it can be seen that the restoration rate does not decrease greatly while the stress is low. As described above, it can be seen that a curable composition characterized by low stress and high elongation can be obtained without reducing the restoration rate, regardless of the type of curing catalyst.

  From the comparison between Example 4 and Comparative Example 4, it can be seen that by adding sodium stearate, the cured product surely becomes high elongation with low stress. Furthermore, it turns out that the adhesiveness with respect to various to-be-adhered bodies and water-resistant adhesiveness of hardened | cured material do not change even if sodium stearate is added. As described above, according to the present invention, it can be seen that a curable composition characterized by low stress and high elongation can be obtained without reducing the adhesiveness of the cured product.

Claims (5)

A polyether polymer (A) having a crosslinkable reactive silicon group and a carboxylate (B) of at least one metal selected from lithium and sodium among alkali metal carboxylates The component (B) is selected from the group consisting of octylic acid, 2-ethylhexanoic acid, capric acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, and stearic acid. A curable composition which is a metal salt of at least one carboxylic acid . The curable composition according to claim 1, wherein the main chain of the polyether polymer (A) is polypropylene oxide. 3. The curable composition according to claim 1, wherein 0.01 to 20 parts by weight of the carboxylic acid alkali metal salt (B) is contained with respect to 100 parts by weight of the polyether polymer (A). The curable composition according to any one of claims 1 to 3 , further comprising a curing catalyst (hereinafter also referred to as a silanol condensation catalyst) as the component (C). It consists of a curable composition in any one of Claims 1-4 , The sealing material characterized by the above-mentioned.