JP5479862B2 - Curable composition - Google Patents

Description

The present invention relates to an organic polymer having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). It relates to the curable composition containing.

The organic polymer having at least one reactive silicon group in the molecule is crosslinked at room temperature by the formation of a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture, etc. It is known to have the property of being obtained.

Among these organic polymers having reactive silicon groups, polyoxyalkylene polymers, saturated hydrocarbon polymers, and poly (meth) acrylic acid ester copolymers having a main chain skeleton are already industrially used. Is widely used in applications such as sealing materials, adhesives, and paints. A curable composition containing an organic polymer having a reactive silicon group generally uses various plasticizers and diluent solvents for the purpose of imparting flexibility and ensuring good workability by reducing viscosity. Yes. However, since the most common low molecular weight plasticizers have migratory properties, when used as a sealing material, there is a problem in that it causes spillage to the surface of the sealing material and accompanying contamination around the sealing joint. In addition, when a paint is applied to the surface of the sealing material, there is also a problem that the plasticizer contaminates the paint.

As a method for solving these problems, Patent Document 1 discloses a polyether having one end of a molecular chain blocked with an organic group instead of a low molecular weight plasticizer and a reactive silicon group at the other end. A method of using is proposed. In Patent Documents 2 and 3, polyethers having a high molecular weight and a high content of reactive silicon groups per molecule are added to a polyether having a low molecular weight and a reactive silicon group content per molecule. A method of using a polyether with a small amount of polyether has been proposed. However, although these methods can improve paint stain resistance, a polyether having a high molecular weight reactive silicon group compared to a low molecular weight plasticizer is used as a reactive plasticizer. There was a problem that the viscosity increased and workability decreased.

On the other hand, Patent Document 4 proposes a method of adding a microballoon not only for the purpose of weight reduction but also for heat insulation and soundproofing. However, although the workability is mentioned, the problem is a decrease in workability due to the collapse of the balloon, and there is no mention of the extrudability and the stringiness when constructed on the ground surface. The composition contains a low-molecular plasticizer such as dioctyl phthalate, and the viscosity of the composition is inherently low, so that workability does not become a big problem.

Japanese Unexamined Patent Publication No. 04-057850 JP 09-095619 A JP 2009-108246 A WO97 / 05201 Publication

In view of the above problems, the present invention has a good workability of the composition, and the cured product has flexibility, and when the cured product is used as a sealing material, an adhesive, etc., the uncured product flows out. It is an object of the present invention to provide a curable composition containing an organic polymer having a reactive silicon group, which is less likely to cause volatilization, volatilization, contamination around the sealing joint, and coating contamination on the surface of the sealing material.

As a result of intensive studies to solve the above-mentioned problems, the inventors have increased the viscosity of the composition and reduced workability by incorporating a polymeric plasticizer having a reactive silicon group. It was found for the first time that the workability such as the stringiness could be improved if the specific gravity of the object itself was kept low, and the present invention was completed.

That is, the present invention provides an organic polymer (A) having an average of 1.2 or more reactive silicon groups per molecule and an average of 0.5 or more and less than 1.2 per molecule. A curable composition comprising a polyoxyalkylene polymer (B) having a reactive silicon group, wherein the specific gravity of the curable composition is 0.9 or more and 1.3 or less. Relates to the composition.

The organic polymer (A) is preferably a polyoxyalkylene polymer having a number average molecular weight of 10,000 or more.

The polyoxyalkylene polymer (B) is preferably a polyoxyalkylene polymer having a number average molecular weight of less than 20,000.

The polyoxyalkylene polymer (B) is preferably a polyoxyalkylene polymer having a number average molecular weight of 3000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less.

Furthermore, it is preferable that the particulate matter (C) having a true specific gravity of 0.01 or more and less than 0.5 is included.

Furthermore, it is preferable to include an organic polymer (D) having a number average molecular weight of 3000 or more and having substantially no reactive silicon group.

The number average molecular weight of the organic polymer (D) is preferably larger than that of the organic polymer (B) used.

The organic polymer (D) preferably contains at least one organic polymer selected from a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a poly (meth) acrylate copolymer.

The organic polymer (D) is preferably a polyoxyalkylene polymer having a number average molecular weight of 5000 to 25000.

Furthermore, at least one compound (E) selected from a carboxylic acid metal salt, a carboxylic acid, an amine compound, and an organotin compound is converted into an organic polymer (A) and / or a polyoxyalkylene polymer (B). ) Curing catalyst and / or as a curing accelerator.

