JP5547871B2 - Curable composition and cured product - Google Patents

Description

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

  An organic polymer having at least one reactive silicon group in the molecule is crosslinked at room temperature by forming a siloxane bond accompanied by a hydrolysis reaction of the reactive silicon group due to moisture or the like to obtain a rubber-like cured product. It is known to have the property of being

  Such a polymer having a reactive silicon group is disclosed in (Patent Document 1) and the like, has already been industrially produced, and is widely used for applications such as sealing materials, adhesives, and paints. Among them, modified silicone resins with polyether as the main chain have low viscosity at room temperature and low temperature, workability is good, and water permeability is good, especially for one-pack type sealing materials. Has a proven track record. In addition, liquid polymers having a crosslinkable silicon group and an acrylic main chain have also been used in a wide range of applications because of their good weather resistance and heat resistance.

  As a curing catalyst for such an organic polymer having a reactive silicon group, as exemplified in (Patent Document 2) and (Patent Document 3), a combination of a carboxylic acid and an amine salt, a carboxylic acid metal salt and an amine are used. In the case of a one-component composition, a tetravalent dialkyltin compound is used from the viewpoint of curability and adhesiveness. Among them, dibutyltin compounds such as dibutyltin dilaurate and dibutyltin bis (acetylacetonate) are actually used because of their high catalytic activity, that is, the curing speed of the composition surface. Because it is fast.

  However, in recent years, the toxicity of dibutyltin compounds to the human body has begun to be pointed out, and an alternative to a curing catalyst other than dibutyltin compounds is desired. For example, as in (Patent Document 4) (Patent Document 5), a technique using a metal catalyst other than tin, such as cerium or titanate, is known, but the surface curability is slow or adhesion to a substrate is not possible. Insufficient, there was a problem to use in general. Further, a technique using a dioctyltin catalyst is also known as (Patent Document 6), but has a defect that surface curability is inferior to that of a dibutyltin catalyst. Further, dimethyltin catalysts are known in combination with dealcohol-free silicones as in (Patent Document 7) (Patent Document 8), but in the case of a silicone main chain having a low polarity and an organic heavy having a relatively high polarity. In the case of coalescence, the rate of hydrolysis of silicon groups is different, so there is a limit to the use in organic polymers. (Patent Document 9) presents an example in which a polyoxyalkylene polymer having a hydrolyzable silicon group and dimethyltin bis (triethoxysilicate) are combined, but the curability of the surface is slow. It was.

In such a situation, the present inventor has discovered that a dimethyltin compound is also used under specific conditions to develop a system with fast surface hardening. In particular, dimethyltin bis (acetylacetonate) is a solid having a melting point of 178 ° C., and when added to a hydrolyzable silicon group-containing organic polymer after being finely pulverized, it does not have a capability as a curing catalyst. It has been found that when used after being dissolved, it not only excels in workability and uniformity, but also exhibits significantly higher catalytic ability. In addition, it has been found that by combining an organic polymer having a specific reactive silicon group and a dimethyltin catalyst, surface curability comparable to that of a curable composition using a current dibutyltin catalyst is developed.
JP-A-52-73998 JP-A-5-117519 Japanese Patent Laid-Open No. 9-12860 JP 2000-313814 A Japanese Patent Laid-Open No. 2002-249672 WO2002 / 102812 JP 2004-315561 A JP 11-193348 A Japanese Patent No. 3449956

  The present invention is a curable composition comprising an organic polymer having a reactive silicon group as a main component, and has a good surface curability and good tensile properties (high strength and high elongation). The purpose is to provide. It is also effective as an alternative to dibutyltin compounds that have been pointed out to the environment.

  The present inventor has investigated a curing catalyst excellent in safety to the human body, handleability, and surface curability, and a curable composition containing a reactive silicon group-containing organic polymer containing the same as a main component. It has been found that by using a tin compound under specific conditions, a system with a fast surface hardening is developed. Moreover, it discovered that the physical property substantially equivalent to the curable composition using the present dibutyltin compound was expressed by combining the organic polymer which has a specific reactive silicon group, and a dimethyltin compound.

That is, the present invention
(I). A curable composition comprising 100 parts by weight of an organic polymer (A) containing silicon that can be crosslinked by forming a siloxane bond, and 0.1 to 10 parts by weight of a dimethyltin catalyst (B), the curing thereof A curable composition characterized in that the time until the surface of the curable composition is cured is less than 40 minutes,
(II). The curable composition according to (I), wherein the dimethyltin catalyst (B) is liquid at 23 ° C. or liquefied with an appropriate organic solvent,
(III). The curable composition according to (I) or (II), wherein the main chain skeleton of the organic polymer (A) is a polyoxyalkylene and / or a (meth) acrylic acid ester polymer,
(IV). The curing according to any one of (I) to (III), wherein the main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer polymerized using a double metal cyanide complex catalyst Sex composition,
(V). 20 to 100% by weight of the organic polymer (A) is represented by the general formula (1):
-SiX ₃ (1)
(In the formula, three X's are each independently a hydroxyl group or a hydrolyzable group, and the three X's may be the same or different.) A curable composition according to any one of (I) to (IV), which is a polymer,
(VI). 20 to 100% by weight of the organic polymer (A) is represented by the general formula (2):
—C (═O) —NR ¹ —R ² —SiX ₃ (2)
(Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 6 carbon atoms, X is the same as above, and three X are the same, The curable composition according to any one of (I) to (IV), which is an organic polymer having a group represented by:
(VII). The curable composition according to any one of (I) to (VI), further comprising a silane coupling agent (C) having an amino group,
(VIII). The curable composition according to any one of (I) to (VII), further comprising colloidal calcium carbonate (D),
(IX). The curable composition according to any one of (I) to (VIII), which is a one-component curable composition,
(X). The curable composition according to any one of (I) to (IX), wherein the dimethyltin catalyst (B) is dimethyltin bis (acetylacetonate),
(XI). A sealing material comprising the curable composition according to any one of (I) to (X),
(XII). An adhesive comprising the curable composition according to any one of (I) to (X),
(XIII). A waterproof material comprising the curable composition according to any one of (I) to (X),
(XIV). A cured product obtained by curing the curable composition according to any one of (I) to (X),
About.

  The curable composition of the present invention is excellent in surface curability, workability, and tensile physical properties (high strength and high elongation). Further, without using a dibutyltin compound, which has been pointed out to have an impact on the environment, it is possible to exhibit excellent physical properties substantially equivalent to those of a curable composition using a dibutyltin compound that has been conventionally used.

  The present invention will be described in detail below.

  The curable composition of the present invention contains an organic polymer (A) having a reactive silicon group as an essential component. The reactive silicon group possessed by the organic polymer (A) is a group having a hydroxyl group or hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond by a reaction accelerated by a silanol condensation catalyst. is there.

As the reactive silicon group of the organic polymer (A), the general formula (3):
-Si (R ³ _3-n ) X _n (3)
(Wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by —OSi (R ′) _3. Where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, When two or more X are present, they may be the same or different, and n represents an integer of 1 to 3.).

  It does not specifically limit as a hydrolysable group represented by X in General formula (3), 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.

Specific examples of R ³ in the general formula (3) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— in which R ′ is a methyl group, a phenyl group or the like. Of these, a methyl group is particularly preferred.

  Specific examples of the reactive silicon group of the general formula (3) when the value of n is 3 include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a methoxydiethoxysilyl group, and an ethoxydimethoxy group. A silyl group is mentioned. From the viewpoint of high activity and good curability, a trimethoxysilyl group and a triethoxysilyl group are more preferable, and a trimethoxysilyl group is particularly preferable.

  Specific examples of the reactive silicon group of the general formula (3) when the value of n is 2 include a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group. Of these, a dimethoxymethylsilyl group is particularly preferred from the viewpoint of storage stability.

  Specific examples when the value of n is 1 include a methoxydimethylsilyl group, an ethoxydimethylsilyl group, and an isopropoxydimethylsilyl group. However, when the value of n is 1, it is not preferable because hydrolyzability is low.

  Of these, a dimethoxymethylsilyl group when the value of n is 2 is most desirable from the viewpoint of curability and stability. In order to increase the surface curability, the ratio of the organic polymer containing a hydrolyzable silicon group having a value of n of 3 is preferably 20 to 100% by weight.

  Introduction of the reactive silicon group may be performed by a known method. That is, for example, the following method can be mentioned.

  (A) An organic polymer having an unsaturated group by reacting an organic polymer having a functional group such as a hydroxyl group in the molecule with an organic compound having an active group and an unsaturated group that are reactive with the functional group. Get. Alternatively, an organic polymer having an unsaturated group is obtained by copolymerization with an epoxy compound having an unsaturated group. Subsequently, hydrosilane having a reactive silicon group is allowed to act on the obtained reaction product to effect hydrosilylation.

  (B) A compound having a mercapto group and a reactive silicon group is reacted with the organic polymer having 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, the method (a) or the method (c) of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group is high in a relatively short reaction time. It is preferable because a 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. The method (c) is preferable because the silicon group introduction step is easier than the method (a).

Specific examples of the hydrosilane compound used when the reactive silicon group of the general formula (3) is introduced by the method (a) include halogenated silanes such as trichlorosilane; trimethoxysilane, triethoxysilane, Alkoxysilanes such as 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; acyloxysilanes such as triacetoxysilane; tris (dimethylketoximate) Examples include, but are not limited to, silane, ketoximate silanes such as tris (cyclohexyl ketoximate) methylsilane, and the like. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, trimethoxysilane or triethoxysilane is easy to obtain, more preferable from the viewpoint of curability of the curable composition containing the obtained organic polymer, and trimethoxysilane is particularly preferable.

  As a synthesis method of (b), for example, a compound having a mercapto group and a reactive silicon group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit.

  When the reactive silicon group of the general formula (3) is introduced by the method (b), specific examples of the compound having a mercapto group and a reactive silicon group include, for example, γ-mercaptopropyltrimethoxysilane, γ- Examples include, but are not limited to, mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  When the reactive silicon group of the general formula (3) is introduced by the method (c), specific examples of the compound having an isocyanate group and a reactive silicon group include, for example, γ-isocyanatopropyltrimethoxysilane, γ- Examples include, but are not limited to, isocyanatopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, and isocyanatemethyltriethoxysilane.

  As a method for obtaining an organic polymer having a trimethoxysilyl group at the terminal, (a) a method of introducing a trimethoxysilyl group at the terminal by the method (a) using trimethoxysilane, (b) triethoxysilane, etc. Using a relatively safe trialkoxysilane, introduce a trialkoxysilyl group at the end by the method (a), and then introduce a trimethoxysilyl group at the end by a transesterification reaction with a compound having a methoxy group such as methanol. (C) using γ-mercaptopropyltrimethoxysilane to introduce a trimethoxysilyl group at the terminal by the method (b), (d) using γ-isocyanatopropyltrimethoxysilane (c) And a method of introducing a trimethoxysilyl group at the terminal by the method.

