JP5596399B2 - Curable composition and cured product thereof - Google Patents

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 an architectural sealant comprising an organic polymer containing a specific reactive silicon group, a filler, a main agent containing moisture, and a curing agent containing a curing catalyst. .

  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. .

  As a form of the sealing material for construction, it is divided into a one-component type and a multi-component type including a two-component type. The one-component type is a curable composition that contains an organic polymer containing a reactive silicon group and a curing catalyst, and has removed moisture. It reacts with moisture in the air from the time it is taken out from a moisture-proof container. Cross-linking proceeds.

  On the other hand, a multi-component type including a two-component type is divided into a main agent including an organic polymer containing a reactive silicon group and a curing agent including a curing catalyst, and a toner including a coloring component as a third component. Sometimes used together. Since there is no need for dehydration in particular, water is mixed in either the main agent or the curing agent, and these main agent, curing agent and, if necessary, the third component are sufficiently mixed before use.

  As the type of reactive silicon group, a methyldimethoxysilyl group has been mainly used. An organic polymer having a methyldimethoxysilyl group is stable in the long term without reacting with silyl groups even in the presence of moisture in the absence of a curing catalyst, and the curing reaction proceeds from that point when the curing catalyst is mixed. This is to show a desirable behavior.

  On the other hand, since the trimethoxysilyl group is a functional group having a higher activity than the methyldimethoxysilyl group, it is suitable for applications that require rapid curing. For example, Patent Document 1, Patent Document 2, Patent Document 3 and the like are shown. ing. In addition, since organic polymers having a trimethoxysilyl group have high activity, the reaction easily proceeds, in other words, lacks storage stability. Agent was essential. Since vinyltrimethoxysilane is a substance that easily volatilizes, it is a concern as a VOC substance, and is an environmentally undesirable substance. Moreover, since these generate | occur | produce methanol, there existed the subject that it was unpreferable from work environment.

  The present invention is mainly used for a sealing material for a building, but when used as a sealing material for an outer wall of a building, a paint may be applied to the entire outer wall at the time of renovation or renovation. In the case of a silicone-based sealant, there is a problem that the surface of the cured sealant cannot be applied due to repelling and cannot be applied. In the case of a sealing material using an organic polymer containing reactive silicon, although a paint can be applied, there are cases where the coating film becomes dirty and the aesthetic appearance is impaired, and improvement has been demanded. In addition, marble and granite are sometimes used on the walls and floors, both indoors and outdoors, to give a sense of quality, and sometimes the surface of the stone changes color and damages the appearance. It was.

Japanese Patent Laid-Open No. 10-245484 Japanese Patent Laid-Open No. 11-21463 JP 2006-63321 A

  The present invention is a multi-component curable composition that can be used mainly as a sealing material for buildings, and even when stored under high temperature and high humidity conditions, the viscosity of the main agent is small and can be used stably over a long period of time. Another object of the present invention is to provide a curable composition that has no or little harmful volatile substances such as a low molecular weight silane coupling agent and methanol, and is harmless to the human body and the environment. Furthermore, the cured product obtained from the present invention has almost no stains on the coating film even when a paint is applied on it, and does not cause discoloration of the stone material even when applied to the joint of the stone material, and maintains a beautiful state for a long time. it can.

  As a result of investigations to solve the above problems, the present inventors, as a result, consisted of an organic polymer having a triethoxysilyl group, a filler, and a high molecular weight plasticizer. The present inventors have found that a multi-component curable composition comprising a curing agent containing the above-mentioned problems can be solved, and completed the present invention.

  In particular, it has not been known that an organic polymer having a triethoxysilyl group is stable even under high temperature and high humidity conditions in a moisture-containing state, despite being a trialkoxysilyl group. Moreover, it discovered newly that storage stability improved further by using together the organic polymer which has 0.5 or more and less than 1.2 reactive silicon groups on the average in 1 molecule.

That is, the present invention
(A) 100 parts by weight of an organic polymer having a triethoxysilyl group, (B) 5 to 500 parts by weight of a filler, and (C) 10 to 400 parts by weight of a high molecular weight plasticizer having a number average molecular weight of 1,000 to 15,000. It is related with the multicomponent type curable composition which consists of a main ingredient containing 2000 parts or more of water | moisture content, and the hardening | curing agent containing 0.1-20 weight part of (D) hardening catalysts.