Furthermore, it is preferable to include at least one curable compound (F) selected from an oxygen curable compound, a photocurable compound, and an epoxy compound.

The number average molecular weight of the organic polymer (A) and the polyoxyalkylene polymer (B) is preferably 5,000 or more.

The content of the polyoxyalkylene polymer (B) is preferably 5 parts by weight or more and 120 parts by weight or less with respect to 100 parts by weight of the organic polymer (A).

Moreover, this invention relates to the construction method which apply | coats the water-based acrylic coating to the surface, after constructing and hardening the sealing material which contains the said curable composition as a component.

The curable composition of the present invention has good workability of the composition, the cured product has flexibility, and when the cured product is used as a sealing material, an adhesive, etc., the uncured product flows out. It is a curable composition containing an organic polymer having a reactive silicon group, which is less likely to volatilize, volatilize, contamination around the sealing joint, and paint contamination on the surface of the sealing material.

The curable composition of the present invention comprises an organic polymer (A) having 1.2 or more reactive silicon groups on average per molecule and 0.5 or more and 1.2 on average per molecule. A curable composition comprising a polyoxyalkylene polymer (B) having less than one reactive silicon group,
The specific gravity of the curable composition is 0.9 or more and 1.3 or less.

The organic polymer (A) used in the present invention can be any polymer as long as it has an average of 1.2 or more reactive silicon groups per molecule. Examples of such polymers include polyoxyalkylene polymers, saturated hydrocarbon polymers, and poly (meth) acrylic acid ester copolymers. Among these, a polyoxyalkylene polymer is preferable in that the glass transition temperature is relatively low and the obtained cured product is excellent in cold resistance.

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

（式中、Ｒ^１およびＲ^２は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、炭素数１〜１０のα―ハロアルキル基またはＲ’_３ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であり、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ^１またはＲ^２が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｘは水酸基または加水分解性基を示し、Ｘが２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。ａは０、１、２または３を、ｂは０、１または２を、それぞれ示す。またｍ個の

(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 ′ may be the same or different). And 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 exist. And they may be the same or different, a represents 0, 1, 2 or 3, b represents 0, 1 or 2, and m

で表される基におけるｂは同一である必要はない。ｍは０〜１９の整数を示す。但し、ａ＋（ｂの和）≧１を満足するものとする。）で表わされる基があげられる。

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. In addition,

（式中、Ｒ^１およびＸは前記と同じ、ａは１、２または３の整数）で表わされる反応性ケイ素基が、入手が容易である点から好ましい。

A reactive silicon group represented by the formula (wherein R ¹ and X are the same as described above, 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 a 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, a trimethoxysilyl group is more reactive than a dimethoxymethylsilyl group, and an organic polymer having a trimethoxysilyl group is more reactive and has a higher curing rate than an organic polymer having a dimethoxymethylsilyl group. The elongation at break tends to be small. It is possible to obtain a curable composition having a high curing rate by using an organic polymer having a trimethoxysilyl group or by using an organic polymer having a trimethoxysilyl group and an organic polymer having a dimethoxymethylsilyl group in combination. it can. 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 organic polymer with high reactivity, such as organic polymer having trimethoxysilyl group, and the ratio of both groups in the same organic polymer, etc., can give the desired elongation at break and curing rate. 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 polyoxypropylene polymer obtained using a _double metal cyanide complex catalyst such as zinc hexacyanocobaltate is alkoxideized, and then reacted with allyl chloride to react with allyloxy (CH ₂ ═CHCH ₂ O—) group-terminated poly Examples thereof include a method of producing an oxypropylene polymer and hydrosilylating it by acting a silane compound such as dimethoxymethylsilane. Alternatively, after hydroxylating the hydroxyl group-terminated polyoxypropylene polymer, it can be reacted with methallyl chloride to produce a methallyloxy group-terminated polyoxypropylene polymer, and hydrosilylated with a silane compound such as dimethoxymethylsilane. When a methallyloxy (CH ₂ ═C (CH ₃ ) CH ₂ O—) group-terminated polyoxypropylene polymer is used, a polymer having a higher silylation rate than an allyloxy group-terminated polyoxypropylene polymer can be obtained. The curable composition using the coalescence can give a cured product having a large mechanical strength. The organic polymer having a reactive silicon group derived from a methallyloxy group-terminated polyoxypropylene polymer can be used by mixing with an organic polymer having a reactive silicon group derived from an allyloxy group-terminated polyoxypropylene polymer.