  As a method of reacting a polymer having a hydroxyl group at the terminal with a compound having an isocyanate group and a reactive silicon group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited.

In the present invention, the silicon-containing group of the organic polymer (A) is represented by the general formula (1):
-SiX ₃ (1)
(Wherein, X is the same as described above, and three Xs may be the same or different). The organic polymer (A) having a silicon-containing group represented by the general formula (1) is preferable in order to exhibit good rapid curability.

The organic polymer (A) having a silicon-containing group represented by the general formula (1) is, for example, the general formula (4):
—O—R ⁴ —CH═CH ₂ (4)
(Wherein R ⁴ is a linear or branched alkylene group having 1 to 4 carbon atoms) and an organic polymer into which an unsaturated group represented by general formula (5):
H-Si (R ³ _3-n ) X _n (5)
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by —OSi (R ′) _3. Where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, When two or more X are present, they may be the same or different, and n represents an integer of 1 to 3). .

In order to obtain an organic polymer (A) having a high silicon group content, the general formula (6):
—O—R ⁵ —C (CH ₃ ) ═CH ₂ (6)
(Wherein R ⁵ represents a divalent organic group having 1 to 20 carbon atoms containing at least one selected from the group consisting of hydrogen, carbon, and nitrogen as a constituent atom). An organic polymer having a group introduced therein and the general formula (5):
H-Si (R ³ _3-n ) X _n (5)
(Wherein R ³ , X, and n are the same as above) may be obtained by addition reaction with a hydrosilane compound.

In the present invention, the silicon-containing group of the organic polymer (A) is represented by the general formula (2):
—C (═O) —NR ¹ —R ² —SiX ₃ (2)
(Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 6 carbon atoms, X is the same as above, and three X are the same, And may be different from each other). The organic polymer (A) having a silicon-containing group represented by the general formula (2) is particularly excellent in rapid curing as compared with the organic polymer (A) having a terminal structure other than the general formula (2). This is preferable.

The organic polymer (A) having a silicon-containing group represented by the general formula (2) is, for example, an organic polymer having a hydroxyl group at the terminal and the general formula (7) as described in the method (c). ):
^{O = C = N-R 6} -SiX 3 (7)
(Wherein R ⁶ is a linear or branched alkylene group having 1 to 4 carbon atoms, X is the same as described above) or an isocyanate group at the terminal. An organic polymer having the general formula (8):
W-R ⁶ -SiX ₃ (8)
(Wherein R ⁶ and X are the same as defined above; W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary)); It can obtain by reaction of.

  The number average molecular weight (Mn) of the organic polymer (A) is 500 to 100,000, more preferably 1,000 to 50,000, particularly preferably 3,000 to 30,000 in terms of polystyrene in GPC. . If the number average molecular weight (Mn) is less than 500, the cured product tends to be disadvantageous in terms of elongation characteristics. If the number average molecular weight (Mn) exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  The molecular weight distribution of the organic polymer (A) is not particularly limited, but is preferably narrow, preferably less than 1.80, more preferably 1.60 or less, and most preferably 1.40 or less. If the molecular weight distribution is greater than 1.8, the viscosity tends to be high, and therefore workability tends to be poor.

  The reactive silicon group of the organic polymer (A) may be at the end of the main chain or the side chain of the polymer molecular chain, or at both ends. In particular, when the reactive silicon group is at the end of the main chain of the molecular chain, the effective network chain length of the polymer component contained in the finally formed cured product is increased, so that the high strength, high elongation, A rubber-like cured product having a low elastic modulus is easily obtained.

The main chain structure of the organic polymer (A) may be linear or branched. In order to express the fast curability of the surface which is the object of the present invention, a structure having a branch is preferable. On the other hand, in order to obtain a rubber-like cured product having high strength and high elongation, it is preferably linear. Moreover, in order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, the reactive silicon group of the organic polymer (A) has an average of 1.0 to 1 in one molecule of the polymer. The number is preferably 3.0, and more preferably 1.1 to 2.7. When the number of reactive silicon groups contained in the molecule is less than 1 on average, curability becomes insufficient and it becomes difficult to exhibit good rubber elastic behavior. If the average number of reactive silicon groups contained in the molecule is greater than 3, there is an inconvenient tendency in terms of elongation characteristics of the cured product.

  The main chain skeleton of the organic polymer (A) is composed of one or more selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom from the viewpoints of adhesion, workability, and deep curability. It is preferable.

  The main chain skeleton of the organic polymer (A) is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxy Polyoxyalkylene polymers such as propylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or butadiene and acrylonitrile and Copolymers with styrene, etc., polybutadiene, isoprene or copolymers of butadiene with acrylonitrile and styrene, and hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers Any hydrocarbon polymer; polyester polymer obtained by condensation of dibasic acid such as adipic acid and glycol or ring-opening polymerization of lactones; compounds such as ethyl (meth) acrylate and butyl (meth) acrylate A (meth) acrylic acid ester polymer obtained by radical polymerization of a polymer; a vinyl polymer obtained by radical polymerization of a compound such as a (meth) acrylic acid ester compound, vinyl acetate, acrylonitrile, styrene; the polymer A graft polymer obtained by polymerizing a vinyl compound in the polymer; a polysulfide polymer; polyamide 6 by ring-opening polymerization of ε-caprolactam, polyamide 6 · 6 by condensation polymerization of hexamethylenediamine and adipic acid, hexamethylenediamine Polyamide 6.10 by condensation polymerization of sebacic acid, epsilon amino Polyamide-based polymers such as polyamide 11 by polycondensation of decanoic acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, a copolymerized polyamide composed of a plurality of the above-mentioned polyamides; polycarbonate by condensation polymerization from bisphenol A and carbonyl chloride, etc. Organic polymers such as polycarbonate polymers; diallyl phthalate polymers; In addition, polysiloxane polymers such as polydiorganosiloxane are also included.

  Among these, the polyoxyalkylene polymer and the organic polymer (A) having a (meth) acrylic acid ester polymer in the main chain skeleton have a relatively low glass transition temperature, and the resulting cured product has a low temperature resistance. It is preferable because it is excellent.

  The glass transition temperature of the organic polymer (A) having a reactive silicon group is not particularly limited, and is preferably 20 ° C. or lower, more preferably 0 ° C. or lower, and −20 ° C. or lower. Particularly preferred. When the glass transition temperature exceeds 20 ° C., the viscosity of the curable composition in winter or cold regions tends to be high and workability tends to be poor, and the flexibility of the resulting cured product is lowered, resulting in a decrease in elongation. Tend to.

  The glass transition temperature can be determined by DSC measurement according to the measurement method defined in JIS K7121.

In addition, a curable composition mainly composed of an organic polymer having a main chain skeleton of a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer has a low molecular weight when used as an adhesive or a sealing material. There is little transfer (contamination) of components to the adherend, and this is more preferable.

  Furthermore, the organic polymer having a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer in the main chain skeleton has high moisture permeability and was used as a main component of a one-pack type adhesive or a sealing material. At this time, the cured product obtained is excellent in deep part curability and has excellent adhesiveness, and an organic polymer having a polyoxyalkylene polymer in the main chain skeleton is most preferable.

The polyoxyalkylene polymer used as the main chain skeleton of the organic polymer (A) is a compound represented by the general formula (9):
-R ⁷ -O- (9)
(R ⁷ is a linear or branched alkylene group having 1 to 14 carbon atoms.)

R ⁷ in the general formula (9) is not particularly limited as long as it is a linear or branched alkylene group having 1 to 14 carbon atoms, and among these, a straight chain having 2 to 4 carbon atoms A branched or branched alkylene group is preferred.

The repeating unit of the general formula (9) described, not particularly limited, for example, _{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H ₅ ) O—, —CH ₂ C (CH ₃ ) ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O— and the like.

  The polyoxyalkylene polymer may be composed of only one type of repeating unit or may be composed of a plurality of types of repeating units. Especially when used for applications such as sealing materials, the organic polymer (A) mainly composed of a propylene oxide polymer as the main chain skeleton is amorphous and has a relatively low viscosity. preferable.

  The production method of the polyoxyalkylene polymer is not particularly limited and includes known methods. For example, a method using an alkali catalyst such as KOH, an organoaluminum compound disclosed in JP-A-61-215623, and Method using transition metal compound-porphyrin complex such as a complex obtained by reacting with porphyrin as a 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 US Pat. No. 3,278,595, US Pat. No. 3,427,256, US Pat. No. 3,427,334, US Pat. No. 3,427,335, and the like, and a polyphosphazene salt disclosed in JP-A-10-273512 , As a catalyst, JP-A-11 A method using a phosphazene compound disclosed in JP 060722 as catalyst.

  The production method of the polyoxyalkylene polymer having a reactive silicon group is not particularly limited, and examples thereof include known methods. For example, JP-B Nos. 45-36319, 46-12154, and JP-A-50-156599 are known. No. 54-6096, No. 55-13767, No. 55-13468, No. 57-164123, No. 3-2450, US Pat. No. 3,362,557, US Pat. No. 4345053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc., JP-A 61-197631, JP-A 61-215622, JP-A 61-215623, JP-A 61-218632, JP-A-3-72527, JP-A-3-47825, High molecular weight (number average molecular weight 6,000 or more) molecules disclosed in JP-A-8-231707 And a method of distribution is narrow (Mw / Mn 1.6 or less) polymer is obtained and the like.

  When the polyoxyalkylene polymer having a reactive silicon group is blended in the curable composition, only one type may be blended or a plurality of types may be blended.

  The (meth) acrylic acid ester polymer used as the main chain skeleton of the organic polymer (A) is a polymer comprising a (meth) acrylic acid ester compound as a repeating unit. In addition, the said description method ((meth) acrylic acid ester) represents acrylic acid ester and / or methacrylic acid ester, and also represents the same meaning also in subsequent description methods.

  The (meth) acrylic acid ester compound used as the repeating unit is not particularly limited. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n -Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, (meth) acrylate n -Hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate , Dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic Stearyl acid, glycidyl (meth) acrylate, γ- (methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoro (meth) acrylic acid Methylmethyl, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylic acid Perfluoroethyl, (meth) a Trifluoromethyl laurate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( Examples include (meth) acrylic acid compounds such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  The (meth) acrylic acid ester polymer includes a copolymer of a (meth) acrylic acid ester compound and a vinyl compound copolymerizable therewith. The vinyl compound is not particularly limited, and for example, styrene compounds such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; silicon groups such as vinyl trimethoxysilane and vinyl triethoxysilane. Vinyl-based compounds having: maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide , Maleimide compounds such as butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; acrylonitrile, meta Vinyl compounds having a nitrile group such as rilonitrile; Vinyl compounds having an amide group such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate; ethylene And alkenes such as propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. A plurality of these can be used as a copolymerization component.

