JP2011153249A - Curable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To keep fine view of a coated film for a long term by improving stain resistance of the overcoated coating with a low modulus curable composition usable as a construction sealant. <P>SOLUTION: There is provided a curable composition comprising (A) an organic polymer having an reactive silicon group, (B) a curing catalyst and (C) a filler and having a 100% modulus of ≤0.4 MPa based on the H-type tension test defined in JIS A1439 and giving cured products having ≥80% gel fraction. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  More specifically, the present invention relates to a sealing material with improved paint contamination, characterized by containing an organic polymer containing a reactive silicon group, a filler, and a curing catalyst. Despite the low modulus of this cured product, the contamination of the paint is improved.

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

  Among these organic polymers containing reactive silicon groups, the main chain skeleton is already a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a poly (meth) acrylate copolymer. Industrially produced and widely used in applications such as sealing materials, adhesives and paints.

  Above all, the market share has been increased for more than 20 years for architectural sealant applications. In particular, in a building using an aluminum panel such as a high-rise building, the panel expands and contracts due to the outside air temperature. The sealing material is used to prevent air and moisture from entering the building, so it is necessary to follow the movement of joints. In joints with large fluctuations, the cured sealing material takes strength at the bonding interface with the base material when stretched, and when the strength is high, the interface breaks down, leading to an accident such as water leakage. In order to prevent this, a curable composition whose cured product is designed to have flexibility and low modulus so as to meet the 25LM category of JIS A1439 type F has been used for joints with large fluctuations. . In order to lower the modulus, adjustments have been made by reducing the rate of introduction of reactive silicon groups into the organic polymer, increasing the relative amount of plasticizer relative to the organic polymer, and the like.

  In recent years, when a building is renovated, a coating material is sometimes applied to a sealing material cured together with an outer wall, and a problem that a coating film on the sealing material becomes dirty has been raised. As a method for solving these problems, Patent Document 1 proposes to use a high molecular weight plasticizer. Patent Document 2 proposes a method using a polyether having one end of a molecular chain blocked with an organic group and a reactive silicon group at the other end instead of a low molecular plasticizer, In Patent Document 3, a polyether having a high molecular weight and a high content of reactive silicon groups per molecule is added to a polyether having a low molecular weight and a low content of reactive silicon groups per molecule. A method of using both is proposed. However, although these methods can improve paint contamination, there are many kinds of paints, and they are not effective for all paints.

Japanese Patent Laid-Open No. 01-279958 Japanese Unexamined Patent Publication No. 04-057850 JP 09-095619 A

  An object of the present invention is to provide a curable composition that can be used mainly as a sealing material for construction, and has a low modulus, but has been solved for contamination to paints. .

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the curable composition is designed to have a low modulus and the gel fraction of the cured product is 80% or more. For the first time, it was found that there was little contamination of the coating film when a water-based emulsion paint that was easily soiled was applied, and the present invention was completed.

That is, the present invention
(A) an organic polymer containing a reactive silicon group, (B) a curing catalyst, (C) a filler, and a 100% modulus in an H-type tensile test prescribed in JIS A1439 is 0.4 MPa or less, And it is related with the curable composition characterized by the gel fraction of hardened | cured material being 80% or more.
In the present invention, the gel fraction of the cured product is preferably 85% or more.
In the present invention, the curing catalyst of component (B) is preferably one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acids, amine compounds, and organotins.
In the present invention, the component (A) is preferably any one or more of a polyoxyalkylene polymer, a polyacrylic polymer, and a hydrocarbon polymer.
In the present invention, the main chain of the component (A) is preferably a polyoxyalkylene polymer.
Further, in the present invention, the component (A) contains (D) an organic polymer containing 0.5 or more and less than 1.2 reactive silicon groups on average per molecule. preferable.
In the present invention, the organic polymer as the component (D) is preferably a polyoxyalkylene polymer.
In the present invention, the reactive silicon group of component (D) is preferably a trialkoxysilyl group.
In the present invention, the reactive silicon group of component (D) is preferably a triethoxysilyl group.
Moreover, it is preferable that this invention further contains the particulate matter of true specific gravity 0.01 or more and less than 0.5 as (E) component.
In the present invention, the curing catalyst of component (B) is preferably a carboxylic acid metal salt and / or an amine compound.
In the present invention, the curing catalyst of component (B) is preferably tin carboxylate.
The present invention also relates to a cured product obtained by curing the curable composition.
Moreover, this invention relates to the construction method which apply | coats the water-based acrylic coating to the surface, after constructing and hardening | curing the said curable composition.

