JP5476119B2 - Curable composition - Google Patents

Description

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

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

  Among these polymers having a reactive silicon group, polyoxyalkylene polymers and polyisobutylene polymers having a main chain skeleton are disclosed in Patent Document 1 and Patent Document 2, and are already industrially used. Produced and widely used in applications such as sealants, adhesives and paints.

  The curable composition containing an organic polymer having a reactive silicon group uses a silanol condensation catalyst to obtain a cured product. As the silanol condensation catalyst, an organic tin-based catalyst having a carbon-tin bond such as dibutyltin bis (acetylacetonate) or dibutyltin dilaurate is generally widely used. However, in recent years, toxicity of organotin compounds has been pointed out, and development of non-organotin catalysts has been demanded.

  Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, and Patent Document 7 disclose carboxylic acid tin salts and other carboxylic acid metal salts as silanol condensation catalysts.

  Further, it is disclosed that the curability is improved by adding an amine compound as a co-catalyst to these catalysts. Further, in consideration of environmental load, a curing catalyst substantially free of metal is desired. In Patent Document 8, a metal-free silanol condensation catalyst can be obtained by using an amine compound in combination with carboxylic acids. It is disclosed.

  Thus, it is known that curability can be improved by using an amine compound in combination with another silanol condensation catalyst. However, when the non-organotin-based catalyst described in the above patent is used, there is room for improvement in adhesion as compared with the case where the organotin-based catalyst is used.

  On the other hand, although there is almost no disclosure of an example in which an amine compound is used alone as a silanol condensation catalyst, Patent Document 9 discloses a technique using a biguanide compound which is one of amine compounds as a silanol condensation catalyst. However, in a system using a biguanide compound alone as a silanol condensation catalyst, there is a problem that the curable composition may not exhibit practical curability.

  Further, in recent years, as a silanol condensation catalyst, a combination of a compound other than carboxylic acids and an amine compound and a composite system have been studied. Patent Document 10 discloses that an amine compound is Lewis Lewis such as boron trifluoride as a silanol condensation catalyst. A technique used in combination with an acid or a complex thereof is disclosed.

  Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14, Patent Document 15, Patent Document 16, Patent Document 17, Patent Document 18, and Patent Document 19 are obtained by reacting an amine compound with a Lewis acid. And a technique using a Lewis acid amine complex as a silanol condensation catalyst, specifically boron trifluoride 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) complex, Examples include boron trifluoride monoethylamine complex.

  However, even in the combined and composite systems described in the above patents, it cannot be said that the practical properties are sufficient. For example, the curable composition does not exhibit sufficient curability or the resulting cured product has a sticky surface. There was a problem that it might be large.

The stickiness on the surface of the cured product becomes a problem when the curable composition is used for exterior applications such as sealing materials and paints. This is because if the surface of the cured product is sticky, dirt and dust are likely to adhere, and it is difficult to remove the attached dust and dirt by washing. There is a risk of damage.
JP-A-52-73998 JP-A 63-6041 Japanese Patent Laid-Open No. 5-39428 Japanese Patent Laid-Open No. 9-12860 JP 2000-313814 A JP 2000-345054 A JP 2003-206410 A JP-A-5-117519 JP 2005-248175 A JP 2006-199730 A WO2005 / 00751 Publication JP 2006-52168 A JP 2006-52296 A JP 2006-169348 A JP 2006-199721 A JP 2006-199725 A JP 2006-199906 A WO 2004/108774 WO 2006/016568

  The present invention is a curable composition containing an organic polymer having a reactive silicon group, does not contain an organotin-based curing catalyst that has been pointed out as a toxic silanol condensation catalyst, has excellent curability, and is obtained. It is an object of the present invention to provide a curable composition in which the stickiness of the surface of the cured product is suppressed and the mechanical strength is also excellent.

In order to solve the above-mentioned problems, the inventors of the present invention focused on an amine compound used in combination or in combination with a Lewis acid and / or a complex of Lewis acid, and as a result of intensive studies,
An organic compound having a reactive silicon group by using a catalyst in which a guanidine compound having a specific structure described in the following general formula (1) and a Lewis acid and / or a complex of Lewis acid are used in combination or combined as a silanol condensation catalyst The curability of the polymer is greatly improved.
・ By selecting a guanidine compound having a specific structure described in the general formula (1), a catalyst system in which an amine compound and a Lewis acid and / or a complex of Lewis acid are used together or combined has not been solved so far. It can specifically improve the stickiness of the surface of the cured product.
It became clear.

  As a result, a non-organotin curing catalyst that can replace the organotin curing catalyst was found, and the present invention was completed.

  The catalyst in which the guanidine compound is combined with a Lewis acid and / or Lewis acid complex is a Lewis acid guanidine complex obtained by reacting a guanidine compound with a Lewis acid and / or Lewis acid complex in advance. That means.