Among the (meth) acrylic acid ester-based polymers obtained from the above compounds, an organic polymer having a main chain skeleton of a copolymer composed of a styrene compound and a (meth) acrylic acid compound is obtained. Is preferable from the viewpoint of excellent physical properties, more preferably an organic polymer having a copolymer consisting of an acrylate compound and a methacrylic acid ester compound in the main chain skeleton, and an organic having a polymer consisting of an acrylate compound in the main chain skeleton Polymers are particularly preferred.

  Since the curable composition has a low viscosity, and the obtained cured product is required to have high elongation, weather resistance, heat resistance, etc., the main chain skeleton of the organic polymer (A) is acrylic acid. What consists of a butyl type compound is more preferable.

  On the other hand, when used for automobile applications, the cured product obtained is required to have excellent oil resistance.

  As the obtained cured product having excellent oil resistance, it is more preferable that the main chain skeleton of the organic polymer (A) is made of a copolymer mainly composed of ethyl acrylate.

  The curable composition containing the organic polymer (A) having a main chain skeleton of a copolymer mainly composed of ethyl acrylate is excellent in oil resistance but slightly inferior in low-temperature characteristics (cold resistance). There is a tendency to replace a part of ethyl acrylate with butyl acrylate for the purpose of improving low temperature characteristics. However, since the good oil resistance tends to be impaired as the ratio of butyl acrylate is increased, the ratio is preferably 40% or less when used in applications requiring oil resistance. Is more preferably 30% or less.

  It is also preferable to use it for copolymer components such as 2-methoxyethyl acrylate and 2-ethoxyethyl acrylate in which oxygen is introduced into the side chain alkyl group in order to improve low temperature characteristics without impairing oil resistance. .

  However, since the resulting cured product tends to be inferior in heat resistance due to the introduction of an alkoxy group having an ether bond in the side chain, the ratio should be 40% or less when used in applications requiring heat resistance. Is preferred.

  As described above, the organic polymer (A) having a main chain skeleton of a copolymer mainly composed of ethyl acrylate is an oil resistance required for the resulting cured product according to various uses and required purposes. In consideration of physical properties such as properties, heat resistance, and low-temperature characteristics, it is possible to obtain a suitable polymer by changing the type and ratio of copolymer components. For example, although not particularly limited, examples of excellent balance of physical properties such as oil resistance, heat resistance, and low temperature characteristics include ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate (40 to 50/20 by weight). To 30/30 to 20).

  In the present invention, these preferred compounds can be copolymerized with other compounds, and further block copolymerized. In this case, these preferred compounds may be contained in a weight ratio of 40% or more. preferable.

  It does not specifically limit as a manufacturing method of a (meth) acrylic-ester type polymer, A well-known method is mention | raise | lifted. Among these, the living radical polymerization method is preferably used because it is easy to introduce a crosslinkable functional group at the molecular chain terminal at a high ratio, and a polymer having a narrow molecular weight distribution and a low viscosity can be obtained.

  A polymer obtained by a normal free radical polymerization method using an azo compound, a peroxide or the like as a polymerization initiator generally has a large molecular weight distribution value of 2 or more and tends to have a high viscosity.

Among the methods for producing a (meth) acrylic acid ester polymer using the “living radical polymerization method”, an “atom” using an organic halide or a sulfonyl halide as an initiator and a transition metal complex as a catalyst In addition to the characteristics of “Living Radical Polymerization”, which has a narrow molecular weight distribution and a low-viscosity polymer is obtained, the “transfer radical polymerization” has a large degree of freedom in selecting initiators and catalysts, and is suitable for functional group conversion reactions. It is more preferable as a method for producing a (meth) acrylic acid ester-based polymer having a specific functional group because it has a relatively advantageous halogen at the terminal. Examples of the atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  The method for producing the (meth) acrylic acid ester-based polymer having a reactive silicon group is not particularly limited, and examples thereof include Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Application Laid-Open No. Hei 6-221922. Examples thereof include a free radical polymerization method using a chain transfer agent disclosed, an atom transfer radical polymerization method disclosed in JP-A-9-272714, and the like.

  A (meth) acrylic ester copolymer comprising a plurality of the (meth) acrylic ester compounds can also be used as the main chain skeleton of the organic polymer (A).

As a specific example of the methacrylic ester copolymer comprising a plurality of (meth) acrylic ester compounds, the main chain skeleton is substantially represented by the general formula (10):
—CH ₂ —C (R ⁸ ) (COOR ⁹ ) — (10)
(Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an alkyl group having 1 to 8 carbon atoms), and a repeating unit having an alkyl group having 1 to 8 carbon atoms represented by the general formula ( 11):
^{_{-CH 2 -C (R 8) (}} COOR 10) - (11)
(Wherein R ⁸ is the same as described above, and R ¹⁰ is an alkyl group having 9 or more carbon atoms), and a copolymer comprising a repeating unit having an alkyl group having 9 or more carbon atoms is exemplified. .

R ⁹ described in the general formula (10) is not particularly limited as long as it is an alkyl group having 1 to 8 carbon atoms. For example, methyl group, ethyl group, propyl group, n-butyl group, t-butyl group And 2-ethylhexyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable. Incidentally, R ⁹ contained in the copolymer is not necessarily limited to one kind of alkyl group.

R ¹⁰ described in general formula (11) is not particularly limited as long as it is an alkyl group having 9 or more carbon atoms, and examples thereof include lauryl group, tridecyl group, cetyl group, stearyl group, and behenyl group. Among these, an alkyl group having 10 to 30 carbon atoms is preferable, and a long-chain alkyl group having 10 to 20 carbon atoms is more preferable. Incidentally, R ¹⁰ contained in the copolymer is not necessarily limited to one kind of alkyl group.

  The (meth) acrylic acid ester-based copolymer is substantially composed of repeating units described in the general formula (10) and the general formula (11). Here, “substantially” means that the total proportion of the repeating units described in the general formulas (10) and (11) in the copolymer exceeds 50% by weight, and occupies the copolymer. The total proportion of the repeating units described in the general formulas (10) and (11) is preferably 70% by weight or more.

Further, the ratio of the repeating units of the general formulas (10) and (11) present in the copolymer is preferably 95: 5 to 40:60 in weight ratio (general formula (10): general formula (11)). 90:10 to 60:40 is more preferable. The (meth) acrylic acid ester copolymer is a copolymer of a (meth) acrylic acid ester compound used as a repeating unit described in the general formulas (10) and (11) and a vinyl compound copolymerizable therewith. Includes coalescence.

  Examples of vinyl compounds include acrylic acid such as acrylic acid and methacrylic acid; amide groups such as acrylamide, methacrylamide, N-methylol acrylamide, and N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, diethylaminoethyl acrylate, Compounds having an amino group such as diethylaminoethyl methacrylate and aminoethyl vinyl ether; and other compounds such as acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, and ethylene.

  In the main chain skeleton of the organic polymer (A), a repeating unit other than the above, for example, having a urethane bond may be present as long as the effect of the present invention is not significantly impaired as required.

  The repeating unit having a urethane bond is not particularly limited, and examples thereof include a repeating unit having a group (hereinafter also referred to as an amide segment) generated by a reaction between an isocyanate group and an active hydrogen group.

The amide segment is represented by the general formula (12):
-NR < ¹¹ > -C (= O)-(12)
(R ¹¹ is a hydrogen atom or an organic group).

  The amide segment is not particularly limited and is, for example, a urethane group generated by a reaction between an isocyanate group and a hydroxyl group; a urea group generated by a reaction between an isocyanate group and an amino group; a group generated by a reaction between an isocyanate group and a mercapto group. And thiourethane groups.

  In the present invention, an organic group generated by a reaction between an active hydrogen in a urethane group, a urea group, and a thiourethane group and an isocyanate group is also defined as an amide segment.

A method for producing an organic polymer having a reactive silicon group having an amide segment in the main chain skeleton is not particularly limited, and examples thereof include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557) and Japanese Patent Publication No. 58-109529. (U.S. Pat. No. 4,374,237), JP-A-62-143030 (U.S. Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP-T-2003-508561 (US Pat. No. 6,1979,912) No. 6-2111879 (U.S. Pat. No. 5,364,955), JP-A No. 10-53637 (U.S. Pat. No. 5,757,751), JP-A No. 11-100197, JP-A No. 2000-169544, JP-A No. 2000-169545, JP2002-212415, Patent 331 360, U.S. Pat. No. 4,067,844, U.S. Pat. No. 3,711,445, JP-A-2001-323040, etc. are reacted with an organic polymer having an organic group having an active hydrogen at the terminal, with an excess amount of a polyisocyanate compound. Thus, after obtaining a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group in the polymer and the general formula (13):
^{_{W-R 12 -SiR 13 3-}} n X n (13)
(In the formula, R ¹² is a divalent organic group, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. (3-n) R ¹³ is a hydrogen atom or an organic group. N is a hydroxyl group or a hydrolyzable group, and n is 1, 2 or 3. W is a group consisting of a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary). A group having at least one active hydrogen, which is more selected, and a method of reacting W in a silicon compound represented by the following formula:

JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6046270), JP-A 58-29818 (US Pat. No. 4345053), JP-A-3-47825 (US) Patent No. 5068304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981, and the like. Group having hydrogen and general formula (14):
_{^{O = C = N-R 12}} -SiR 13 3-n X n (14)
(However, in the formula, R ¹² , R ¹³ , X, and n are the same as those in the general formula (13).) A method of reacting an isocyanate group of an isocyanate compound having a reactive silicon group is exemplified.

  The organic polymer having a group having an active hydrogen at the terminal is not particularly limited. For example, an oxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydroxyl group at the terminal. A hydrocarbon polymer (polyolefin polyol), a polythiol compound, a polyamine compound and the like can be mentioned.

  Among these, polyether polyols, polyacrylic polyols, and organic polymers having a polyolefin polyol component in the main chain skeleton are preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

  An organic polymer containing a polyether polyol component is particularly preferred because it has a low viscosity and good workability, and the resulting cured product has good deep curability and adhesiveness. Moreover, the curable composition using the organic polymer which has a polyacryl polyol and a saturated hydrocarbon type polymer component is more preferable from the favorable weather resistance and heat resistance of the hardened | cured material obtained.

  As the polyether polyol, those having an average of at least 0.7 hydroxyl groups per molecule are preferred.