  The curable composition of the present invention has good workability, and when cured, the cured product has flexibility and low modulus, and when a coating is applied on the cured product, the coating film However, it is useful as a curable composition that does not get dirty for a long time and maintains its aesthetic appearance.

  The present invention comprises (A) an organic polymer containing a reactive silicon group, (B) a curing catalyst, and (C) a filler. The 100% modulus in the H-type tensile test defined in JIS A1439 is 0. 4 MPa or less, and the gel fraction of the cured product is 80% or more.

  In order to evaluate the tensile properties of a cured product such as a sealing material, a so-called H-type test body sandwiched between two aluminum plate base materials, a sheet-shaped test body having a thickness of about 2 to 4 mm, a dumbbell type or a strip type For example, a method of pulling a test specimen punched into a sheet is known. These differ in the value of the modulus, which is the tensile stress, because the cross-sectional area and the stretching speed of the specimen during stretching are different. In the present invention, the modulus value in the H-type test body defined in JIS A1439 which describes the evaluation method of the sealing material for building is adopted.

  Sealing materials are available in high modulus, medium modulus, and low modulus depending on the application. Especially when used in locations where joint movement is large in architectural sealing materials, adhesion to the joint is ensured. Those are preferably used. JIS A5758 defines the type of architectural sealant, and the present invention relates to type F class 25LM applications, and the 100% modulus needs to be 0.4 MPa or less.

  In the present invention, it has been found that if the gel fraction of the cured product is 80% or more, it is difficult to get dirty even if a paint is applied on the surface of the cured product. The value of the gel fraction is a value obtained by the method described in the Examples section. The value of the gel fraction is preferably 80% or more, more preferably 85% or more, and most preferably 90% or more.

  The organic polymer (A) used in the present invention can be any polymer as long as it contains a reactive silicon group in the molecule. Such a polymer is preferably at least one polymer selected from polyoxyalkylene polymers, polyacrylic polymers, and hydrocarbon polymers. Among these, a polyoxyalkylene polymer is more preferable in that the glass transition temperature is relatively low and the obtained cured product is excellent in cold resistance.

  The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit or may contain other repeating units. Examples of the repeating unit include repeating units derived from ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide and the like. In particular, a polymer containing propylene oxide as a main component and containing propylene oxide units of 80% by weight or more, preferably 90% by weight or more is preferable because it is amorphous or has a relatively low viscosity.

  As a method for synthesizing a polyoxyalkylene polymer, for example, a polymerization method using an alkali catalyst such as KOH, a transition such as a complex obtained by reacting an organoaluminum compound and a porphyrin as disclosed in JP-A-61-215623. Polymerization by metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Examples include a polymerization method using a double metal cyanide complex catalyst shown in Japanese Patent No. 3427335, a polymerization method using phosphazene shown in Japanese Patent Application Laid-Open No. 11-60723, and the double metal cyanide complex catalyst for reasons such as production cost. The polymerization method by is preferred.

  The reactive silicon group contained in the organic polymer (A) containing a reactive silicon group has a hydroxyl group bonded to a silicon atom or a hydrolyzable group and forms a siloxane bond by a reaction catalyzed by a curing catalyst. This is a group that can be crosslinked. A typical example is represented by the following general formula (1).

(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and α-haloalkyl groups having 1 to 10 carbon atoms. Or triorganosiloxy represented by R ′ ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′s may be the same or different). When two or more R ¹ or R ² are present, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and two or more X are present. And they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2. m number of the following general formula (2)

B in the group represented by the above need not be the same. m shows the integer of 0-19. However, a + (sum of b) ≧ 1 is satisfied. ).

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

  The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and a + (sum of 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 may be one or two or more. In the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms. The following general formula (3)

A reactive silicon group represented by the formula (wherein R ¹ and X are the same as described above, and a is an integer of 1, 2 or 3) is preferable from the viewpoint of easy availability.

Specific examples of R ¹ and R ² in the above chemical formula include, for example, alkyl groups such as methyl and ethyl groups, cycloalkyl groups such as cyclohexyl groups, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, α An α-chloroalkyl group such as a chloromethyl group, and a triorganosiloxy group represented by R ′ ₃ SiO— in which R ′ is a methyl group, a phenyl group, or the like. Among these, a methyl group is preferable because the balance between curability and stability of the polymer is good, and an α-chloromethyl group is preferable because the curing rate of the cured product is particularly high. Among these, a methyl group is particularly preferable because of availability.

  Specific examples of the reactive silicon group include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, α-chloro Examples thereof include a methyldimethoxysilyl group and α-chloromethyldiethoxysilyl.