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

(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 main chain skeleton of the polyoxyalkylene polymer may be composed 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 mainly composed of polypropylene oxide containing propylene oxide units of 80% by weight or more, preferably 90% by weight or more is preferable from the viewpoint of being amorphous or having 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.

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. No. 4,960,844, Number average molecular weight of 6,000 or more, Mw / Mn proposed in JP-A-61-197631, JP-A-61-215622, JP-A-61-215623, JP-A-6-218632, and JP-A-3-72527 A polyoxypropylene polymer having a high molecular weight of 1.6 or less and a narrow molecular weight distribution is dimerized by hydrosilylation or the like. Which introduce a carboxy reactive silicon group such as a methyl silyl group can be exemplified. The polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.

The organic polymer (A) having a reactive silicon group may be linear or branched. If the molecular weight is the same, 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). ) Becomes too low, the curing rate decreases, and the viscosity of the organic polymer tends to be too high, making it difficult to handle. Only one type of organic polymer (A) having a reactive silicon group may be used, or a plurality of types may be used.

The number average molecular weight of the organic polymer (A) having a reactive silicon group is defined in JIS K 1557, the method for measuring the hydroxyl value of JIS K 1557, and the organic polymer precursor before the introduction of the reactive silicon group. The number average molecular weight obtained by directly measuring the end group concentration by titration analysis based on the principle of the iodine value measurement method and considering the structure of the organic polymer (the degree of branching determined by the polymerization initiator used) Is defined as the molecular weight corresponding to (end group molecular weight). As a method for measuring the number average molecular weight of the organic polymer (A), a calibration curve of polystyrene-converted number average molecular weight (GPC molecular weight) obtained by general GPC measurement of the organic polymer precursor and the above-mentioned end group molecular weight is prepared. It can be obtained by converting the GPC molecular weight of the organic polymer (A) 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) is defined as the average number obtained by a method of quantifying protons on carbon to which reactive silicon groups are directly bonded by high resolution ¹ H-NMR measurement. ing. In the calculation of the average number of reactive silicon groups in the organic polymer (A), the silicon groups are introduced when the reactive silicon groups are introduced into the organic polymer precursor before the introduction of the reactive silicon groups. The organic polymer precursor (A) having the same main chain structure is also used for the modified organic polymer precursor in which the by-product reactive silicon group is not introduced and the modified organic polymer precursor. As a part of the calculation, the average number of reactive silicon groups in one molecule is included in the population parameter (number of molecules).

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 is preferable for a sealant application of a building that it is desirable to have.

The polyoxyalkylene polymer (B) having 0.5 or more and less than 1.2 reactive silicon groups on average per molecule used in the present invention is an organic polymer (A ) As a reactive plasticizer. Examples of the polyoxyalkylene polymer (B) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer. Etc. are exemplified. Of these, polyoxypropylene is preferred.

About the number average molecular weight of a polyoxyalkylene type polymer (B), 3000 is preferable and, as for a minimum, 5000 is more preferable. The upper limit is preferably 20000, more preferably 15000. If the molecular weight is too low, the reactive plasticizer condensate or unreacted reactive plasticizer produced by reacting only the reactive plasticizers with each other will flow out over time due to heat or rain, It tends to cause contamination around the sealing joint and contamination of the paint 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 (B) is preferably smaller from the viewpoint of viscosity reduction, 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 (B) 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 average number of reactive silicon groups in the polyoxyalkylene polymer (B) is 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 0.00. Seven is preferred. 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. In addition, as a reactive silicon group of a polyoxyalkylene type polymer (B), the same thing as the reactive silicon group of the organic polymer (A) which has the said reactive silicon group can be mentioned. The average number of reactive silicon groups per molecule in the polyoxyalkylene polymer (B) is the number determined by the same method as the average number of reactive silicon groups in the organic polymer (A). Only one type of organic polymer (B) having a reactive silicon group may be used, or a plurality of types may be used.

The amount of the polyoxyalkylene polymer (B) used is preferably 5 parts by weight, more preferably 10 parts by weight, and 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. Part is more preferred. The upper limit is preferably 120 parts by weight, and more preferably 100 parts by weight. If the amount is less than 5 parts by weight, the effect as a plasticizer is hardly exhibited. If the amount exceeds 120 parts by weight, the mechanical strength of the cured product tends to be insufficient. In addition, what is necessary is just to mix | blend a polyoxyalkylene type polymer (B), 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 (B) is preferably smaller than that of the organic polymer (A) from the viewpoint of viscosity reduction effect. It is preferable from the point of workability | operativity at the low temperature of a composition that it is 1/2 or less of a number average molecular weight.