  The production method is not particularly limited and includes known methods. For example, at least two polymerization methods using an alkali metal catalyst, at least two per molecule as an initiator in the presence of a double metal cyanide complex or cesium. Examples thereof include a polymerization method of alkylene oxide using a polyhydroxy compound having a hydroxyl group.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex has a low degree of unsaturation, a narrow molecular weight distribution (Mw / Mn), and a low-viscosity polymer can be obtained. The acid resistance and weather resistance of the resin are preferred.

  The polyacryl polyol refers to a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule.

  The production method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the resulting polymer has a narrow molecular weight distribution and can be reduced in viscosity. Further, a polymerization method based on a so-called SGO process in which an alkyl acrylate ester compound disclosed in JP-A-2001-207157 is continuously bulk-polymerized at high temperature and high pressure is preferable. Examples of the polyacryl polyol include Alfon UH-2000 manufactured by Toagosei Co., Ltd.

The polyisocyanate compound is not particularly limited, and examples thereof include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. It is done.

  The silicon compound represented by the general formula (13) is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and N-phenyl-γ-. Silanes having amino groups such as aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Compound; Silane compound having a hydroxy group such as γ-hydroxypropyltrimethoxysilane; Silane compound having a mercapto group such as γ-mercaptopropyltrimethoxysilane;

  Further, as the silicon compound described in the general formula (13), JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), Michael addition reaction products of various α, β-unsaturated carbonyl compounds and silane compounds having a primary amino group disclosed in JP-A Nos. 2000-169544 and 2000-169545, or various types of (meth) Examples include a Michael addition reaction product of a silane compound having an acryloyl group and a compound having a primary amino group.

  The isocyanate compound having a reactive silicon group described in the general formula (14) is not particularly limited. For example, γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ -Methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like.

  Furthermore, as the isocyanate compound having a reactive silicon group described in the general formula (14), an excessive amount of the silicon compound described in the general formula (8) disclosed in JP-A No. 2000-119365 (US Pat. No. 6,046,270) Examples include reaction products of polyisocyanate compounds.

  Since the workability of the curable composition is good, the surface curability has a practical speed, and the resulting cured product has excellent mechanical properties (high strength, high elongation, etc.), The main chain skeleton of the organic polymer (A) is preferably a polyoxyalkylene polymer and / or a (meth) acrylic acid ester polymer.

  In the present invention, a dimethyltin catalyst (B) is used as a silanol condensation catalyst for the purpose of promoting the reaction of the reactive silicon group.

Specific examples of the dimethyltin catalyst (B) include dimethyltin dichloride, dimethyltin dibromide, dimethyltin methoxide, dimethyltin ethoxide, dimethyltin dibutoxide, dimethyltin dihexanoate, dimethyltin dioctanoate, dimethyltin bis (2-ethylhexanoate) ), Dimethyltin didecanoate, dimethyltin diversate, dimethyltin dilaurate, dimethyltin diacetate, dimethyltin bis (acetylacetonate), dimethyltin bis (ethylacetoacetate), dimethyltin maleate, dimethyltin phthalate, dimethyltin bis (methyl) Maleate), dimethyltin bis (ethyl maleate), dimethyltin bis (butyl maleate), dimethyltin bis (octyl maleate), dimethyltin bis (tridecyl maleate) Dimethyltin bis (benzyl maleate), dimethyltin bis (nonylphenoxide), dimethyltin oxide, dimethylhydroxyoleate tin, dimethyltin (methyldimethoxysilicate), dimethyltin bis (ethyldimethoxysilicate), dimethyltin bis (butyl) Dimethoxysilicate), dimethyltin bis (methyldiethoxysilicate), dimethyltin bis (ethyldiethoxysilicate), dimethyltin bis (butyldiethoxysilicate), dimethyltin bis (dimethylmethoxysilicate), dimethyltin bis (diethylmethoxysilicate) ), Dimethyltin bis (dibutylmethoxysilicate), dimethyltin bis (dimethylethoxysilicate), dimethyltin bis (diethylethoxysilicate), dimethyltin bis (dibutylethoxy) Silicate) dimethyltin bis (trimethoxysilicate), dimethyltin bis (triethoxysilicate), dimethyltin bis (tributoxysilicate), dimethyldi (dodecylthio) tin, dimethylbis [[(6-methylheptyloxycarbonyl) methyl] thio ], Etc. are mentioned.

  Among the dimethyltin catalysts (B), dimethyltin bis (acetylacetonate), dimethyltin diversate, and dimethylhydroxyoleate tin are preferable because of their high activity.

  The dimethyltin catalyst (B), which is solid at room temperature, does not act as a curing catalyst even if it is added after being finely pulverized. Examples of the solid dimethyltin catalyst (B) include dimethyltin bis (acetylacetonate) and dimethyltin dichloride.

  The organic solvent is not particularly limited, and examples thereof include alcohols, acetone, toluene, ethers, and chlorine-containing solvents such as methylene chloride and chloroform. Chlorine-containing solvents such as methylene chloride and chloroform are preferred because of their high ability to dissolve dimethyltin compounds (B), particularly dimethyltin bis (acetylacetonate). The chlorine-containing solvent has been pointed out to have adverse effects on the human body and it is not preferable that the chlorine-containing solvent remains in the curable composition, but by reducing the pressure while stirring in the final step of producing the curable composition, It is possible to remove the organic solvent.

  As the usage-amount of said organic solvent, the solvent amount from which the density | concentration of the solution which dissolved the dimethyltin catalyst (B) will be 0.1 to 50% is preferable, and the solvent amount which becomes 1 to 20% is more preferable. If the concentration of the solution is less than 0.1%, the amount of solvent is large and not economical. On the other hand, when the concentration of the solution exceeds 50%, the amount of solvent is small and the dimethyltin catalyst (B) is not dissolved, which is not preferable.

  Although the temperature which melt | dissolves a solid dimethyltin catalyst (B) is not specifically limited, 0 degreeC or more and less than 150 degreeC are preferable, and 10 degreeC or more and less than 100 degreeC are more preferable. By selecting an appropriate organic solvent, it can be dissolved at room temperature, and is most preferably dissolved at room temperature.

  In addition, dimethyltin diversate and dimethylhydroxyoleate tin, when combined with an organic polymer (A) having a silicon group to which three hydrolyzable groups are bonded, have a surface curability of less than 40 minutes. To express.

  The amount of the dimethyltin catalyst (B) used is preferably 0.01 to 20 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). . If the dimethyltin catalyst (B) is less than 0.01 parts by weight, the surface curability and the development of strength are delayed. On the other hand, when the amount of the dimethyltin catalyst (B) exceeds 20 parts by weight, the curability is so fast that the time for working cannot be secured, and the adhesion with the substrate may be deteriorated.

In the present invention, the dimethyltin catalyst (B) is used as the silanol condensation catalyst, but other curing catalysts can be used in combination so as not to reduce the effects of the present invention. Specific examples include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, carboxyl Carboxylic acid metal salts such as iron oxide, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diiso Titanium compounds such as propoxytitanium bis (ethylacetoacetate); aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminumethyl Aluminum compounds such as cetoacetate; Zirconium compounds such as zirconium tetrakis (acetylacetonate); Various metal alkoxides such as tetrabutoxyhafnium; Organic acidic phosphates; Organic sulfonic acids such as trifluoromethanesulfonic acid; Hydrochloric acid, Examples include inorganic acids such as phosphoric acid and boronic acid.

  By using these curing catalysts in combination, the catalytic activity is increased, and improvement in deep part curability, thin layer curability, adhesion and the like is expected. As the usage-amount of these curing catalysts, 0.01-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and 0.1-10 weight part is more preferable.

In addition, a carboxylic acid can be used in combination as a cocatalyst to such an extent that the effect of the present invention is not lowered. Specific examples 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 , Fizetheric acid, myristoleic 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, cetoleic acid Erucic acid, brassic acid, ceracolein Monoene unsaturated fatty acids such as ximenic acid, lumectric acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linoleic acid, 10,12-octadecadienoic acid, Hiragonic 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, succinic acid, nisic acid, docosahexaene Polyene unsaturated fatty acids such as acids; 1-methylbutyric acid, isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculosis Aric acid, pivalic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2-methylvaleric acid, 2,2 -Branches such as diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid, neodecanoic acid, versatic acid Fatty acids; fatty acids having triple bonds such as propiolic acid, talylic acid, stearolic acid, crepenic acid, xymenic acid, 7-hexadesinic acid; naphthenic acid, malvalic acid, sterlic acid, hydnocarbic acid, sorghumulinic acid, Gorulic acid, 1-methylcyclopentanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 2-methylbicyclo [2.2.1]- -Alicyclic carboxylic acids such as heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2.2.2] octane-1-carboxylic acid Acetoacetic acid, ethoxyacetic acid, glyoxylic acid, glycolic acid, gluconic acid, sabinic acid, 2-hydroxytetradecanoic acid, iprolic acid, 2,2-dimethyl-3-hydroxypropionic acid, 2-hydroxyhexadecanoic acid, yarapinolic acid, uniperine Acid, ambretoleic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10-dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, ricanoic acid, ferronic acid, cereblon Acid, 2-methyl-7-oxabici Oxygenated fatty acids such as chloro [2.2.1] -5-heptene-2-carboxylic acid; halogen substituted products of monocarboxylic acids such as chloroacetic acid, 2-chloroacrylic acid and chlorobenzoic acid. Aliphatic dicarboxylic acids include adipic acid, azelaic acid, pimelic acid, speric acid, sebacic acid, ethylmalonic acid, glutaric acid, oxalic acid, malonic acid, succinic acid, oxydiacetic acid, dimethylmalonic acid, ethylmethylmalonic acid Diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 1,2,2-trimethyl-1,3-cyclopentanedicarboxylic acid and other saturated dicarboxylic acids And unsaturated dicarboxylic acids such as maleic acid, fumaric acid, acetylenedicarboxylic acid, and itaconic acid. Examples of the aliphatic polycarboxylic acid include tricarboxylic acids such as aconitic acid, 4,4-dimethylaconitic acid, citric acid, isocitric acid, and 3-methylisocitric acid. Aromatic carboxylic acids include aromatic monocarboxylic acids such as benzoic acid, 9-anthracenecarboxylic acid, atrolactic acid, anisic acid, isopropylbenzoic acid, salicylic acid, toluic acid; phthalic acid, isophthalic acid, terephthalic acid, carboxyphenyl And aromatic polycarboxylic acids such as acetic acid and pyromellitic acid. By using these curing catalysts in combination, the catalytic activity is increased, and improvements in curability and deep curability are expected. As usage-amount of carboxylic acid, 0.01-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and 0.1-10 weight part is more preferable.