  As the number of hydrolyzable groups bonded to the silicon atom, particularly the same silicon atom, increases the reactivity of the reactive silicon group, the curing rate of the curable composition increases, The elongation at break tends to decrease. For example, trimethoxysilyl groups are more reactive than dimethoxymethylsilyl groups, and organic polymers containing trimethoxysilyl groups are more reactive and faster than organic polymers containing dimethoxymethylsilyl groups. The elongation at break of the object tends to be small. By using an organic polymer containing a trimethoxysilyl group, or by combining an organic polymer containing a trimethoxysilyl group and an organic polymer containing a dimethoxymethylsilyl group, a curable composition having a high curing rate can be obtained. Obtainable. Moreover, a curable composition having a high curing rate can also be obtained by introducing both groups into the same organic polymer. The amount of highly reactive organic polymer such as an organic polymer containing a trimethoxysilyl group, the ratio of both groups in the same organic polymer, etc. can provide the desired elongation at break and cure rate of the cured product. As appropriate.

  Introduction of the reactive silicon group can be performed by a known method. That is, the organic polymer having a functional group such as an unsaturated group such as a hydroxyl group or vinyl group, an epoxy group or an isocyanate group in the molecule has a functional group and a reactive silicon group that are reactive with the functional group. The compound is reacted. For example, the following methods are mentioned.

(B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Next, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation. In particular, a hydroxyl group-terminated oxypropylene polymer obtained using a _double metal cyanide complex catalyst such as zinc hexacyanocobaltate is alkoxylated and then reacted with allyl chloride to form an allyloxy (CH ₂ ═CHCH ₂ O—) group-terminated oxypropylene. There is a method of producing a polymer and hydrosilylating it by reacting a silane compound such as dimethoxymethylsilane. Alternatively, after hydroxylating the hydroxyl group-terminated oxypropylene polymer, it can be reacted with methallyl chloride to produce a methallyloxy group-terminated oxypropylene polymer and hydrosilylated by the action of a silane compound such as dimethoxymethylsilane. When a methallyloxy (CH ₂ ═C (CH ₃ ) CH ₂ O—) group-terminated oxypropylene polymer is used, a polymer having a higher silylation rate than an allyloxy group-terminated polyoxypropylene polymer can be obtained. The curable composition using can give a cured product having high mechanical strength. The polymer containing a reactive silicon group derived from a methallyloxy group-terminated oxypropylene polymer can be used by mixing with a polymer containing a reactive silicon group derived from an allyloxy group-terminated oxypropylene polymer.

  (B) An organic 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) An organic 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, among the methods (a) and (c), the method of reacting a polymer having a hydroxyl group with a compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. It is preferable because a high conversion rate can be obtained. Furthermore, the organic polymer having a reactive silicon group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c), The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

  Of the methods (a) and (b), a method in which a compound having a reactive silicon group is reacted at the end of the organic polymer is preferable.

  The organic polymer (A) containing a reactive silicon group may be linear or branched. If the molecular weight is the same, the use of a linear organic polymer increases the elongation at break of the cured product compared to the branched organic polymer, but increases the viscosity of the composition before curing. It tends to be difficult to handle. The lower limit of the number average molecular weight of the organic polymer (A) is preferably 10,000. The upper limit is preferably 50,000, more preferably 30,000, and even more preferably 25,000. When the number average molecular weight is less than 10,000, the elongation property at break of the cured product of the obtained reactive silicon group-containing organic polymer is deteriorated, and when it exceeds 50,000, the crosslinkable functional group concentration (reactive silicon group concentration). ) Is too low, the curing rate is slow, and the viscosity of the organic polymer tends to be too high, making it difficult to handle.

  The number average molecular weight of the organic polymer (A) containing a reactive silicon group can be directly determined by titration analysis based on the principle of the hydroxyl value measurement method of JISK1557 and the iodine value measurement method defined in JISK0070. The molecular weight (terminal molecular weight) corresponding to the number average molecular weight obtained by measuring the terminal group concentration and taking into consideration the structure of the organic polymer (branching degree determined by the polymerization initiator used) was defined. As a relative measurement method of the number average molecular weight of the organic polymer (A), a calibration curve of the number average molecular weight in terms of polystyrene (GPC molecular weight) obtained by general GPC measurement of the organic polymer precursor and the above end group molecular weight is prepared. In addition, the GPC molecular weight of the organic polymer (A) can be obtained by converting it into a terminal group molecular weight.