  In the present invention, the triethoxysilyl group of the component (A) is preferably bonded to the end of the organic polymer.

  In the present invention, the curing catalyst of component (D) 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 main chain of the component (A) is preferably one or more of a polyoxyalkylene polymer, a polyacrylic polymer, and a hydrocarbon polymer.

  In the present invention, the content of the silane coupling agent is preferably 1 part by weight or less.

  In the present invention, the filler of component (B) is preferably calcium carbonate.

  In addition, the present invention preferably contains 2 to 50 parts by weight of a particulate material having a true specific gravity of 0.01 or more and less than 0.5 as the component (E).

  In the present invention, the curing catalyst of component (D) is preferably a carboxylic acid metal salt and / or an amine compound.

  In the present invention, the curing catalyst of component (D) is preferably tin carboxylate.

  Moreover, it is preferable that 0.1-20 weight part of water is added to a main ingredient as (F) component in this invention.

  Moreover, this invention may contain 5 to 200 parts by weight of an organic polymer having 0.5 or more and less than 1.2 reactive silicon groups on average per molecule as the component (G). preferable.

  In the present invention, the reactive silicon group of component (G) is preferably a triethoxysilyl group.

  In the present invention, the cured product preferably has a low modulus with a 100% modulus of 0.4 MPa or less.

  Moreover, it is preferable that this invention is the sealing material for buildings which consists of the said curable composition.

  Moreover, it is preferable that this invention is a sealing material used for the joint of the stone material which consists of the said curable composition.

  Moreover, this invention relates to the hardened | cured material after constructing and hardening | curing the said curable composition.

  The curable composition of the present invention can be stably used for a long period of time because of little increase in viscosity even when stored under high temperature and high humidity conditions. In addition, since the amount of VOC substance and methanol released is small, it is a material that has almost no adverse effects on the human body or the environment. Further, when the coating is applied on the cured product, the coating film is not soiled, and even if the coating is applied to the joints of the stone, discoloration of the stone is less likely to occur and the aesthetics can be maintained for a long time.

  The present invention comprises (A) an organic polymer having a triethoxysilyl group, (B) a filler, (C) a high molecular weight plasticizer, a main agent containing 2000 ppm or more of water, and (D) a curing agent containing a curing catalyst. It is characterized by being a multi-component curable composition.

  The organic polymer (A) used in the present invention can be any polymer as long as it contains a triethoxysilyl 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 triethoxysilyl group contained in the organic polymer (A) containing a triethoxysilyl group has a hydrolyzable group bonded to a silicon atom and forms a siloxane bond by a reaction catalyzed by a curing catalyst. It is a group that can be crosslinked by 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 hydrolyzable group, and when three or more X are present, They may be the same or different, a is 3 and b is 0, 1 or 2, and m are represented by 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) ≧ 3 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 3 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 represents 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.

  In the present invention, the organic polymer (A) containing a triethoxysilyl group is essential, but other organic polymers having a hydrolyzable silyl group may be used in combination. Examples of this organic polymer include compounds having a reactive silicon group in which a is represented by 1 or 2 in the general formula (1). Specific examples include a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, an α-chloromethyldimethoxysilyl group, and an α-chloromethyldiethoxysilyl group. Among these, as those that effectively express the present invention, a diethoxymethylsilyl group and an α-chloromethyldiethoxysilyl group are more preferable.

  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, triethoxysilyl groups are more reactive than diethoxymethylsilyl groups, and organic polymers containing triethoxysilyl groups are more reactive and faster than organic polymers containing diethoxymethylsilyl groups. The elongation at break of the cured product tends to be small. A curable composition having a high curing rate by using an organic polymer containing a triethoxysilyl group or using an organic polymer containing a triethoxysilyl group and an organic polymer containing a diethoxymethylsilyl group in combination. Can be obtained. 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 the highly reactive organic polymer such as an organic polymer containing a triethoxysilyl group, the ratio of both groups in the same organic polymer, etc. can provide the desired elongation at break and curing 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 acting a silane compound such as triethoxysilane. Alternatively, after hydroxylating the hydroxyl-terminated oxypropylene polymer, it can be reacted with methallyl chloride to produce a methallyloxy-terminated oxypropylene polymer and hydrosilylated by the action of a silane compound such as triethoxysilane. 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 triethoxysilyl 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 triethoxysilyl group is 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 triethoxysilyl group in the organic polymer (A) has an average of 1.2 or more in one molecule of the polymer, but is preferably 1.3 or more. 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 triethoxysilyl groups in the organic polymer (A) in the present invention is defined as the average number obtained by a method of quantifying protons on carbon to which silyl groups are directly bonded by high resolution ¹ H-NMR measurement. doing. In the calculation of the average number of triethoxysilyl groups in the organic polymer (A) in the present invention, when the silyl group is introduced into the organic polymer precursor before the silyl group is introduced, the silyl group is introduced. As a part of the component of the organic polymer (A) having the same main chain structure with respect to the organic polymer precursor which has not been introduced and the modified organic polymer precursor into which the by-product silyl group is not introduced In addition, the calculation is performed by including it in the parameter (number of molecules) when calculating the average number of silyl groups in one molecule.