  In this invention, dialkyl tin compounds other than a dimethyltin catalyst (B) can also be used together. Specifically, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin bis (acetylacetonate), dioctyltin maleate, dioctyltin bis (triethoxysilicate), dilauryltin dilaurate, dilauryltin diacetate, dilauryltin bis (acetyl) Acetonate), dilauryl tin maleate, dilauryl tin bis (triethoxysilicate), dibutyltin dilaurate, dibutyltin diacetate, dibutyltin bis (acetylacetonate), dibutyltin maleate, dibutyltin bis (triethoxysilicate), dibutyltin Examples include oxides. As a usage-amount of dialkyl tin compounds other than a dimethyltin catalyst (B) and a dibutyltin compound, 0.01-20 weight part is preferable with respect to 100 weight part of organic polymers (A), 0.1-10 weight Part is more preferred. Dibutyltin compounds are preferably not used since toxicity to humans has been pointed out in recent years.

  In the present invention, it is preferable to use a silane coupling agent (C) having an amino group. The silane coupling agent having an amino group is a compound having a reactive silicon group and an amino group, and improves the adhesiveness of the curable composition of the present invention by combining with the organic polymer (A) of the present invention. In addition, it has the effect of increasing the curability of the composition and further increasing the strength and hardness (hardness) of the resulting cured product.

  The effect of the silane coupling agent (C) having an amino group added to the curable composition of the present invention is such that various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, When used on an organic base material such as polyvinyl chloride, polyacrylic, polyester, polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable.

  As an example of the reactive silicon group which the silane coupling agent (C) which has an amino group has, the thing whose X of the groups represented by General formula (3) is a hydrolysable group can be mentioned, for example. Specific examples of the hydrolyzable group include the groups already exemplified, and a methoxy group, an ethoxy group, and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more. The primary amino group is more preferable because it has a high effect of improving adhesiveness and an effect of increasing the strength and hardness (hardness) of the resulting cured product.

  Specific examples of the silane coupling agent (C) having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) -Γ-aminopropyltriethoxysilane, N- (2-aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -γ-aminopropyltriisopropoxysilane, N- (6 -Aminohexyl) -γ-aminopropyltrimethoxysilane, 3- (N- Ethylamino) -2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane, γ -Ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltri Ethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N— And phenylaminomethyltrimethoxysilane.

  The usage-amount of the silane coupling agent (C) which has an amino group is 0.1-20 weight part with respect to 100 weight part of organic polymers (A), Preferably it is 0.5-10 weight part. When the compounding quantity of a silane coupling agent (C) is less than this range, the adhesiveness and physical property improvement effect may not be enough. When the compounding quantity of a silane coupling agent (C) exceeds this range, there exists a tendency for hardened | cured material to become low elongation and there exists a tendency for deep part sclerosis | hardenability to worsen.

  In the present invention, it is preferable to use colloidal calcium carbonate (D). Collagen calcium carbonate has the effect of reducing the cost of the curable composition of the present invention and increasing the strength and hardness (hardness) of the resulting cured product by combining with the organic polymer (A) of the present invention. It is particularly preferable because of having it. The colloidal calcium carbonate (D) preferably has an average particle size of 0.5 μm or less and the particle surface is treated with a fatty acid or a fatty acid salt.

  The amount of colloidal calcium carbonate (D) used is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the organic polymer (A). If the amount of colloidal calcium carbonate (D) is below this range, the physical property improving effect may not be sufficient. When the compounding amount of the colloidal calcium carbonate (D) exceeds this range, the cured product tends to have a low elongation, and it tends to be a highly viscous composition, resulting in poor workability.

  A filler other than the colloidal calcium carbonate (D) can be added to the composition of the present invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, magnesium carbonate, diatomaceous earth, Baked clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride resin organic micro Examples thereof include fillers such as balloon, PVC powder, PMMA powder and the like; resin fillers such as asbestos, glass fibers and filaments. Among these, heavy calcium carbonate is preferable because of its excellent balance between cost and physical properties of the cured product.

Moreover, silane coupling agents other than the silane coupling agent (C) which has an amino group can be added to the composition of this invention. Specific examples of the silane coupling agent other than the silane coupling agent having an amino group include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, and γ-isocyanatepropylmethyl. Silanes having an isocyanate group such as dimethoxysilane, trimethoxysilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate; ketimines such as N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Silanes: γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane , Silanes having a mercapto group such as mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane and other silanes having an epoxy group; β-carboxyethyltriethoxysilane, β-carboxy Carboxysilanes such as ethylphenylbis (2-methoxyethoxy) silane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltrieth Silanes having vinyl type unsaturated groups such as silane, methacryloyloxymethyltrimethoxysilane; silanes having halogen such as γ-chloropropyltrimethoxysilane; isocyanurates such as tris (3-trimethoxysilylpropyl) isocyanurate Silanes etc. can be mentioned. In addition, derivatives obtained by modifying these can also be used as silane coupling agents.

  Specific examples of the adhesion imparting agent other than the silane coupling agent include, for example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like. The adhesiveness-imparting agent may be used alone or in combination of two or more.

  A plasticizer can be added to the curable composition of the present invention. The plasticizer has a function of adjusting the viscosity and slump property of the curable composition and a function of adjusting mechanical properties such as tensile strength and elongation property of the obtained cured product.

  Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, etc. Non-aromatic dibasic acid esters; aliphatic esters such as butyl oleate and methyl acetylricinoleate; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffins Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate, polyethylene glycol, polypropylene glycol, Polyether polyol or hydroxyl ester groups of these polyether polyols such as polytetramethylene glycol, polyethers such as derivatives obtained by converting such an ether group.

  Among these, polypropylene glycol, di (2-ethylhexyl) phthalate, diisodecyl phthalate, and the like are preferable from the viewpoint of compatibility with the organic polymer (A), mechanical properties, cost, and the like.

  These plasticizers may be blended alone or in combination of two or more. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

  The amount of the plasticizer is preferably 1 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A). If it is less than 1 part by weight, the effect as a plasticizer tends not to be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  In addition to these plasticizers, a polymer plasticizer can be added. Compared with the addition of a low molecular weight plasticizer, which is a plasticizer that does not contain a polymer component in the molecule, the curable composition can maintain the initial characteristics over a long period of time. The effect of improving the drying property (also referred to as paintability) when an alkyd paint is applied to the cured product is exhibited.

  The polymer plasticizer is not particularly limited, and vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Polyester plasticizers obtained from dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; polystyrene and poly Polystyrenes such as -α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.

  Among these polymer plasticizers, vinyl polymers are preferred because of their high compatibility with the organic polymer (A) and good weather resistance and heat resistance of the resulting cured products. Among them, acrylic polymers are preferred. Polymers and / or methacrylic polymers are more preferred, and acrylic polymers such as polyacrylic acid alkyl esters are particularly preferred.

  The method for producing the polyacrylic acid alkyl ester is not particularly limited, but a living radical polymerization method is preferable and an atom transfer radical polymerization method is more preferable because the molecular weight distribution is narrow and viscosity can be reduced. Further, a method of continuous bulk polymerization of an alkyl acrylate ester compound disclosed in JP-A No. 2001-207157 called SGO process under high temperature and high pressure is particularly preferable.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, 800 to 10,000, more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, and 1,000 to Most preferred is 3,000. If the molecular weight of the polymer plasticizer is too low, the plasticizer will flow out from the cured product over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time, which may cause contamination due to dust adhesion. Yes, alkyd paintability tends to be inferior. On the other hand, if the molecular weight is too high, the viscosity of the curable composition tends to be high and workability tends to be poor.

  The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow, less than 1.80, preferably 1.70 or less, more preferably 1.60 or less, further preferably 1.50 or less, and 1.40 or less. Is particularly preferred, with 1.30 or less being most preferred.

  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 may or may not have a reactive silicon group in the molecule, but when a polymer plasticizer having a reactive silicon group was added, the polymer plasticizer was incorporated into the curing reaction and obtained. This is preferable because migration of the plasticizer from the cured product can be prevented.

  As the polymeric plasticizer having a reactive silicon group, the average number of reactive silicon groups per molecule is preferably 1 or less, and more preferably 0.8 or less. When adding a plasticizer having a reactive silicon group, particularly an oxyalkylene polymer having a reactive silicon group, the number average molecular weight should be lower than that of the organic polymer (A) in order to obtain a sufficient plasticizing effect. preferable.

  Only one type of polymer plasticizer may be added, or a plurality of types may be added in combination. Moreover, you may add together a low molecular plasticizer and a high molecular plasticizer. In addition, you may add these plasticizers at the time of manufacture of an organic polymer (A).

  The amount of the polymer plasticizer added is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A). If it is less than 5 parts by weight, the effect as a plasticizer tends not to be expressed, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  If necessary, a silicate may be added to the curable composition of the present invention. The silicate acts as a crosslinking agent for the organic polymer (A) and has a function of improving the restoration property, durability, and creep resistance of the obtained cured product.

  Further, by adding silicate, the obtained cured product is improved in adhesion and water-resistant adhesion and adhesion durability under high temperature and high humidity. The silicate is not particularly limited, and examples thereof include tetraalkoxysilane or a partial hydrolysis condensate thereof. More specifically, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxy Tetraalkoxysilanes (tetraalkyl silicates) such as triethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, and , And their partial hydrolysis condensates.

  When adding silicate, 0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.5-10 weight part is more preferable.

  The partially hydrolyzed condensate of tetraalkoxysilane is not particularly limited, and examples thereof include a product obtained by adding water to tetraalkoxysilane and partially hydrolyzing and condensing it.

  It is preferable to add a partially hydrolyzed condensate of tetraalkoxysilane because the effect of improving the restorability, durability, and creep resistance of the resulting cured product is greater than the curable composition to which tetraalkoxysilane is added. .

  As the partially hydrolyzed condensate of tetraalkoxysilane, for example, methyl silicate 51, ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.) and the like are commercially available, and these can be used as additives.

For the purpose of preventing the surface curability of the curable composition from being changed by storage, the silicate is a reactive silicon group in which a hydrolyzable group bonded to a silicon atom is present in the organic polymer (A). It is preferable to select the same type as the hydrolyzable group. That is, when the organic polymer (A) has a methoxysilyl group, a silicate having a methoxysilyl group is selected. When the organic polymer (A) has an ethoxysilyl group, a silicate having an ethoxysilyl group is selected. Is preferred.

  A tackifier may be added to the curable composition of the present invention as necessary.