  The number of reactive silicon groups in the organic polymer (A) is 1.2 or more on average in one molecule of the polymer, but 1.3 or more is preferable. The upper limit is not particularly limited, but is preferably 3.0 or less, more preferably 2.4 or less, and even more preferably 2.1 or less. If the number of reactive silicon groups contained in the molecule is less than 1.2 on average, the curability is insufficient, and if it is too large, the network structure becomes too dense to exhibit good mechanical properties. .

The average number of reactive silicon groups in the organic polymer (A) in the present invention is the average number obtained by a method of quantifying protons on carbon directly bonded with reactive silicon groups by a high resolution ¹ H-NMR measurement method. It is defined as In the calculation of the average number of reactive silicon groups in the organic polymer (A) in the present invention, when the reactive silicon group is introduced into the organic polymer precursor before introducing the reactive silicon group, Organic polymer (A) having the same main chain structure with respect to an organic polymer precursor in which no group is introduced and a modified product of an organic polymer precursor in which no by-product reactive silicon group is introduced As a part of the component, the calculation is performed by including in the parameter (number of molecules) when calculating the average number of reactive silicon groups in one molecule.

  The reactive silicon group of the organic polymer (A) may exist as a side chain inside the molecular chain or may exist at the terminal, but when the reactive silicon group exists as a side chain, finally Since the amount of effective network chain contained in the cured product to be formed becomes small, it becomes easy to obtain a rubber-like cured product having a high elastic modulus and low elongation at break. On the other hand, if a reactive silicon group is present near the end of the molecular chain, the amount of effective network chain contained in the finally formed cured product increases, so that the rubber exhibits high strength, high elongation at break and low elastic modulus. It becomes easier to obtain a cured product. In particular, when a reactive silicon group is present at the end of a molecular chain, the amount of effective network chain contained in the finally formed cured product is the largest, so that the tensile properties are large in elongation at break and flexible rubber elasticity. It becomes easy to obtain a rubber-like cured product having it, which is suitable for use as a sealant for a building.

  Regarding the introduction of reactive silicon groups into the polyoxyalkylene polymer, JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, 55-13767, Those proposed in publications such as US Pat. Nos. 55-13468, 57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. Number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less proposed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, and JP-A-61-218632 Reaction of dimethoxymethylsilyl group, etc. with high molecular weight and narrow molecular weight distribution by hydrosilylation, etc. And those which introduce a gender silicon group, those proposed in JP-A-3-72527 can be exemplified.

  In the present invention, (A) the organic polymer containing a reactive silicon group further comprises (D) an organic polymer containing 0.5 or more and less than 1.2 reactive silicon groups on average per molecule. It is preferable to contain a coalescence.

  Moreover, the organic polymer of (D) component can use the thing similar to the organic polymer mentioned by the organic polymer (A), Among these, a polyoxyalkylene type polymer is preferable. Furthermore, as the reactive silicon group of the component (D), the same reactive silicon group as mentioned in the organic polymer (A) can be used, among which a trialkoxysilyl group is preferable, and a triethoxysilyl group is preferred. Is more preferable.

  (D) As a polyoxyalkylene polymer containing 0.5 or more and less than 1.2 reactive silicon groups on average per molecule of component, polyoxyethylene, polyoxypropylene, polyoxybutylene, Examples include polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Of these, polyoxypropylene is preferred.

  The polyoxyalkylene polymer as the component (D) works like a plasticizer in the organic polymer (A) containing a reactive silicon group. The lower limit of the number average molecular weight is preferably 3000, and more preferably 5000. The upper limit is preferably 20,000, and more preferably 15,000. If the molecular weight is too low, only the reactive plasticizers react with each other to produce a relatively low molecular weight condensate of the reactive plasticizer or unreacted reactive plasticizer due to heat or rain. It becomes easy to cause the contamination around the sealing joint, and after the coating material is applied to the surface of the sealing material. On the other hand, if the molecular weight is too high, the viscosity becomes high and the workability tends to be poor. The number average molecular weight is a molecular weight corresponding to the number average molecular weight obtained by the end group analysis, similarly to the molecular weight used for the organic polymer (A), and is measured by the same method as used for the organic polymer (A). I can do it.

  The molecular weight distribution Mw / Mn of the polyoxyalkylene polymer as the component (D) is preferably smaller from the viewpoint of reducing the viscosity, and is preferably 1.6 or less, and more preferably 1.5 or less. The molecular weight distribution (Mw / Mn) is measured using GPC (polystyrene conversion).

  The polyoxyalkylene polymer as component (D) may be produced by a polymerization method using a normal caustic, but is produced by a polymerization method using a double metal cyanide complex such as zinc hexacyanocobaltate as a catalyst. Can also be used.