  The triethoxysilyl group of the organic polymer (A) may be present as a side chain inside the molecular chain or may be present at the terminal. However, when a reactive silicon group is present 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. No. 4,960,844, etc. 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 Introducing reactive silicon groups to oxypropylene polymers with high molecular weight and narrow molecular weight distribution by hydrosilylation, etc. Those proposed in JP-A-3-72527 can be exemplified.

  In the present invention, it is preferable to further contain (G) an organic polymer containing 0.5 or more and less than 1.2 reactive silicon groups on average per molecule.

  Moreover, the organic polymer of (G) component can use the same thing as 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 (G), 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.

  The polyoxyalkylene polymer containing 0.5 to less than 1.2 reactive silicon groups on average per molecule of the component (G) includes polyoxyethylene, polyoxypropylene, polyoxybutylene, Examples include polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer and the like. Of these, polyoxypropylene is preferred.

  The organic polymer of component (G) 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 organic polymer as the component (G) 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 organic polymer of component (G) may be one produced by a conventional polymerization method using caustic, but one produced by a polymerization method using a double metal cyanide complex such as zinc hexacyanocobaltate as a catalyst. Can be used.

  The reactive silicon group of the organic polymer of component (G) 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. Preferably. 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 organic polymer (G) used is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the organic polymer (A) containing a triethoxysilyl group. More preferably. If the amount is less than 5 parts by weight, the effect of lowering the modulus is hardly exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product tends to be insufficient. In addition, what is necessary is just to mix | blend this (G) component, 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 organic polymer as the component (G) is preferably smaller than the organic polymer (A) from the viewpoint of the effect of reducing the viscosity, and the organic polymer (A) It is preferable from the point of workability | operativity at low temperature of a composition that it is 1/2 or less of a number average molecular weight.

  Examples of the filler (B) 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.

  The amount of the filler (B) 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 triethoxysilyl group. When it is desired 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. is mainly used. When the organic polymer (A) containing an ethoxysilyl group is used within a range of 5 to 200 parts by weight, preferable results are obtained. Among these fillers, calcium carbonate is most preferable because it is easily available, inexpensive, and has a good balance of physical properties. 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 substance (E) 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, 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 the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, 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 triethoxysilyl 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 a polymer plasticizer (C) having a number average molecular weight of 1,000 to 15,000. The polymer plasticizer is a polymer compound having a number average molecular weight of 1,000 to 15,000 and substantially not containing a reactive silicon group.

  Generally, by adding a plasticizer to the curable composition, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. A commonly used plasticizer is a phthalate ester plasticizer. However, when a low molecular plasticizer such as a phthalate ester plasticizer is used, when the coating is applied after the curable composition is cured, the low molecular plasticizer moves to the coating and the coating is contaminated. This often occurs. On the other hand, by using the polymer plasticizer of component (C), the transition to the coating film is suppressed, and a good state can be maintained without causing contamination for a long time.

  Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; polyalkylene glycol esters such as polyethylene glycol dibenzoate and pentaerythritol ester; sebacic acid and adipic acid Polyester plasticizers obtained from dibasic acids such as azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polyethylene glycol having a molecular weight of 1000 or more, polypropylene glycol, Polyether polyols such as polytetramethylene glycol or the hydroxyl groups of these polyether polyols can be converted to acyl groups such as acetoxy groups, methoxy groups, ethoxy groups, butoxy groups, allyloxy groups. Polyethers such as derivatives converted to alkoxy groups, etc .; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. Is not to be done.