In the curable composition of the present invention, the number average molecular weight of the organic polymer (A) and the polyoxyalkylene polymer (B) is preferably 5000 or more, more preferably 7000 or more. If it is less than 5,000, there is a tendency that the paint contamination property and the contamination property around the joint are deteriorated. Although an upper limit is not specifically limited, 25000 are preferable and 20000 are more preferable. When it exceeds 25000, the viscosity tends to be high and the workability tends to be poor. Here, the number average molecular weight of the organic polymer (A) and the polyoxyalkylene polymer (B) is calculated from the combined weight and molecular weight of each mole, and the combined weight is the mole of each polymer. It is the molecular weight obtained by dividing by the sum of numbers.

The curable composition of the present invention preferably contains a particulate material (C) having a true specific gravity of 0.01 or more and less than 0.5. The lower limit of the true specific gravity is preferably 0.02, and the upper limit is preferably 0.4. If it is less than 0.01, it may be inhaled at the time of handling such as weighing, and the component (c) may be sucked to cause a health hazard or cause a weighing error in the formulation. If the ratio exceeds 0.5, the contribution to weight reduction of the curable composition is small, so a large amount of use is required.

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

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

The 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 a balloon is used, the anti-slip agent as described in JP-A No. 2000-154368 and the surface of the cured product as described in JP-A No. 2001-164237 are matted in addition to the uneven state. An amine compound, 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 (C) 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 an organic polymer (D) having a number average molecular weight of 3000 or more and having substantially no reactive silicon group from the viewpoint of economy.

Examples of the organic polymer (D) include polyoxyalkylene polymers, saturated hydrocarbon polymers, and poly (meth) acrylic acid ester copolymers. Among these, a polyoxyalkylene polymer and a poly (meth) acrylic acid ester copolymer are preferable, and a polyoxyalkylene polymer is more preferable in terms of good workability. Moreover, 5000-25000 are preferable and, as for a number average molecular weight, 10,000-20000 are more preferable. Furthermore, it is preferable that the number average molecular weight of an organic polymer (D) is larger than the organic polymer (B) to be used. Furthermore, the lower limit of the number average molecular weight is preferably 1.2 times the number average molecular weight of the organic polymer (B) used, and the upper limit is not particularly limited, but is preferably smaller than the number average molecular weight of the organic polymer (A). When the number average molecular weight of the organic polymer (B) is less than 5,000, the contamination around the joints and the paint contamination tend to deteriorate.

“Substantially having no reactive silicon group” means that it has no average of 0.1 or more reactive silicon groups per molecule.

The amount of the organic polymer (D) used is preferably 0.1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive silicon group. The upper limit is more preferably 100 parts by weight, and the lower limit is more preferably 5 parts by weight. If it is less than 1 part by weight, the workability improving effect is insufficient, and if it exceeds 200 parts by weight, the paint contamination tends to be insufficient.

The curable composition of the present invention comprises at least one compound (E) selected from a carboxylic acid metal salt, a carboxylic acid, an amine compound, and an organotin compound, an organic polymer (A) and / or a polyoxyalkylene. It is preferable to contain as a curing catalyst and / or a curing accelerator for the system polymer (B).

Carboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid , Stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicinic acid, laccellic acid and other linear saturated fatty acids; Acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclepic acid, vaccenic acid, gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, Ceracoleic acid, ximenic acid, ru Monoene unsaturated fatty acids such as citric acid; 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 Polyene unsaturated fatty acids such as 4,8,12,15,18-eicosapentaenoic acid, sardine acid, nisinic acid, docosahexaenoic acid; isoacid, antiisoic acid, tuberculostearic acid, pivalic acid, 2-ethylhexanoic acid Branched fatty acids such as neodecanoic acid and versatic acid; taliphosphoric acid, stearolic acid, crepenic acid, xymenic acid, 7-he Fatty acids having triple bonds such as oxadesic acid; alicyclic carboxylic acids such as naphthenic acid, malvalic acid, sterlic acid, hydonocarbic acid, sholmoulinic acid, gorulinic acid; sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperic acid, ambrettelic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, Examples include oxygen-containing fatty acids such as camlorenic acid, licanoic acid, ferronic acid, and cerebronic acid; and dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, and sebacic acid. 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 of 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 diethylhexanoate, dibutyltin dimethyl maleate, dibutyltin diethyl maleate, dibutyltin dibutyl maleate, 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, dibutyl Reaction products of dibutyltin oxide and phthalic acid esters, such as tetravalent tin compound in the reaction products of a dibutyltin oxide and a silicate. These compounds (E) may be used independently and may use 2 or more types together.