  The reactive silicon group of the polyoxyalkylene polymer of component (D) has an average of 0.5 or more and 1.2 in one molecule of the polymer, but the upper limit is preferably 1.1, and the lower limit is 0.7 is preferable. When the average number of reactive silicon groups is less than 0.5, the tendency of the coating film to become dirty tends to be poor, and when it exceeds 1.2, the elongation of the cured product tends to decrease, It is not preferable.

  The amount of the polyoxyalkylene polymer used as the component (D) is preferably 5% by weight, more preferably 10% by weight, based on the total weight of the organic polymer (A) containing a reactive silicon group, and 20 More preferred is weight percent. The upper limit is preferably 60% by weight, and more preferably 50% by weight. If it is less than 5% by weight, the effect of lowering the modulus is difficult to be exhibited, and if it exceeds 60% by weight, the mechanical strength of the cured product tends to be insufficient. In addition, what is necessary is just to mix | blend these polyoxyalkylene type polymers, when manufacturing a curable composition. Moreover, it is also possible to mix and mix in advance with the organic polymer (A) or other compounding agents.

  In the curable composition of the present invention, the number average molecular weight of the polyoxyalkylene polymer as the component (D) is preferably smaller than that of the organic polymer (A) from the viewpoint of the effect of reducing the viscosity, and the organic polymer (A It is preferable from the viewpoint of workability at a low temperature of the composition that the number average molecular weight of

  The curing catalyst (B) used in the present invention is preferably one or more compounds selected from carboxylic acids, carboxylic acid metal salts, amine compounds, and organic tins. Further, a curing catalyst comprising a carboxylic acid metal salt and an amine compound or tin carboxylate is more preferable.

  Carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid , Linear saturated fatty acids such as palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, mellicic acid, and laccellic acid; undecylenic acid, lindelic acid, tuzuic acid Monoenes such as phyzeteric acid, myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, asclepinic acid, vaccenic acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, ceracoleic acid, ximenoic acid, lumenic acid Unsaturated fatty acids; linoleic acid, 10, 12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13-docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18-eicosapentaenoic acid, Polyene unsaturated fatty acids such as sardine acid, nisinic acid, docosahexaenoic acid; branched fatty acids such as isoacid, anteisoic acid, tuberculostearic acid, pivalic acid, 2-ethylhexanoic acid, neodecanoic acid, versatic acid; Fatty acids having triple bonds such as acid, stearoleic acid, crepenic acid, ximenic acid, 7-hexadesinic acid; naphthenic acid, malic acid Alicyclic carboxylic acids such as valic acid, sterlic acid, hydnocarbic acid, sorghumulinic acid, gorulinic acid; sabinic acid, 2-hydroxytetradecanoic acid iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettol Oxygen such as acid, alluric acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid, cerebronic acid Fatty acids: Dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid and the like. Among these, caprylic acid, 2-ethylhexanoic acid, and versatic acid are preferable in view of availability and catalyst activity.

  The carboxylic acid metal salt is a metal salt of the aforementioned carboxylic acid, for example, calcium salt, vanadium salt, iron salt, titanium salt, potassium salt, barium salt, manganese salt, nickel salt, cobalt salt, zirconium salt, tin salt. Lead salts, bismuth salts, hafnium salts, cerium salts and the like. Among these, tin salts, bismuth salts, and zirconium salts are preferable from the viewpoint of availability and catalytic activity, and carboxylic acid tin salts are particularly preferable from the viewpoint of balance between mechanical properties of the cured product and no coloring. Further, among carboxylic acid tin salts, versatic acid tin salt, 2-ethylhexanoic acid tin salt, neodecanoic acid tin salt, and vivalic acid tin salt are more preferable because of their high curing speed and little coloration of the cured product.

  Amine compounds include butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, 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). Of these, laurylamine and diethylaminopropylamine are preferred in view of availability and catalytic activity.

  Examples of organotin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethylmaleate, dibutyltin diethyl maleate, dibutyltin dibutylmaleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl maleate , Dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutyltin oxide, dibutyltin diacetylacetonate, dioctyltin diacetylacetonate, dibutyltin Diethyl acetoacetonate, dibutyls The reaction product of oxide and phthalic acid esters, such as tetravalent tin compound in the reaction products of a dibutyltin oxide and a silicate. These compounds (B) may be used alone or in combination of two or more.