  Of these polymer plasticizers, those compatible with the polymer of component (A) are preferred. From this point, polyethers and vinyl polymers are preferable. Further, when polyethers are used as a plasticizer, the surface curability and deep part curability are improved, and the curing delay after storage does not occur. Polypropylene glycol is more preferred. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers and / or methacrylic polymers are preferred, and acrylic polymers such as polyacrylic acid alkyl esters are more preferred. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 1,000 to 15,000, more preferably 2,000 to 13,000, and still more preferably 3,000 to 12,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.50 or less is more preferable, and 1.30 or less is most preferable.

  The number average molecular weight is measured by a terminal group analysis method in the case of a polyether polymer, and by the GPC method in the case of other polymers. Moreover, molecular weight distribution (Mw / Mn) is measured by GPC method (polystyrene conversion).

  The polymer plasticizer of component (C) may be used alone or in combination of two or more.

  (C) As usage-amount of a component, it is 10-400 weight part with respect to 100 weight part of polymers of (A) component, Preferably it is 20-200 weight part, More preferably, it is 30-120 weight part. If the amount is less than 10 parts by weight, the effect as a plasticizer is not exhibited, and if it exceeds 400 parts by weight, the mechanical strength of the cured product is insufficient.

  Moreover, you may use plasticizers other than (C) component to such an extent that the effect of this invention is not impaired. Specifically, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate Non-aromatic dibasic acid esters such as isodecyl succinate; Aliphatic esters such as butyl oleate and methyl acetylricillinoleate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; Process oils; Epoxys such as epoxidized soybean oil and benzyl epoxystearate It can be mentioned plasticizers.

  The curing catalyst (D) 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 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 diethylhexanolate, 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 (D) may be used independently and may use 2 or more types together.

  The amount of the curing catalyst (D) used is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, based on 100 parts by weight of the organic polymer (A) containing a triethoxysilyl 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 water as the component (F). The present invention is a multicomponent curable composition, and in order for the (A) component having a triethoxysilyl group to be cured, the curing catalyst and water of the (D) component are essential. Normally, the (F) component is not essential because the filler of the (B) component contains water, but it can be cured by intentionally adding the water of the (F) component. it can. Examples of water include tap water, industrial water, agricultural water, distilled water, ion exchange water, mineral water, river water, seawater, and the like, but tap water, industrial water, and distilled water are preferable.

  Component (F) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the polymer of component (A). If the amount is less than 0.1 parts by weight, the effect of addition does not appear. If the amount exceeds 20 parts by weight, problems such as a decrease in thixotropy occur.

  The present invention is a multi-component curable composition containing moisture of 2000 ppm or more. Component (A) is an organic polymer having a hydrolyzable triethoxysilyl group. (D) In the presence of a curing catalyst and 2,000 ppm or more of water, component (A) is uniformly rubbery. It can be an excellent cured product. Since it is not necessary to perform physical dehydration such as heating or reduced pressure or dehydration accompanied by a chemical reaction in preparing the present curable composition, it should contain 2000 ppm or more of moisture when working in the presence of moderate moisture. Become. In particular, in the present invention, since the filler is used as the component (B), moisture is brought in from the filler that has absorbed moisture during storage and transportation. For the purpose of enhancing the performance of the thixotropic agent used, when the present curable composition is obtained through a heating step, or when a sufficiently dry filler is used, the water content in the composition is 2000 ppm or less. Sometimes. In such a case, it is desirable to add water as the component (F).

  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 a photosensitive resin having a cinnamoyl group as a photosensitive group, in which polyvinyl alcohol is esterified with cinnamic acid, and many polyvinyl cinnamate derivatives are exemplified. 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) containing a triethoxysilyl group. preferable. 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 per 100 parts by weight of the organic polymer (A) containing a triethoxysilyl 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 triethoxysilyl 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 used in an amount of preferably 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 triethoxysilyl group. The

  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 the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a triethoxysilyl 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 triethoxysilyl 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 per 100 parts by weight of the organic polymer (A) containing a triethoxysilyl 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; 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 100 parts by weight with respect to 100 parts by weight of the organic polymer (A) containing a triethoxysilyl 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 compound and the organic polymer (A) containing a triethoxysilyl group are used before use. Can be prepared as a two-component type or a multi-component type.