  The tackifying resin is not particularly limited as long as it is normally used regardless of whether it is solid or liquid at room temperature. For example, a styrene block copolymer, a hydrogenated product thereof, a phenol resin, a modified phenol resin (For example, cashew oil modified phenolic resin, tall oil modified phenolic resin, etc.), terpene phenolic resin, xylene-phenolic resin, cyclopentadiene-phenolic resin, coumarone indene resin, rosin resin, rosin ester resin Resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer resin, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.) , Hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin, etc.Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The styrenic block copolymer and its hydrogenated product are not particularly limited. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene. Examples include butylene-styrene block copolymer (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), and styrene-isobutylene-styrene block copolymer (SIBS).

  When the tackifier is added, the addition amount is preferably 5 to 1,000 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In the curable composition of the present invention, if necessary, a solvent or diluent other than the purpose for dissolving the dimethyltin catalyst (B) may be added. Solvents and diluents are not particularly limited. For example, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers Etc. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  When a solvent or diluent is added, the boiling point of the solvent or diluent is preferably 150 ° C. or higher, preferably 200 ° C. or higher, in order to prevent the diffusion of volatile components into the air when the curable composition is used indoors. Is more preferable.

  You may add a physical property modifier to the curable composition of this invention as needed. The physical property modifier has a function of adjusting the tensile properties and hardness of the cured product to be produced.

  The physical property modifier is not particularly limited, and examples thereof include alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropeno Alkylisopropenoxysilanes such as xysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethyl Methoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethyl Alkoxysilanes having a functional group such as Kishishiran; silicone varnishes; polysiloxanes and the like, it may be added only one kind, may be a more mixed added.

  Among the physical property modifiers, those that produce a compound having a monovalent silanol group in the molecule by hydrolysis are preferred because they have an action of reducing the modulus without deteriorating the stickiness of the surface of the resulting cured product, Among these, those that generate trimethylsilanol by hydrolysis are more preferable.

The compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis is not particularly limited. For example, compounds disclosed in JP-A-5-117521, and alkyls such as hexanol, octanol, decanol, etc. Derivatives of alcohols, compounds that produce an organosilicon compound represented by R ₃ SiOH such as trimethylsilanol by hydrolysis, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc. disclosed in JP-A-11-241029 And polyhydric alcohol derivatives having 3 or more hydroxyl groups in one molecule thereof, and compounds that generate an organosilicon compound represented by R ₃ SiOH such as trimethylsilanol by hydrolysis.

Further, a derivative of an oxypropylene polymer disclosed in JP-A-7-258534, which generates an organosilicon compound represented by R ₃ SiOH such as trimethylsilanol by hydrolysis, and further JP-A-6-279893. And a group having a silicon group capable of forming a compound having a monovalent silanol group by hydrolysis and a group having a crosslinkable hydrolyzable silicon disclosed in (1).

  When adding a physical property modifier, the addition amount is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  If necessary, a thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention. The thixotropy-imparting agent means one having a function of preventing the curable composition from sagging and improving workability.

  The thixotropic 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. Further, rubber powder having a particle size of 10 to 500 μm disclosed in JP-A-11-349916 and organic fibers disclosed in JP-A-2003-155389 are exemplified. One of these thixotropic agents (anti-sagging agents) may be added, or a plurality of them may be added in combination.

  When the thixotropic agent is added, the addition amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In the curable composition of this invention, you may add the compound which has an epoxy group in 1 molecule as needed. By adding a compound having an epoxy group, the restorability of the obtained cured product can be enhanced.

  The compound having an epoxy group is not particularly limited, and examples thereof include epoxidized unsaturated fats and oils; epoxidized unsaturated fatty acid esters; alicyclic epoxy compounds; compounds such as epichlorohydrin derivatives; and mixtures thereof. It is done. More specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is preferred.

When adding an epoxy compound, as the addition amount, 0.5-50 weight part is preferable with respect to 100 weight part of organic polymers (A).

  In the curable composition of this invention, you may add a photocurable substance as needed. The photo-curing substance is a substance in which the molecular structure undergoes a chemical change in a short time by the action of light, causing a change in physical properties such as curing. When a photocurable substance is added to the curable composition, a film of the photocurable substance is formed on the surface of the resulting cured product, and the stickiness and weather resistance of the cured product are improved.

  The photo-curing substance is not particularly limited, and examples thereof include organic monomers, oligomers, resins or compositions containing them, such as unsaturated acrylic compounds, polyvinyl cinnamates, or azidation. Examples thereof include resins.

  Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or more acrylic or methacrylic unsaturated groups in one molecule. Specific examples thereof include propylene (or butylene, ethylene). ) Monomers such as glycol di (meth) acrylate and neopentyl glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. More specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; M-305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400 (all Aronix made by Toa Gosei Co., Ltd.) ) Etc. Among these, a compound having an acrylic functional group is preferable, and a compound having an average of 3 or more acrylic functional groups in one molecule is more preferable.

  Examples of the polyvinyl cinnamate include a photosensitive resin having a cinnamoyl group as a photosensitive group, a compound obtained by esterifying polyvinyl alcohol with cinnamic acid, and many other polyvinyl cinnamate derivatives.

  The azide resin is known as a photosensitive resin having an azido 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). (Nippon Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), there are detailed examples. These are used alone or in combination, and a sensitizer is added as necessary. be able to.

  Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect.

  When adding a photocurable substance, 0.1-20 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.5-10 weight part is more preferable. If it is 0.1 parts by weight or less, there is almost no effect of improving the weather resistance of the obtained cured product, and if it is 20 parts by weight or more, the obtained cured product tends to be too hard and tends to crack.

  If necessary, an oxygen curable material may be added to the curable composition of the present invention. An oxygen curable substance can be cured by reacting with oxygen in the air. By adding an oxygen curable substance, a cured film is formed near the surface of the resulting cured product, and the surface of the cured product becomes sticky. And can prevent adhesion of dust and dust.

The oxygen curable substance is not particularly limited as long as it is a compound having an unsaturated compound capable of reacting with oxygen in the air. For example, dry oils such as drill oil and linseed oil, and various types obtained by modifying the compound Alkyd resin; acrylic polymer modified with drying oil, epoxy resin, silicone resin; obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene -Liquid polymers such as polybutadiene, 1,4-polybutadiene, and C5 to C8 diene polymers; vinyl compounds such as acrylonitrile and styrene copolymerizable with these diene compounds, diene compounds, and diene compounds. Liquid copolymers such as NBR and SBR obtained by copolymerization to become the main component, and further Seed modified product (maleic modifications thereof, such as boiled oil modified product) are and the like. Of these, drill oil and liquid diene polymers are preferred. Only one kind of oxygen curable substance may be added, or a plurality of kinds may be added in combination.

  Note that the effect of the oxygen curable substance may be enhanced by adding a catalyst or a metal dryer that accelerates the curing reaction. The catalyst and the metal dryer that accelerate the curing reaction are not particularly limited, and examples thereof include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds. .

  When the oxygen curable substance is added, the addition amount is preferably 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). When the amount added is less than 0.1 parts by weight, the resulting cured product has a tendency to improve the stain resistance, and when it exceeds 20 parts by weight, the tensile properties of the resulting cured product tend to be impaired.

  Further, the oxygen curable substance is preferably mixed with a photocurable substance as disclosed in JP-A-3-160053.

  You may add antioxidant in the curable composition of this invention as needed. By adding an antioxidant, the heat resistance of the resulting cured product can be increased.

  The antioxidant is not particularly limited, and examples thereof include hindered phenol type, monophenol type, bisphenol type, and polyphenol type antioxidants. Of these, hindered phenol antioxidants are preferred. In addition, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals 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 Sankyo Lifetech Co., Ltd.) And hindered amine light stabilizers such as Specific examples of the antioxidant are also disclosed in JP-A-4-283259 and JP-A-9-194731.

  When adding antioxidant, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.2-5 weight part is more preferable.

  If necessary, a light stabilizer may be added to the curable composition of the present invention. Addition of the light stabilizer can prevent photooxidation deterioration of the obtained cured product.

  The light stabilizer is not particularly limited, and examples thereof include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Of these, hindered amine light stabilizers are preferred.

When adding a light stabilizer, the addition amount is preferably 0.1 to 10 parts by weight and more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the organic polymer (A). Specific examples of the light stabilizer are also disclosed in JP-A-9-194731.

  When a photocurable material such as an unsaturated acrylic compound is added to the curable composition of the present invention, a hindered amine light stabilizer having a tertiary amine group is added as disclosed in JP-A-5-70531. The addition is more preferable because the storage stability of the curable composition is improved.

  The hindered amine light stabilizer having a tertiary amine group is not particularly limited. For example, Tinuvin 622LD, Tinuvin 144, CHIMASSORB 119FL (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.); ADK STAB LA-57, LA- 62, LA-67, LA-63 (all are manufactured by ADEKA Corporation); Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all above Sankyo Lifetech Co., Ltd.) Manufactured).

  In the curable composition of this invention, you may add a ultraviolet absorber as needed. By adding the ultraviolet absorber, the surface weather resistance of the obtained cured product is improved.

  The ultraviolet absorber is not particularly limited, and examples thereof include benzophenone series, benzotriazole series, salicylate series, substituted tolyl series and metal chelate series compounds.

  Of these, benzotriazole-based ultraviolet absorbers are preferred.

  When adding a ultraviolet absorber, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the addition amount, 0.2-5 weight part is more preferable.

  The antioxidant, light stabilizer and ultraviolet absorber are preferably added together in the curable composition. For example, phenolic or hindered phenolic antioxidants, hindered amine light stabilizers and benzotriazole ultraviolet rays. It is preferable to mix and add an absorbent.

  You may add a flame retardant to the curable composition of this invention as needed. It does not specifically limit as a flame retardant, For example, you may add flame retardants, such as phosphorus flame retardants, such as ammonium polyphosphate and tricresyl phosphate; Aluminum hydroxide, magnesium hydroxide, and thermally expansible graphite. Only one type of flame retardant may be added, or multiple types may be added in combination.

  When adding a flame retardant, as the addition amount, 5-200 weight part is preferable with respect to 100 weight part of organic polymers, and 10-100 weight part is more preferable.

  In the curable composition of the present invention, various additives other than those described above may be added as necessary for the purpose of adjusting various physical properties of the curable composition or the obtained cured product. Such additives include, for example, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, anti-anticides, Examples include fungicides. Specific examples thereof are disclosed in JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and the like. ing. Moreover, these additives may add only 1 type and may add it in combination of multiple types.

The curable composition is desirably a one-component curable composition. The reason for this is that the present invention is a composition having a fast surface curability, and therefore it is necessary to construct the final shape at an early stage. Therefore, it is preferable to store in a moisture-proof container such as a cartridge and take it out of the container when used to react with moisture in the air so that curing proceeds. In the case of a two-component type or a multi-component type, it takes time to mix each component, and since curing proceeds during stirring, the adhesiveness and tensile properties of the cured product after construction may deteriorate.