  The amount of the curing catalyst (B) used is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group. . If it is less than 0.1 parts by weight, the curing rate tends to be slow, and the curing reaction tends not to proceed sufficiently. On the other hand, if it exceeds 20 parts by weight, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

  Examples of the filler (C) used in the present invention include fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and reinforcing filler such as carbon black; Calcium, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA Examples thereof include fillers such as powders such as resin powders; fibrous fillers such as asbestos, glass fibers and filaments. When the filler is used, the amount used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the organic polymer (A) containing a reactive silicon group.

  To obtain a cured product with low strength and high elongation at break, a filler selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, balloons, etc. If it is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the organic polymer containing a functional silicon group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases.

  When you want to obtain a cured product with relatively high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface A filler selected from treated fine calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and in the range of 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group. Preferred results are obtained when used.

  Of course, these fillers may be used alone or in combination of two or more. Fatty acid surface-treated colloidal calcium carbonate can be used in combination with calcium carbonate having a particle size of 1 μm or more, such as heavy calcium carbonate that has not been surface-treated.

  The curable composition of the present invention preferably contains a particulate material (E) having a true specific gravity of 0.01 or more and less than 0.5. The lower limit of true specific gravity is preferably 0.02, and the upper limit is preferably 0.4. If it is less than 0.01, there is a possibility of inhaling at the time of measurement and causing health damage or a measurement error in blending. If it exceeds 0.5, the contribution to weight reduction of the curable composition is small. This is because a large amount of use is required.

  Examples of the particulate matter (E) include balloons, volcanic ash, sand represented by yellow sand, soot, dust, sea salt and the like.

  The balloon referred to here is a spherical filler with a hollow inside. Examples of the material for the balloon include inorganic materials such as glass, shirasu, and silica, and organic materials such as phenol resin, urea resin, polystyrene, saran, and acrylonitrile, but are not limited thereto. An inorganic material and an organic material can be combined or laminated to form a plurality of layers. An inorganic or organic balloon or a combination of these can be used. The balloons used may be the same balloon or a mixture of different types of balloons. Furthermore, the balloon can be used by processing or coating the surface thereof, or can be used by treating the surface with various surface treatment agents. For example, an organic balloon may be coated with calcium carbonate, talc, titanium oxide, or the like, or an inorganic balloon may be surface treated with a silane coupling agent. The particle size of the balloon is preferably 3 to 200 μm, and particularly preferably 10 to 110 μm. If the thickness is less than 3 μm, the contribution to weight reduction is small, so a large amount of addition is necessary, and if it is 200 μm or more, the surface of the cured sealing material tends to be uneven or the elongation tends to decrease.

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

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

  The amount of the particulate material (E) used is preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. The lower limit is more preferably 0.1 parts by weight, and the upper limit is more preferably 20 parts by weight. If it is less than 0.01 part by weight, there is no workability improvement effect, and if it exceeds 30 parts by weight, the elongation and breaking strength of the cured product tend to be low.

  The curable composition of the present invention preferably contains at least one compound selected from a photocurable compound and an oxygen curable compound as a surface modifier for the cured product.

  When a photocurable compound is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less. Specifically, for example, a special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups In addition, a compound containing an average of 3 or more functional groups per molecule is preferable (all Aronix is a product of Toagosei Co., Ltd.). Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  The amount of the photocurable compound used is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group. preferable. If the amount is 0.01 parts by weight or less, the effect of increasing the weather resistance is small.

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

  The curable composition of the present invention preferably contains an epoxy compound for the restorability of the cured product. The epoxy compound is not particularly limited as long as it has an epoxy group. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. In order to improve the restoring property of the cured product, it is particularly preferable to use a compound having one epoxy group in the molecule. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group.

  You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethyl Examples include alkoxysilanes having a functional group such as toxisilane; silicone varnishes; polysiloxanes.

In particular, a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product. Particularly preferred are compounds that produce trimethylsilanol. As a compound which produces | generates the compound which has a monovalent silanol group in a molecule | numerator by hydrolysis, the compound described in Unexamined-Japanese-Patent No. 5-117521 can be mention | raise | lifted. Further, compounds that are derivatives of alkyl alcohols such as hexanol, octanol, decanol, and the like, that generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylol described in JP-A-11-241029 Examples thereof include a compound of a polyhydric alcohol having 3 or more hydroxyl groups such as propane, glycerin, pentaerythritol or sorbitol, which generates a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis.

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

  By using the physical property modifier, the hardness when the composition used in the present invention is cured can be increased, or conversely, the hardness can be decreased and elongation at break can be produced. The said physical property modifier may be used independently and may be used together 2 or more types.

  The physical property modifier is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) containing a reactive silicon group. .

  A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is preferably used in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer containing a reactive silicon group.