  In the case of a one-component curable composition, it is necessary to remove moisture from the system, so it is necessary to reduce the moisture in advance by heating or depressurizing the compounding agent. In the present invention, such a step is unnecessary. is there. However, when there is a possibility that the raw material to be used is altered by water, a water removal step may be included. In the case of a one-component curable composition, it is common to use a silane compound having a high dehydrating ability such as vinyltrimethoxysilane. However, vinyl silane is a substance that easily volatilizes, and is particularly undesirable when used indoors because vinyl trimethoxysilane affects the working environment. In the present invention, a chemical dehydrating agent such as vinyltrimethoxysilane is not required, but it may be used depending on the raw material used.

  It is preferable not to use silane coupling agents such as vinyltrimethoxysilane used as a dehydrating agent and aminosilane, epoxy silane, mercaptosilane used as an adhesion-imparting agent in the present invention. Is preferred. Specifically, 1 part by weight or less is preferable with respect to 100 parts by weight of the organic polymer (A) containing a triethoxysilyl group, and a range of 0.1 to 0.8 part by weight is more preferable and not used. Is most preferred.

  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 types of architectural sealant, and the present invention relates to the use of type F class 25LM, and it is desirable that the 100% modulus is 0.4 MPa or less.

  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)
Polypropylene glycol is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is about 28,500 (Tosoh's HLC-8120GPC is used as the liquid feeding system, and the column is Tosoh's TSK-GEL H. The type was used, and the solvent was a polypropylene oxide having a molecular weight in terms of polystyrene measured using THF. Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization.

  After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by vacuum devolatilization. As a result, a bifunctional polypropylene oxide (a-1) having a number average molecular weight of about 28,500 having an allyl group at the end was obtained.

For 100 parts by weight of the allyl group-terminated polypropylene oxide (a-1), 1.48 parts by weight of triethoxysilane and 150 ° C. for 2 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. By reacting, a triethoxysilyl group-terminated polypropylene oxide (polymer A) was obtained. According to the measurement of ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the average number of triethoxysilyl groups at the end of polymer A is 1.6 per molecule. confirmed.

(Synthesis Example 2)
Based on 100 parts by weight of the triethoxysilyl group-terminated polypropylene oxide (Polymer A) obtained in Synthesis Example 1, 0.24% by weight of 0.5 wt% hydrochloric acid in methanol was used as a catalyst, and 20 parts by weight of methanol was added. The resultant was mixed and stirred at 70 ° C. for 2 hours to convert the terminal triethoxysilyl group into a trimethoxysilyl group. Finally, methanol was removed by devolatilization under reduced pressure. Thus, a trimethoxysilyl group-terminated polyoxypropylene polymer (Polymer B) was obtained. Similarly to the above, as a result of ¹ H-NMR measurement, the average number of trimethoxysilyl groups at the end of polymer B was 1.6 per molecule.

(Synthesis Example 3)
With respect to 100 parts by weight of the allyl group-terminated polypropylene oxide (a-1) obtained in Synthesis Example 1, 0.94 parts by weight of methyldimethoxysilane and 90 parts by weight of 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Reaction was carried out at 2 ° C. for 2 hours to obtain methyldimethoxysilyl group-terminated polypropylene oxide (Polymer C). As above, as a result of ¹ H-NMR measurement, it was confirmed that the average number of methyldimethoxysilyl groups at the end of polymer C was 1.6 per molecule.

(Synthesis Example 4)
Polyoxypropylene having a butoxy group end and a hydroxyl group in one molecule (Sanyo Kasei Kogyo Co., Ltd .: Newpol LB285) as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average Polypropylene oxide having a molecular weight of about 8,000 (same as above, polystyrene-equivalent molecular weight measured by GPC) was obtained. Subsequently, a methanol solution of NaOMe equivalent to 1.2 times the hydroxyl group of polypropylene oxide having a hydroxyl group only at one end is added to distill off methanol, and allyl chloride is further added to convert the end hydroxyl group to allyl. Converted to the base. Unreacted allyl chloride was removed by vacuum devolatilization.

  After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by vacuum devolatilization. As described above, polypropylene oxide (b-1) having an allyl group only at one end and a number average molecular weight of about 8,000 was obtained.

With respect to 100 parts by weight of the obtained polypropylene oxide (b-1) having an allyl group only at one end, 3.28 parts by weight of triethoxysilane using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst, Reaction was performed at 90 ° C. for 2 hours to obtain polypropylene oxide (polymer D) having a triethoxysilyl group only at one end. Similar to the above, ¹ H-NMR measurement confirmed that the average number of triethoxysilyl groups at the end of polymer D was 0.8 per molecule.