  When the curable composition is a one-component type, since all the ingredients are pre-blended, curing may proceed during storage if moisture is present in the blend. Therefore, it is preferable to add the moisture-containing blending component after dehydrating and drying in advance, or dehydrating it during decompression or the like during blending and kneading.

  When the curable composition is a two-component type or a multi-component type, it is not necessary to add a curing catalyst to the main agent containing an organic polymer having a reactive silicon group, so that the formulation contains some moisture. However, there is little concern about the progress of curing (gelation), but when long-term storage stability is required, dehydration and drying are preferred.

  As the dehydration and drying method, use heat drying method or vacuum dehydration method when the compound is a solid such as powder, and use vacuum zeolite dehydration method or synthetic zeolite, activated alumina, silica gel, quick lime, magnesium oxide, etc. The dehydration method is preferred. Further, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxy An alkoxysilane compound such as silane; an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine; or an isocyanate compound added to the curable composition, A dehydration method performed by reacting with water contained therein is also preferable. Thus, the storage stability of a curable composition improves by addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound.

  As an addition amount when using an alkoxysilane compound that can react with water such as vinyltrimethoxysilane for the purpose of drying, 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the organic polymer (A). 0.5-10 weight part is more preferable.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described compounding components are prepared and kneaded using a mixer, roll, kneader, or the like at room temperature or under heating, and a suitable solvent. A known method such as a method in which a small amount is used and the compounding components are dissolved and then mixed can be employed.

  As a method for producing a one-component curable composition, a filler such as calcium carbonate and a pigment such as titanium dioxide or carbon black are respectively weighed and heated under a temperature of about 70 to 120 ° C. or stirred under reduced pressure. The water contained in each component is removed. An organic polymer (A), an anti-aging agent, a thixotropic agent, etc. are weighed and added thereto, and mixed with stirring. At this time, moisture removal is promoted by heating at about 70 to 120 ° C. and reducing the pressure. Next, a liquid material such as a plasticizer and a dehydrating agent is added and mixed. Thereafter, an adhesion-imparting agent such as aminosilane or epoxysilane and a dimethyltin catalyst (B) are added and mixed well to obtain a uniform state, and then low-boiling compounds and bubbles are removed under reduced pressure conditions. A small amount of the curable composition thus obtained is taken out and the curing time is measured. When the curing time is a predetermined value, a curable composition is obtained by filling a moisture-proof container such as a cartridge without a gap.

As a method for producing a two-component curable composition, an organic polymer (A), a filler such as calcium carbonate, a plasticizer, an anti-aging agent, a pigment, and an adhesion-imparting agent are weighed and put into a mixer or the like. , Mix and disperse. In order to disperse well, it may be heated. In order to remove bubbles, the pressure is reduced and the dispersibility is inspected before filling into a predetermined container. This is a component called a base. Note that the container filled with the base material does not require strict moisture resistance. As the curing agent, a plasticizer and a filler such as calcium carbonate are mixed and dispersed in an apparatus capable of stirring and mixing. Thereafter, the dimethyltin catalyst (B) is weighed and added, mixed and dispersed, and then defoamed under reduced pressure. Then, although it fills a specific container, in the case of a hardening | curing agent, it preserve | saves on the conditions which do not touch air. The colorant is a component called a toner, and a plasticizer and a pigment are weighed and put into an apparatus, and mixed and dispersed. After inspecting for a desired color, a specific container is filled. When using a two-component curable composition, mix the above base, curing agent, and colorant in a predetermined ratio, and stir and mix thoroughly to make all components uniform. Use after defoaming.

  The solid dimethyltin catalyst (B) is preferably dissolved in advance by stirring and mixing with an appropriate organic solvent. When an organic solvent having a high boiling point is used, it remains in the cured product for a long period of time as a plasticizer after being applied as a sealing material or an adhesive. On the other hand, when an organic solvent having a low boiling point is used, it is removed as vapor in the final defoaming step of the curable composition manufacturing step. When chlorinated solvents such as chloroform and methylene chloride are used, these organic solvents generally have a low boiling point. Therefore, they are removed from the curable composition by reducing the pressure while stirring at 30 to 60 ° C. The

  When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.

  The curable composition of the present invention comprises: an adhesive; a sealing material for buildings, ships, automobiles, roads, etc .; an adhesive; a waterproofing material; a mold taking agent; a vibration isolating material; It is preferably used as a spraying material, and among these applications, the resulting cured product is excellent in flexibility and adhesiveness, so that it is more preferably used as a sealing material, an adhesive, or a waterproofing material. preferable.

  In addition, the curable composition of the present invention includes an electric / electronic component material such as a solar cell back surface sealing material; an electric insulating material such as an insulating coating material for electric wires and cables; an elastic adhesive; a contact type adhesive; Materials; Crack repair materials; Tiling adhesives; Powder coatings; Cast materials; Medical rubber materials; Medical adhesives; Medical equipment seal materials; Food packaging materials; Sealing materials for exterior materials such as siding boards Coating materials; primers; conductive materials for shielding electromagnetic waves; thermal conductive materials; hot melt materials; potting agents for electrical and electronic use; films; gaskets; various molding materials; and meshed glass and laminated glass end faces (cut parts) It can be used for various applications such as a sealing material for rust prevention and waterproofing; a liquid sealant used in automobile parts, electrical parts, various machine parts and the like.

  In addition, 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, so it can be used as various types of sealing compositions and adhesive compositions. It is.

  Further, the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, Adhesives for vehicle panels, Adhesives for electrical / electronic / precision equipment assembly, Sealing materials for direct glazing, Sealing materials for double glazing, Sealing materials for SSG construction methods, Sealing materials for working joints of buildings, Waterproofing materials Can also be used.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Synthesis Example 1)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of polyoxypropylene diol having a molecular weight of about 2,000 and polyoxypropylene triol having a molecular weight of about 3,000 as an initiator. A polypropylene oxide having a number average molecular weight of about 19,000 (polystyrene equivalent molecular weight measured using Tosoh's HLC-8120GPC as the liquid feeding system, TOS-GEL H type as the column, and THF as the solvent). It was. Subsequently, a methanol solution of 1.2 times equivalent of NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. 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 devolatilization under reduced pressure. As described above, a trifunctional polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained. 100 parts by weight of the allyl group-terminated polypropylene oxide was reacted with 1.35 parts by weight of methyldimethoxysilane for 5 hours at 90 ° C. using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. Silyl group-terminated polypropylene oxide (A-1) was obtained. It was confirmed by measuring ¹ H-NMR (measured in CDCl ₃ solvent using JNM-LA400 manufactured by JEOL Ltd.) that the methyldimethoxysilyl group introduction rate at the terminal was 70%.

(Synthesis Example 2)
A 2 L flask was charged with 8.39 g (58.5 mmol) of cuprous bromide and 112 mL of acetonitrile, and heated and stirred at 70 ° C. for 30 minutes in a nitrogen stream. To this was added 17.6 g (48.8 mmol) of diethyl 2,5-dibromoadipate and 224 mL (1.56 mol) of butyl acrylate, and the mixture was further heated and stirred at 70 ° C. for 45 minutes. To this, 0.41 mL (1.95 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. Subsequently, heating and stirring were continued at 70 ° C., and 895 mL (6.24 mol) of butyl acrylate was intermittently added dropwise over 160 minutes from 80 minutes after the start of the reaction. During this period, 1.84 mL (8.81 mmol) of triamine was added. 375 minutes after the start of the reaction, 288 mL (1.95 mol) of 1,7-octadiene and 4.1 mL (19.5 mmol) of triamine were added, followed by continued heating and stirring at 70 ° C., and heating was stopped 615 minutes after the start of the reaction. The reaction solution was diluted with toluene and filtered, and the filtrate was heated under reduced pressure to obtain a polymer [1]. The number average molecular weight of the obtained polymer [1] was 24,000, and the molecular weight distribution was 1.3.

  Under a nitrogen atmosphere, the polymer obtained above, 11.9 g (0.121 mol) of potassium acetate and 900 mL of dimethylacetamide were charged in a 2 L flask, and the mixture was heated and stirred at 100 ° C. for 11 hours. The reaction solution was heated under reduced pressure to remove dimethylacetamide, and toluene was added for filtration. An adsorbent (200 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700PEL) was added to the filtrate, and the mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen stream. After removing the adsorbent by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [2].

In a 1 L pressure-resistant reaction vessel, polymer [2] (648 g), dimethoxymethylhydrosilane (25.5 mL, 0.207 mol), methyl orthoformate (7.54 mL, 0.0689 mol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 3 × 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The mixture was heated and stirred at 100 ° C. for 2 hours. The volatile content of the mixture was distilled off under reduced pressure to obtain a methyldimethoxysilyl-terminated acrylic polymer (A-2). The number average molecular weight of the obtained polymer was 30,000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3. By measuring ¹ H-NMR (the same method as in Synthesis Example 1), it was confirmed that the methyldimethoxysilyl group introduction rate at the terminal was 95%.

(Synthesis Example 3)
Polymerization of propylene oxide using a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to give a number average molecular weight of about 26,000 (polystyrene equivalent molecular weight in the same manner as in Synthesis Example 1) Polypropylene oxide was obtained. A 1.2 times equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide to distill off the methanol, and 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 devolatilization under reduced pressure. Thus, a trifunctional polypropylene oxide having a number average molecular weight of about 26,000 and having an allyl group at the end was obtained. Using 100 parts by weight of the allyl group-terminated trifunctional polypropylene oxide as a catalyst, 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex was reacted with 2.0 parts by weight of trimethoxysilane at 90 ° C. for 5 hours. Trimethoxysilyl group-terminated polypropylene oxide (A-3) was obtained. It was confirmed by measurement of ¹ H-NMR (the same method as in Synthesis Example 1) that the introduction rate of trimethoxysilyl group into the terminal was 78%.

(Synthesis Example 4)
Neostan U-360, which is a mercaptotin-based catalyst, is added to 3.3 parts by weight of γ-isocyanatopropyltrimethoxysilane to 100 parts by weight of Sumika Bayer Urethane, ACLAIM POLYOL 12200 (polypropylene glycol having a number average molecular weight of about 11,000). (Nitto Kasei Co., Ltd.) The reaction was carried out at 90 ° C. for 2 hours in the presence of 30 ppm. The disappearance of the isocyanate group peak (2272 cm ⁻¹ ) was confirmed by IR to terminate the reaction, and trimethoxysilyl-terminated polypropylene oxide (A-4) was obtained. It was confirmed by measurement of ¹ H-NMR (the same method as in Synthesis Example 1) that the introduction rate of trimethoxysilyl group into the terminal was 95%.