  An antioxidant (antiaging agent) can be used in the curable composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group. 5 parts by weight.

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

When a photocurable substance is blended in the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 119FL (all are manufactured by Ciba Japan Co., Ltd.); Light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

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

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

  In the curable composition of the present invention, components such as a curing catalyst, a filler and a plasticizer are blended separately as a curing agent, and the organic polymer (A) containing the compounding material and a reactive silicon group is used before use. Can be prepared as a two-component type to be mixed. Moreover, all the compounding components can be preliminarily blended and stored, and prepared as a one-component type that is cured by moisture in the air after construction.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is of a two-component type, it is not necessary to add a curing catalyst to the main ingredient containing the polymer (A) having a reactive silicon group, so that the compounding agent contains some moisture. However, there is little concern about gelation, but when long-term storage stability is required, dehydration and drying are preferred. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a reactive silicon group. The range of 0.5 to 10 parts by weight is more preferable.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

Example 1
Made by Kaneka Co., Ltd., trade name "Kaneka MS Polymer S810" 100 parts by weight, polymer B: a polyoxypropylene polymer having a number average molecular weight of 8000 and having a reactive silyl group only at one end of the molecule, 80 parts by weight of polyoxypropylene polymer containing 0.8 dimethoxymethylsilyl groups in one molecule, 130 parts by weight of colloidal calcium carbonate (product name “Shiraka Hana CCR-B” manufactured by Shiroishi Kogyo Co., Ltd.), heavy Quality calcium carbonate (Shiraishi Calcium Industry Co., Ltd., trade name “Whiteon SB”) 70 parts by weight, Epoxy plasticizer (New Nippon Rika Co., Ltd., trade name “E-PS”) 25 parts by weight, sagging prevention 5 parts by weight (trade name “Disparon # 308” manufactured by Enomoto Kasei Co., Ltd.), 1 part by weight of UV absorber (trade name “Tinuvin 326” manufactured by Ciba Japan Co., Ltd.), light stabilizer (Sankyo) Lifetech Co., Ltd., trade name "Sanol LS770" 1 part by weight, surface modifier (Toagosei Co., Ltd., trade name "Aronix M-309") 3 parts by weight, micro balloon (Matsumoto Yushi Seiyaku Co., Ltd.) ), Trade name "Microsphere MFL-80GCA") 10 parts by weight, titanium oxide (Ishihara Sangyo Co., Ltd., trade name "Taipeku R-820") 5 parts by weight, and knead well with three paint rolls After that, 3 parts by weight of tin octylate and 0.6 part by weight of laurylamine were added as a curing catalyst and kneaded uniformly to obtain a curable composition.

(Example 2)
In Example 1, instead of using the polymer B, the polymer C: a polyoxypropylene polymer having a number average molecular weight of 8000 and having a reactive silyl group only at one end of the molecule, A curable composition was obtained in the same manner as in Example 1 except that 80 parts by weight of a polyoxypropylene polymer containing 8 trimethoxysilyl groups was used.

(Example 3)
In Example 1, instead of using the polymer B, the polymer D: a polyoxypropylene polymer having a number average molecular weight of 8000 and having a reactive silyl group only at one end of the molecule, A curable composition was obtained in the same manner as in Example 1 except that 80 parts by weight of a polyoxypropylene polymer containing 8 triethoxysilyl groups was used.

Example 4
In Example 1, instead of using the MS polymer S810, a polymer A: a polyoxypropylene polymer having a number average molecular weight of 26000 and containing 2.1 dimethoxymethylsilyl groups in one molecule was used. A curable composition was obtained in the same manner as in Example 1 except that parts by weight were used.

(Comparative Example 1)
In Example 1, instead of using the polymer B, Example 1 except that 80 parts by weight of a polypropylene glycol plasticizer having a number average molecular weight of 12000 (manufactured by Bayer Co., Ltd., trade name “Acclaim11200”) is used. In the same manner, a curable composition was obtained.

(Comparative Example 2)
In Example 1, instead of using the polymer B, the same procedure as in Example 1 was conducted except that 80 parts by weight of a phthalate plasticizer (product name “DINP” manufactured by J Plus Co., Ltd.) was used. Thus, a curable composition was obtained.

(Comparative Example 3)
In Example 4, instead of using the polymer B, a curable composition was obtained in the same manner as in Example 4 except that 80 parts by weight of a phthalate ester plasticizer was used.