Example 1
100 parts by weight of the triethoxysilyl-terminated polymer (Polymer A) obtained in Synthesis Example 1, polypropylene glycol plasticizer (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name “Actol P-23”, number average molecular weight 3, 000) 80 parts by weight, colloidal calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name “Hakuenka CCR-B”), 130 parts by weight, heavy calcium carbonate (manufactured by Shiroishi Calcium Industry Co., Ltd., trade name “Whiteon SB”) ) 70 parts by weight, epoxy plasticizer (trade name “E-PS” manufactured by Shin Nippon Rika Co., Ltd.), 25 parts by weight, sagging inhibitor (trade name “Disparon # 308” manufactured by Enomoto Kasei Co., Ltd.) Parts, 1 part by weight of an ultraviolet absorber (Ciba Japan, trade name “Tinubin 326”), 1 part by weight of a light stabilizer (trade name “Sanol LS770”, manufactured by Sankyo Lifetech Co., Ltd.), surface modification Agent (Toagosei Co., Ltd., trade name “Aronix M-309”, Microballoon (Matsumoto Yushi Seiyaku Co., Ltd., trade name “Matsumoto Microsphere MFL-80GCA”) 10 parts by weight, titanium oxide (Ishihara Sangyo) 5 parts by weight and 0.5 parts by weight of water were added and kneaded well with three paint rolls, and this was used as the main agent. Were added and mixed uniformly with 3 parts by weight of tin octylate and 0.6 parts by weight of laurylamine to obtain a curable composition.

(Example 2)
In Example 1, instead of using the polypropylene glycol plasticizer “Actocol P-23”, a polypropylene glycol plasticizer (manufactured by Bayer Co., Ltd., trade name “Acclaim 11200”, number average molecular weight 12,000) was used. A main ingredient and a curable composition were obtained in the same manner as in Example 1 except that 80 parts by weight were used.

(Example 3)
In Example 1, instead of using the polypropylene glycol plasticizer “Actocol P-23”, the main component was the same as in Example 1 except that 80 parts by weight of the polymer D obtained in Synthesis Example 4 was used. A curable composition was obtained.

(Comparative Example 1)
In Example 1, instead of using the polymer A, a base material and a curable composition were obtained in the same manner as in Example 1 except that 100 parts by weight of the polymer B obtained in Synthesis Example 2 was used.

(Comparative Example 2)
In Example 1, instead of using the polymer A, a base material and a curable composition were obtained in the same manner as in Example 1 except that 100 parts by weight of the polymer C obtained in Synthesis Example 3 was used.

(Comparative Example 3)
In Example 1, instead of using the polypropylene glycol plasticizer “Actocol P-23”, 80 parts by weight of a phthalate ester plasticizer (trade name “DINP” manufactured by Jay Plus Co., Ltd.) is used. A base material and a curable composition were obtained in the same manner as in Example 1 except that.

The main agent and the curable composition were evaluated by the following methods, and the results are shown in Table 1.
(1) When measuring the viscosity of the main agent, it was allowed to stand for 24 hours or more at 23 ° C. and 50% RH, and the measurement was performed in a stable state. The viscosities were measured with a BS type viscometer manufactured by Tokimec and a rotor No. 7 was measured under the conditions of 23 ° C. and 50% RH.
(2) The storage stability under high temperature and high humidity conditions was preserved by placing the main agent in a disposable cup, capping with aluminum foil, opening several small holes and allowing air to pass through. This was put into a constant temperature and humidity machine of 40 ° C. and 80% RH, taken out after 1 week, 2 weeks and 4 weeks, respectively, and the viscosity was measured under the condition (1). The viscosity increase rate in Table 1 is calculated by comparing the viscosity at 2 rpm with the initial value.
(3) 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 100% and the strength at break were measured.
(4) The state after 5 hours after mixing the main agent and the curing agent is to put the curable composition mixed with each in a disposable cup and leave it at 23 ° C. and 50% RH, and after 5 hours, use a microspatula. Judged by touching. Those whose surface was already skinned were not usable, and those in the same state as the initial state were usable.
(5) The paint contamination was evaluated by the following method. Using each curable composition, a sheet-like test body having a thickness of 3 mm was prepared, allowed to stand 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 left 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.