(Synthesis Example 5)
Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst using polypropylene glycol as an initiator to obtain polypropylene oxide having a number average molecular weight of about 28,500 (polystyrene equivalent molecular weight in the same manner as in Synthesis Example 1). A 1.2 times equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide to distill off the methanol, and allyl chloride was added to convert the terminal hydroxyl group into an allyl group. 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 devolatilization under reduced pressure. As a result, a bifunctional polypropylene oxide having a number average molecular weight of about 28,500 having an allyl group at the end was obtained. 100 parts by weight of the obtained allyl group-terminated polypropylene oxide was reacted with 0.94 parts by weight of trimethoxysilane for 5 hours at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution containing 3 wt% platinum as a platinum vinylsiloxane complex as a catalyst. Silyl group-terminated polypropylene oxide (A-5) was obtained. It was confirmed by measurement of ¹ H-NMR (the same method as in Synthesis Example 1) that the introduction rate of trimethoxysilyl group into the terminal was 78%.

(Examples 1-4, Comparative Examples 1-6)
In accordance with the formulation shown in Table 1, 100 parts by weight of the silicon group-containing organic polymer (A-1, A-2, A-3, or A-4) obtained in Synthesis Examples 1 to 4, surface-treated colloidal carbonate 120 parts by weight of calcium (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Shiraka Hana CCR), 55 parts by weight of a polypropylene glycol plasticizer having a molecular weight of 3,000 (trade name: Actol P-23, made by Mitsui Takeda Chemical Co., Ltd.) , 20 parts by weight of titanium oxide (Ishihara Sangyo Co., Ltd., trade name: Tyco R-820), 2 parts by weight of a thixotropic agent (trade name: Disparon 6500, manufactured by Enomoto Kasei Co., Ltd.), UV absorber (Ciba・ Weigh up to 1 part by weight of Specialty Chemicals Co., Ltd., trade name: Tinuvin 326), and 1 part by weight of light stabilizer (Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) and mix roughly with a spatula. After, over a period of 3 passes on a three-roll paint, it was a main agent what was well dispersed. To these main agents, dimethyltin bisacetylacetonate (manufactured by Gelest Co., Ltd., trade name: SND4062, melting point 178 ° C.) is added as a silanol condensation catalyst according to the formulation shown in Table 1, or dimethyl A 10% solution of tin bisacetylacetonate dissolved in chloroform was added, or any of dibutyltin bisacetylacetonate) (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-220H) was added. Immediately after the addition of each catalyst, stirring and defoaming were performed using a rotation / revolution mixer (trade name: Awatori Rentaro ARE-250, manufactured by Shinkey Co., Ltd.), and the resulting curable composition The surface curability (skinning time) was evaluated in the following manner. The results are shown in Table 1.

(Examples 5 to 11 and Comparative Examples 7 and 8)
According to the formulation shown in Table 2, the silicon group-containing organic organic polymers (A-1, A-3, A-4) obtained in Synthesis Examples 1, 3, and 4 are used alone or in combination, and the same method as above The main agent was prepared respectively. With respect to these main ingredients, according to the formulation shown in Table 2, 2 parts by weight of vinyltrimethoxysilane (made by Momentive Co., Ltd., trade name: A-171) and γ-aminopropyltrimethoxysilane (made by Momentive Co., Ltd.) Product name: A-1110) 5 parts by weight were added, and as a silanol condensation catalyst, dimethyltin bisacetylacetonate was dissolved in chloroform to make a 10% solution, dimethyltin diversate (manufactured by Gelest Co., Ltd., product) Name: SND4220, melting point −6 ° C.), dimethylhydrothiooleate tin (manufactured by Gelest Co., Ltd., trade name: SND4240, liquid at 23 ° C.) was added. In the same manner as above, a curable composition was prepared to evaluate surface curability, and the results are shown in Table 2.

(Examples 12-14, Comparative Examples 9, 10)
In accordance with the formulation shown in Table 3, 100 parts by weight of the silicon group-containing organic polymer obtained in Synthesis Example 1 or Synthesis Example 5, 120 parts by weight of surface-treated colloidal calcium carbonate (product name: Shiroishi Hana CCR, manufactured by Shiroishi Kogyo Co., Ltd.) Polypropylene glycol plasticizer having a molecular weight of 3,000 (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Actol P-23), 55 parts by weight, titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: Taipei R-820 20 parts by weight, 2 parts by weight of a thixotropic agent (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500), 1 part by weight of an ultraviolet absorber (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Tinuvin 326) , Weigh up to 1 part by weight of light stabilizer (Sankyo Lifetech Co., Ltd., trade name: Sanol LS770), mix roughly with a spatula, Over Kai, it was well dispersed. Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or less, 2 parts by weight of vinyltrimethoxysilane (product name: A-171, manufactured by Momentive Co., Ltd.) as a dehydrating agent, and imparting adhesiveness 3 parts by weight of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (trade name: A-1120, manufactured by Momentive Co., Ltd.) was added and mixed. Thereafter, according to the formulation shown in Table 3, as a silanol condensation catalyst, dimethyltin bisacetylacetonate dissolved in chloroform to give a 10% solution, dibutyltin bisacetylacetonate, dibutyltin dilaurate (three-covalent synthesis ( (Trade name: STANN BL) was added and kneaded, kneaded in a substantially water-free state, and finally depressurized for 5 minutes with stirring. In this step, the chloroform used to dissolve dimethyltin bisacetylacetonate was recovered. Thereafter, the composition was sealed in a cartridge which is a moisture-proof container to obtain a one-component curable composition.

(Surface curability)
Each curable composition was filled in a mold having a thickness of about 5 mm, and the surface was adjusted to a flat surface. This time was set as the curing start time, the surface was touched with a stainless steel microspatula, and the time when the composition did not adhere to the microspatula was measured as the skinning time. The skinning time was measured under conditions of 23 ° C. and 50% RH.

  As another method, tack free time was measured. The same test body as described above was prepared, the surface of the curable composition was touched with a finger, and the time when the composition no longer adhered to the finger was measured as a tack-free time. The conditions for the evaluation are the same as above.

(Viscosity at 23 ° C.)
Each curable composition was filled in a 100 cc container under the conditions of 23 ° C. and 50% RH, and a BS type viscometer manufactured by Tokimec Co., Ltd. 7 was used to measure viscosities at 2 and 10 rpm.

(Deep part curability)
Under conditions of 23 ° C. and 50% RH, each curable composition was filled in a polyethylene tube having a diameter of 12 mm so as not to cause bubbles, and the surface was flattened with a spatula to obtain a test specimen. After standing for 7 days under the same conditions, the cured portion of the surface layer was turned off, the uncured portion was removed cleanly, and the thickness of the cured portion was measured with calipers.

(Elongation properties of cured product)
Each curable composition was filled in a polyethylene mold so as not to contain air bubbles, and cured at 23 ° C. and 50% RH for 3 days, and further at 50 ° C. for 4 days, from a cured sheet having a thickness of 3 mm. This was punched into No. 3 dumbbell mold, and subjected to a tensile test (tensile speed: 200 mm / min) at 23 ° C. and 50% RH, and 50% modulus, 100% modulus, strength at break, and elongation at break were measured.

  As can be seen from Table 1, dimethyltin bisacetylacetonate requires more than 6 hours for the surface to harden when added in powder form, but when used after being dissolved in a suitable organic solvent. Expresses rapid cure within 40 minutes. This achieves surface curability equivalent to that of the dibutyltin catalyst conventionally used. In addition, when added as a powder, fine particles were observed on the surface when the curable composition was used, and it was not uniformly dispersed. When a liquid material is used, there is an advantage that weighing is easy, workability is good, and compatibility is good.

  Further, as can be seen from Table 2, dimethyltin diversate and dimethylhydroxyoleate tin require a surface curability of 6 hours or more when combined with the silicon group-containing organic polymer (A) having two hydrolyzable groups. However, when a silicon group-containing organic polymer having three hydrolyzable groups is combined, the skinning time is within 25 minutes despite the use amount being reduced to 1/10, and the curability is dramatic. Faster.

As can be seen from Table 3, the viscosity, depth curable property, and tensile property of the cured product as a one-component curable composition also showed physical properties comparable to those of conventionally used dibutyltin catalysts.

Claims (12)

An organic polymer containing reactive silicon groups that can be crosslinked by forming siloxane bonds;
The reactive silicon group has the general formula (3):
-Si (R ³ _3-n ) X _n (3)
(In the formula, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a triorganosiloxy group represented by —OSi (R ′) _3. Where R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, X represents a hydroxyl group or a hydrolyzable group, When two or more X are present, they may be the same or different, and n represents an integer of 2 to 3.)
100 parts by weight of an organic polymer (A) whose main chain skeleton is polyoxyalkylene and / or a (meth) acrylic acid ester polymer;
A curable composition containing 0.1 to 10 parts by weight of a dimethyltin catalyst (B),
The dimethyltin catalyst (B) is liquid at 23 ° C., or liquefied with an appropriate organic solvent, and the time until the surface of the curable composition is cured is less than 40 minutes. A curable composition characterized. The curable composition according to claim 1, wherein the main chain skeleton of the organic polymer (A) is a polyoxyalkylene polymer polymerized using a double metal cyanide complex catalyst. 20 to 100% by weight of the organic polymer (A) is represented by the general formula (1):
-SiX ₃ (1)
(In the formula, three X's are each independently a hydroxyl group or a hydrolyzable group, and the three X's may be the same or different.) It is a polymer, The curable composition of Claim 1 or 2 characterized by the above-mentioned. 20 to 100% by weight of the organic polymer (A) is represented by the general formula (2):
—C (═O) —NR ¹ —R ² —SiX ₃ (2)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a divalent hydrocarbon group having 1 to 6 carbon atoms, X is the same as above, and three X are the same, the curable composition according to claim 1 or 2, characterized in that an organic polymer having a group which may be represented by different or may be.). The curable composition according to any one of claims 1 to 4, characterized in that further comprising a silane coupling agent having an amino group (C). Furthermore, colloidal calcium carbonate (D) is included, The curable composition in any one of Claims 1-5 characterized by the above-mentioned. The curable composition according to any one of claims 1 to 6, characterized in that a one-part curable composition. Dimethyl tin catalyst (B) The curable composition according to any one of claims 1 to 7, characterized in that dimethyl tin bis (acetylacetonate). The sealing material which uses the curable composition in any one of Claims 1-8 . The adhesive agent using the curable composition in any one of Claims 1-8 . The waterproof material which uses the curable composition in any one of Claims 1-8 . Hardened | cured material which hardened the curable composition in any one of Claims 1-8 .