The amount of the compound (E) 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) having 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.

The curable composition of the present invention preferably contains at least one curable compound (F) selected from a photocurable compound, an oxygen curable compound, and an epoxy compound.

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 And a compound containing 3 or more of the same functional groups on average in one 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, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. If it is 0.01 parts by weight or less, the effect of increasing the weather resistance is small, and if it is 20 parts by weight or more, the cured product becomes too hard and cracks occur, which is not preferable.

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 by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group. Part. 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 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. For the purpose of enhancing the restorability of the cured product, it is 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) having a reactive silicon group.

In the curable composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and α-isocyanatemethyltrimethoxysilane. Isocyanate group-containing silanes such as α-isocyanatomethyldimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl)- -Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ Amino group-containing silanes such as aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane , Γ-mercaptopropylmethyldiethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- Epoxy group-containing silanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis ( 2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane and other carboxysilanes; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, Vinyl-type unsaturated group-containing silanes such as γ-acryloyloxypropylmethyltriethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; Isocyanurs such as tris (trimethoxysilyl) isocyanurate Examples thereof include rate silanes. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . The silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of organic polymer (A) which has a reactive silicon group. In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

Various fillers can be mix | blended with the curable composition of this invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, carbonic acid Filling such as resin powder such as magnesium, 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 powder Agents; fibrous fillers such as asbestos, glass fibers and filaments. When the filler is used, the amount used is 1 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the organic polymer (A) having a reactive silicon group.

When you want to obtain a hardened material with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and it is used in an amount of 1 to 200 parts by weight per 100 parts by weight of the organic polymer (A) having a reactive silicon group. Favorable results are obtained. In addition, when it is desired to obtain a cured product having a low strength and a large elongation at break, a filler mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. Is preferably used in an amount of 5 to 200 parts by weight per 100 parts by weight of the organic polymer (A) having a reactive silicon group. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. 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.

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. 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.

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 a silicon compound that generates R ₃ SiOH such as trimethylsilanol by hydrolysis, and trimethylolpropane described in JP-A-11-241029 In addition, there can be mentioned compounds that are derivatives of polyhydric alcohols having 3 or more hydroxyl groups such as glycerin, pentaerythritol and sorbitol, and which generate silicon compounds that generate 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 which can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) having 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 used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) having 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; CHIMASSORB944LD, CHIMASSORB119FL (all of which are manufactured by Ciba Japan Co., Ltd.); ADK STAB LA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, ADK STAB LA-68 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 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. 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 used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. 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 contained as a hindered amine light stabilizer as described in JP-A-5-70531. Use of a hindered amine light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all are manufactured by Ciba Japan Co., Ltd.); Adeka Stub LA-57, LA-62, LA-67, LA-63 (all above) 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 5 parts per 100 parts by weight of the organic polymer (A) having a reactive silicon group. 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.

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

When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. As the dehydration and drying method, a heat drying method is preferable 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 0.1 to 20 parts by weight, preferably 100 parts by weight of organic polymer (A) having a reactive silicon group, preferably A range of 0.5 to 10 parts by weight is preferred.

The specific gravity of the curable composition of the present invention is 0.9 or more and 1.3 or less. The lower limit is preferably 1.0, and the upper limit is preferably 1.28. If it is less than 0.9, a large amount of filler such as calcium carbonate cannot be filled, and the strength of the cured product will be low, and if it exceeds 1.3, the weight per volume is heavy, This is because there is a possibility that the sealing material hangs down when it is constructed on a vertical joint.

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 cause the plasticizer to flow out to the surface of the sealing material and the resulting contamination around the sealing joint. It does not contaminate the paint. Urethane sealants cannot be used in areas where weather resistance is an issue, but sealants containing the curable composition as a component can also be applied to areas where the weather resistance issue is not applied. It can also be used as a single sealing material for the portion where the coating is applied.

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.