  The results are shown in Table 1.

  As can be seen from Examples 1 to 3 in Table 1, when the main agent using an organic polymer having a triethoxysilyl group is stored under high temperature and high humidity conditions, a comparison using a methyldimethoxysilyl end which is currently widely used The thickening rate is the same level as in Example 2 and is good. In particular, Example 3 using an organic polymer (D) having an average of 0.8 triethoxysilyl groups per molecule has a lower viscosity increase and better stability than Comparative Example 2. Recognize. On the other hand, Comparative Example 1 using an organic polymer having a trimethoxysilyl group is low in initial viscosity but has a large increase in viscosity when stored under high temperature and high humidity conditions. I can't.

  Further, Comparative Example 1 using an organic polymer having a trimethoxysilyl group has a high modulus of a cured product and is not suitable as a sealing material for building, but an example using an organic polymer having a triethoxysilyl group. 1 to 3 all have a low modulus and can exhibit the same level of rubber elasticity as Comparative Example 2.

  Although Comparative Example 1 and Comparative Example 2 generate methanol, Examples 1 to 3 are ethanol with low toxicity, and therefore have an advantage that they are environmentally good particularly when used indoors.

  The present invention is a multi-component curable composition, and curing starts when all of the main component and the curing agent are mixed. When used as a wood floor or tile adhesive or a building sealing material, if the curability of these curable compositions is too early, the adhesive cannot be applied to a large area, resulting in poor work efficiency. When used in such applications, it is advantageous to exhibit moderately slow curability. In Examples and Comparative Examples, the main agent and the curing agent were mixed and the state of the curable composition after 5 hours was examined. As a result, Comparative Example 1 and Comparative Example 2 were skinned, and the adhesive was used. As it was no longer usable. On the other hand, Examples 1-3 and Comparative Example 3 are in a state where they can be used even after 5 hours have passed since mixing, and can be used without waste.

  In Examples 1 to 3 using a high molecular weight plasticizer, the coating film applied to the cured product is hardly soiled, but in Comparative Example 3 using a phthalate ester plasticizer, the soiling is severe and the appearance is inferior. Met.

  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 not only as a sealing material for buildings but also as a sealant for buildings, ships, automobiles, roads and the like.

  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 (15)

(A) 100 parts by weight of an organic polymer having a triethoxysilyl group, (B) 5 to 500 parts by weight of a filler, and (C) 10 to 400 parts by weight of a high molecular weight plasticizer having a number average molecular weight of 1,000 to 15,000. part containing a main agent containing water or 2000 ppm, the triethoxysilyl group in Ri Do a curing agent comprising (D) a curing catalyst 0.1 to 20 parts by weight, the organic polymer (a), the polymer Ru der 1.2 or more on average in one molecule, a multi-component curable composition.   The curable composition according to claim 1, wherein the triethoxysilyl group of the component (A) is bonded to the terminal of the organic polymer.   The curing catalyst of component (D) is one or more compounds selected from the group consisting of carboxylic acid metal salts, carboxylic acids, amine compounds, and organotins, according to any one of claims 1-2. The curable composition according to 1.   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 content of the silane coupling agent is 1 part by weight or less.   The curable composition according to any one of claims 1 to 5, wherein the filler of component (B) is calcium carbonate.   The curable composition according to any one of claims 1 to 6, comprising 2 to 50 parts by weight of a particulate material having a true specific gravity of 0.01 or more and less than 0.5 as the component (E).   The curable composition according to any one of claims 1 to 7, wherein the curing catalyst of component (D) is a carboxylic acid metal salt and / or an amine compound.   The curable composition according to claim 1, wherein the curing catalyst of component (D) is tin carboxylate.   (F) 0.1 to 20 weight part of water is added to a main ingredient as a component, The curable composition in any one of Claims 1-9 characterized by the above-mentioned. The component (G) contains 1 to 200 parts by weight of an organic polymer having 0.5 or more and less than 1.2 triethoxysilyl groups on average per molecule as a main component. The curable composition in any one of 1-10. The curable composition according to any one of claims 1 to 11 , wherein a 100% modulus of the cured product has a low modulus of 0.4 MPa or less. The curable composition was used, building sealing material according to any one of claims 1 to 12. Billing using the curable composition according to any one of claim 1 to 12, a sealing material used for joints of stone. Cured product obtained by curing the curable composition according to any one of claims 1-14.