This curable composition was evaluated by the following method, and the results are shown in Table 1.
(1) The paint contamination was evaluated by the following method. Each curable composition was used to prepare a sheet having a thickness of 3 mm, left at 23 ° C. for 3 days, and then cured at 50 ° C. for 4 days. A water-based acrylic emulsion paint (manufactured by SK Kaken Co., Ltd., trade name “please coat”) was applied to the surface of this sheet, and was further allowed to stand at 23 ° C. for 7 days. Thereafter, 67 black made by Shinto Porcelain Co., Ltd. was used as silica sand, and the sample surface was uniformly applied. After 3 hours, the state when the silica sand was lightly wiped with a brush was observed, and the results were expressed by a six-step evaluation. Good (no silica sand sticking) 6 points → Bad (many sticks on one side): 1 point.
(2) The gel fraction was evaluated by the following method. Each curable composition was allowed to stand at 23 ° C. for 3 days and then cured at 50 ° C. for 4 days. A small piece of the cured product was placed in a wire mesh and immersed in acetone at 23 ° C. for 3 days. Subsequently, the cured product residue in a state where it was taken out from acetone and contained in a wire mesh was placed in a dryer at 105 ° C. for 2 hours to evaporate the acetone, and the weight was measured. The weight after immersion in acetone relative to the initial weight was calculated and determined as the gel fraction.
(3) Viscosity was measured with a BS type viscometer and a rotor No. 7 was measured under the conditions of 23 ° C. and 50% RH.
(4) The tensile properties were evaluated by the following method based on JIS A1439. A primer (manufactured by Yokohama Rubber Co., Ltd., No. 40) was applied twice to the anodized aluminum base and allowed to stand for 30 minutes to 1 hour, after which the curable composition was 12 × 12 × between the two aluminum bases. The specimen was filled so as to have a shape of 50 mm, and a test specimen was prepared. After being allowed to stand at 23 ° C. and 50% RH for 7 days and then cured and cured at 50 ° C. for 7 days, tensile measurement was performed using an autograph manufactured by Shimadzu Corporation. The modulus when stretched 50% and 100%, and the strength and elongation at break were measured.

  The results are shown in Table 1.

  When the curable composition of the present invention is used as a sealing material, the coating material is hardly contaminated even when a water-based acrylic coating is applied to the surface of the sealing material.

  The curable composition of the present invention can be used as a sealant for buildings, ships, automobiles, roads 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. . In addition to a normal adhesive, it can be used as a contact adhesive. Furthermore, it is also useful as a food packaging material, cast rubber material, molding material, and paint.

  Moreover, in the enforcement method of this invention, after applying and sealing the sealing material which contains the said curable composition as a component, a water-based acrylic coating material is apply | coated to the surface. In the sealing material containing the curable composition as a component, the plasticizer does not flow out to the surface of the sealing material, and when the paint is applied to the surface of the sealing material, the plasticizer does not contaminate the paint.

Claims (14)

  (A) an organic polymer having a reactive silicon group, (B) a curing catalyst, (C) a filler, 100% modulus in an H-type tensile test specified in JIS A1439 is 0.4 MPa or less, and A curable composition having a gel fraction of a cured product of 80% or more.   The curable composition according to claim 1, wherein the cured product has a gel fraction of 85% or more.   The curing catalyst of component (B) is one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acids, amine compounds, and organotins, according to claim 1 or 2. Curable composition.   The main chain of the component (A) is any one or more of a polyoxyalkylene polymer, a polyacrylic polymer, and a hydrocarbon polymer, according to any one of claims 1 to 3. Curable composition.   The curable composition according to any one of claims 1 to 4, wherein the main chain of the component (A) is a polyoxyalkylene polymer.   The component (A) contains (D) an organic polymer having 0.5 to less than 1.2 reactive silicon groups on average per molecule. The curable composition in any one.   The curable composition according to claim 6, wherein the organic polymer as the component (D) is a polyoxyalkylene polymer.   The curable composition according to claim 6 or 7, wherein the reactive silicon group of the component (D) is a trialkoxysilyl group.   The reactive silicon group of (D) component is a triethoxysilyl group, The curable composition in any one of Claims 6-8 characterized by the above-mentioned.   (E) The curable composition in any one of Claims 1-9 containing the particulate matter of true specific gravity 0.01 or more and less than 0.5 as a component.   The curable composition according to any one of claims 1 to 10, wherein the curing catalyst of component (B) is a carboxylic acid metal salt and / or an amine compound.   The curable composition according to any one of claims 1 to 10, wherein the curing catalyst of component (B) is tin carboxylate.   Hardened | cured material obtained by hardening the curable composition in any one of Claims 1-12. The construction method which applies a water-system acrylic coating to the surface, after constructing and hardening | curing the curable composition in any one of Claims 1-12.