(Synthesis Example 1)
Polymerization of propylene oxide was performed using polypropylene triol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-terminated polyoxypropylene polymer having a branched structure having a number average molecular weight (terminal group molecular weight) of 18,000. Subsequently, 1.2 times equivalent of a methanol solution of NaOCH ₃ with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene polymer was added to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group to an allyl group. Converted to. A 2,6 di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent were added to 2000 g of an oligomer obtained by carrying out a desalting purification treatment, and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and then purged with nitrogen. On the other hand, by adding 270 μl of an isopropanol solution of a platinum vinylsiloxane complex having a platinum content of 3% by weight and stirring, 22.0 g of dimethoxymethylsilane was reacted at 90 ° C. for 2 hours to obtain a number average molecular weight of 18000 (feeding). Tosoh HLC-8120GPC was used as the liquid system, the column was a Tosoh TSK-GEL H type, and the solvent was dimethoxymethylsilyl of the terminal group molecular weight calculated based on the polystyrene equivalent molecular weight measured using THF. A polyoxypropylene polymer having a branched structure having a group (polymer A) was obtained. As a result of measurement of ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of dimethoxymethylsilyl groups was 2.1 on average per molecule.

(Synthesis Example 2)
Polymerization of propylene oxide was performed using polypropylene glycol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a linear hydroxyl group-terminated polyoxypropylene polymer having a number average molecular weight of 14,000. Subsequently, 1.2 times equivalent of a methanol solution of NaOCH ₃ with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene polymer was added to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group to an allyl group. Converted to. A 2,6 di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent were added to 2000 g of an oligomer obtained by carrying out a desalting purification treatment, and azeotropic dehydration was performed at 90 ° C. Hexane was distilled off under reduced pressure and then purged with nitrogen. On the other hand, by adding 270 μl of an isopropanol solution of a platinum vinylsiloxane complex having a platinum content of 3% by weight and stirring, 23.0 g of dimethoxymethylsilane was reacted at 90 ° C. for 2 hours, thereby dimethoxy having a number average molecular weight of 14,000. A branched polyoxypropylene polymer (polymer B) having a methylsilyl group was obtained. ^{As a result of 1} H-NMR measurement (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of dimethoxymethylsilyl groups was 1.6 on average per molecule.

(Synthesis Example 3)
Polyoxypropylene monobutyl ether is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, has a linear structure with a number average molecular weight of 5000, one end is blocked with butyl ether, and the other end Thus, a hydroxyl group-terminated polyoxypropylene polymer having a hydroxyl group was obtained. Subsequently, 1.2 times equivalent of a methanol solution of NaOCH ₃ with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene polymer was added to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group to an allyl group. Converted to. 2,500 di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent are added to 500 g of an oligomer obtained by carrying out desalting and purification treatment, and azeotropic dehydration is performed at 90 ° C. Hexane was distilled off under reduced pressure and then purged with nitrogen. On the other hand, by adding 270 μl of an isopropanol solution of a platinum vinylsiloxane complex having a platinum content of 3% by weight and stirring the mixture, 42.0 g of dimethoxymethylsilane was reacted at 90 ° C. for 2 hours, whereby the number average molecular weight was 5000. A polyoxypropylene polymer (polymer C) having a dimethoxymethylsilyl group only at one end of a molecular chain having a chain structure was obtained. As a result of measurement of ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of dimethoxymethylsilyl groups was 0.8 on average per molecule.

(Synthesis Example 4)
Polymerization of propylene oxide was performed using polypropylene glycol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl group-terminated polyoxypropylene polymer having a number average molecular weight of 9000 and having a linear structure. Subsequently, 1.2 times equivalent of a methanol solution of NaOCH ₃ with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene polymer was added to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group to an allyl group. Converted to. 2,500 di-tert-butyl-p-cresol as an antioxidant and hexane as an azeotropic solvent are added to 500 g of an oligomer obtained by carrying out desalting and purification treatment, and azeotropic dehydration is performed at 90 ° C. Hexane was distilled off under reduced pressure and then purged with nitrogen. On the other hand, by adding 270 μl of an isopropanol solution of a platinum vinylsiloxane complex having a platinum content of 3% by weight and stirring, 20.0 g of dimethoxymethylsilane was reacted at 90 ° C. for 2 hours, thereby dimethoxy having a number average molecular weight of 9000. A branched polyoxypropylene polymer having a methylsilyl group (Polymer D) was obtained. As a result of measurement of ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of dimethoxymethylsilyl groups was 0.8 on average per molecule.

(Synthesis Example 5)
Polymerization of propylene oxide was performed using polypropylene glycol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a hydroxyl-terminated polyoxypropylene polymer having a linear structure with a number average molecular weight of 12,000. After washing with water, hexane is added as an azeotropic solvent and azeotropic dehydration is performed at 90 ° C., and hexane is distilled off under reduced pressure. The number average molecular weight is 12,000, the hydroxyl group is present, and no reactive silicon group is present. A polyoxypropylene polymer (Polymer E) was obtained.

(Synthesis Example 6)
In the same manner as in Synthesis Example 3, a polyoxypropylene polymer having a linear structure having a number average molecular weight of 5000 and having one end blocked with butyl ether and having a hydroxyl group only at one end is obtained. A 1.2-fold equivalent methanol solution of NaOCH ₃ with respect to the hydroxyl group of the propylene polymer was added to distill off the methanol, and further methallyl chloride was added to convert the terminal hydroxyl group to a methallyl group. A desalting and purification treatment was performed, 2,6 di-tert-butyl-p-cresol was added as an antioxidant, and hexane was added as an azeotropic solvent, followed by azeotropic dehydration at 90 ° C. After distilling off hexane under reduced pressure, 24.2 g of dimethoxymethylsilane is reacted with 500 g of the resulting methallyl-terminated polyoxypropylene polymer using a suitable amount of an isopropanol solution of a platinum-vinylsiloxane complex with a platinum content of 3% by weight as a catalyst. As a result, a polyoxypropylene polymer (polymer F) having a dimethoxymethylsilyl group only at one end of a molecular chain having a linear structure with a number average molecular weight of 5000 was obtained. As a result of measurement by ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of dimethoxymethylsilyl groups was 0.95 on average per molecule.

Example 1
100 parts by weight of Polymer A obtained in Synthesis Example 1 (a polyoxypropylene polymer having a number average molecular weight of 18000 and a branched structure containing 2.1 dimethoxymethylsilyl groups in one molecule), Synthesis Example 3 Polymer C (number average molecular weight of 5000 and a polyoxypropylene polymer having a reactive silyl group only at one end of the molecule, and 0.8 dimethoxymethylsilyl groups in one molecule) Polyoxypropylene polymer containing 80 parts by weight of colloidal calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name “Hakuenka CCR-B”) 130 parts by weight, heavy calcium carbonate (Shiroishi Calcium Industry Co., Ltd.) ), Product name “Whiteon SB”) 70 parts by weight, epoxy compound (manufactured by Shin Nippon Rika Co., Ltd., product name “E-PS”) 25 parts by weight, sagging inhibitor (Enomoto Kasei ( ), Trade name “Disparon # 308”) 5 parts by weight, UV absorber (Ciba Japan, trade name “Tinubin 326”) 1 part by weight, light stabilizer (Sankyo Lifetech Co., Ltd., trade name “ 1 part by weight of Sanol LS770 "), 3 parts by weight of a photocurable compound (manufactured by Toagosei Co., Ltd., trade name" Aronix M-309 "), 3 parts by weight of Tung oil, and microballoon (Matsumoto Yushi Seiyaku) 10 parts by weight, trade name “Microsphere MFL-80GCA”, average particle size 10-30 μm, 5 parts by weight of titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name “Typaque R-820”) In addition, after thoroughly kneading with three paint rolls, as a curing catalyst, 3 parts by weight of tin octylate and 0.6 parts by weight of laurylamine were added and uniformly kneaded to obtain a curable composition.

This curable composition was evaluated by the following method, and the results are shown in Table 1.
(specific gravity)
It measured based on JIS A1439.
(Number average molecular weight of component (A) and component (B))
(viscosity)
It measured under 23 degreeC using BS type | mold viscosity meter.
(Workability)
The curable composition was put in a cartridge and evaluated from the extrusion property and the degree of occurrence of stringing when it was applied on the surface of the joint at 23 ° C. and 5 ° C.
Good (good workability, no stringing) 6 points → Bad (poor extrudability or stringing occurs) 1 point (paint contamination)
Using the curable composition, a sheet having a thickness of 3 mm was prepared, allowed to stand at 23 ° C. and 50% humidity for 3 days, and further 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 left for 7 days at 23 ° C. and 50% humidity. 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 adhesion) 6 points → Evil (a lot of adhesion on one side): 1 point

(Examples 2-6, Comparative Examples 1-4)
Based on the composition shown in Table 1, a curable composition was prepared and evaluated in the same manner as in Example 1.
The results are shown in Table 1.

Polymer A: A polyoxypropylene polymer having a branched structure having a number average molecular weight of 18,000 and having an average of 2.1 dimethoxymethylsilyl groups in one molecule.
Polymer B: A polyoxypropylene polymer having a number average molecular weight of 14,000 and having an average of 1.6 dimethoxymethylsilyl groups in one molecule.
Polymer C: a polyoxypropylene polymer having a number average molecular weight of 5000 and having a reactive silyl group only at one end of the molecular chain, and 0.8 dimethoxymethylsilyl groups on average in one molecule A polyoxypropylene polymer having:
Polymer D: A polyoxypropylene polymer having a number average molecular weight of 9000 and having 0.7 dimethoxymethylsilyl groups on average in one molecule.
Polymer E: A polyoxypropylene polymer having a number average molecular weight of 12,000, having a hydroxyl group at the molecular end, and containing no reactive silicon group.
Polymer F: a polyoxypropylene polymer having a number average molecular weight of 5000 and having a reactive silyl group only at one end of the molecular chain, and having an average of 0.95 dimethoxymethylsilyl groups in one molecule A polyoxypropylene polymer having:

From the results of Table 1, in the curable compositions of the present invention of Examples 1 to 6, the viscosity is higher than that of the composition of Comparative Example 1 using a low molecular plasticizer. It can be seen that the property is greatly improved when the viscosity is taken into consideration, and the paint contamination is also reduced.

When the curable composition of the present invention is used for a sealing material, an adhesive, etc., there is no outflow or volatilization of uncured material, so there is little contamination around the sealing joint, and a water-based acrylic paint is applied to the surface of the sealing material. However, since the paint is less contaminated, it can be used with one sealant both when the paint is not applied and when the paint is applied after filling the sealant.

Claims (12)

Organic polymer having an average of 1.2 or more reactive silicon groups per molecule (A) having an average of 0.5 to less than 1.2 dimethoxymethylsilyl groups per molecule polyoxyalkylene-based polymer (B), an organic polymer (a) filler 10 to 200 parts by weight per 100 parts by weight, 0. 1 to 20 parts by weight of a particulate material (C) having a true specific gravity of 0.02 or more and less than 0.4 , and at least one curable compound selected from a photocurable compound, an oxygen curable compound and an epoxy compound ( F) and a curable composition containing fatty acid surface-treated colloidal calcium carbonate and non-surface-treated heavy calcium carbonate as fillers ,
A curable composition having a specific gravity of 1.0 or more and 1.3 or less. The curable composition according to claim 1, wherein the organic polymer (A) is a polyoxyalkylene polymer having a number average molecular weight of 10,000 or more. The curable composition according to claim 1 or 2, wherein the polyoxyalkylene polymer (B) is a polyoxyalkylene polymer having a number average molecular weight of less than 20,000. The polyoxyalkylene polymer (B) is a polyoxyalkylene polymer having a number average molecular weight of 3000 or more and a molecular weight distribution (Mw / Mn) of 1.6 or less. The curable composition of any one of 1-3. The curable composition according to any one of claims 1 to 4, further comprising an organic polymer (D) having a number average molecular weight of 3000 or more and substantially having no reactive silicon group. object. The number average molecular weight of an organic polymer (D) is larger than the organic polymer (B) to be used, The curable composition of Claim 5 characterized by the above-mentioned. The organic polymer (D) includes at least one organic polymer selected from a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a poly (meth) acrylate copolymer. The curable composition according to claim 5 or 6. The curable composition according to claim 7, wherein the organic polymer (D) is a polyoxyalkylene polymer having a number average molecular weight of 5000 to 25000. Furthermore, at least one compound (E) selected from a carboxylic acid metal salt, a carboxylic acid, an amine compound, and an organotin compound is converted into an organic polymer (A) and / or a polyoxyalkylene polymer (B). The curable composition according to claim 1, wherein the curable composition is a curing catalyst and / or a curing accelerator. The curable composition according to any one of claims 1 to 9 , wherein the number average molecular weight of the organic polymer (A) and the polyoxyalkylene polymer (B) is 5000 or more. Polyoxyalkylene polymer (B) content is organic polymer (A) any one of claims 1 to 10, wherein the 5 or less parts by weight to 120 parts by weight per 100 parts by weight The curable composition according to 1. After claim 1 and applying a sealing material containing as a component a curable composition according to any one of 11, and cured, the construction method of applying a water-based acrylic paints to the surface.