That is, the present invention
(I). An organic polymer (A) having a silicon group that can be crosslinked by forming a siloxane bond,
General formula (1):
R ¹ N = C (NR ¹ ₂ ) ₂ (1)
(One of the five R ¹ groups is an aryl group. The remaining R ¹ groups are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and a saturated hydrocarbon group. at least is one selected from the group consisting of.) represented by the guanidine compound (B),
And Lewis acid and / or Lewis acid complex (C),
A curable composition comprising,
(II). A complex (C) of the guanidine compound (B) a Lewis acid and / or Lewis acid, curable composition according to (I) containing a Lewis acid guanidine complex consisting (D),
(III). The guanidine compound (B) has the general formula (2):

(The four R ^{1 s} are each independently at least one selected from the group consisting of a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and a saturated hydrocarbon group. Each R ² is at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and an organic group, and a is an integer of 1 to 4. Curable composition according to (I) or (II), which is a guanidine compound represented by:
(IV). Guanidine compound (B) is 1-phenyl guanidine, or 1- (o-tolyl) guanidine down, curable composition according to any one of (I) ~ (III),
(V). The curable composition according to any one of (I) to (IV), wherein the Lewis acid and / or Lewis acid complex (C) comprises a metal halide or a boron halide,
(VI). The curable composition according to any one of (I) to (V), wherein the Lewis acid and / or Lewis acid complex (C) comprises boron trifluoride,
(VII). The main chain skeleton of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. The curable composition according to any one of I) to (VI),
(VIII). The curable composition according to (VII), wherein the polyoxyalkylene polymer is a polyoxypropylene polymer,
(IX). A sealing material comprising the curable composition according to any one of (I) to (VIII),
(X). An adhesive comprising the curable composition according to any one of (I) to (VIII),
About.

  The curable composition of the present invention is excellent in environmental compatibility because it does not contain an organotin-based compound that has recently been pointed out to be toxic. In addition, by using a guanidine compound having a specific structure in combination with or in combination with a Lewis acid and / or Lewis acid complex, it effectively acts as a curing catalyst for an organic polymer having a reactive silicon group and is cured. Provided is a curable composition that is excellent in properties and has a cured product that is less sticky on the surface and also excellent in mechanical strength.

  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 organic polymer (A) has at least one reactive silicon group on average per molecule. Here, the reactive silicon group is an organic group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom.

  The organic polymer (A) having a reactive silicon group has a characteristic that a siloxane bond is formed by a reaction accelerated by a silanol condensation catalyst and is crosslinked.

As the reactive silicon group, the general formula (3):
-SiR ³ _b X ¹ _3-b (3)
(B R ³ is independently 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, and —OSi (R ′) ₃ (R 'Is each independently a hydrocarbon group having 1 to 20 carbon atoms.) Is selected from the group consisting of triorganosiloxy groups (3-b) X ¹ is Each independently represents a hydroxyl group or a hydrolyzable group, and b is an integer of 0 to 2.).

  The curable composition of the present invention uses an organic polymer (A) having a reactive silicon group as a main component, but is a curing catalyst as compared with the one using an inorganic polymer such as polydimethylsiloxane as a main component. Since it has good compatibility with the guanidine compound (B), it has the characteristics of excellent curability and adhesiveness.

  For the same reason, the main chain skeleton of the organic polymer (A) is preferably composed of one or more selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom.

  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, copolyamides composed of a plurality of the above polyamides; polycarbonates by polycondensation from bisphenol A and carbonyl chloride, etc. Organic polymers such as polycarbonate polymers; diallyl phthalate polymers;

  Among these, organic hydrocarbons having saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers in the main chain skeleton. The coalescence (A) is preferable because the glass transition temperature is relatively low and the resulting cured product is excellent in cold resistance.

  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.

  A curable composition mainly composed of an organic polymer having a saturated hydrocarbon polymer, a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer as a main chain skeleton is used as an adhesive or a sealing material. When used as, it is more preferable because there is little migration (contamination) of low molecular weight components to the adherend.

  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) has the general formula (4):
—R ⁴ —O— (4)
(R ⁴ is a linear or branched alkylene group having 1 to 14 carbon atoms).

R ⁴ in the general formula (4) 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 (4) described is not particularly limited, for example, _{-CH 2 O -, - CH 2} CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 _{H 5) O -, - CH} 2 C (CH 3) 2 O -, - CH 2 CH 2 CH 2 CH 2 O-
Etc.

  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 saturated hydrocarbon polymer used as the main chain skeleton of the organic polymer (A) refers to a polymer having substantially no carbon-carbon unsaturated bond other than an aromatic ring in the molecule, It has the characteristics which are excellent in a weather resistance, durability, and moisture barrier property.

  The saturated hydrocarbon polymer is not particularly limited, and (i) a polymer composed of an olefin compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene and isobutylene as a repeating unit, (ii) repeating Examples thereof include a polymer comprising a diene compound such as butadiene and isoprene as a unit, and (iii) a polymer obtained by a method of copolymerizing the diene compound and the olefin compound and then hydrogenating the copolymer. Among these, isobutylene-based polymers and hydrogenated polybutadiene-based polymers are preferable because functional groups are easily introduced at the ends, molecular weight is easily controlled, and the number of terminal functional groups can be adjusted. Is more preferable.

  In the isobutylene polymer, all of the repeating units may be formed from isobutylene, or may be a copolymer with another compound. When an isobutylene-based copolymer is used as the main chain skeleton, a polymer having 50% by weight or more of repeating units derived from isobutylene per molecule is preferable because the rubber properties of the resulting cured product are excellent. % Or more is more preferable, and a polymer having 90 to 99% by weight is particularly preferable.

  The production method of the saturated hydrocarbon polymer is not particularly limited, and various conventionally known polymerization methods can be mentioned. Among these, the living polymerization method which has been developed in recent years is preferable. For example, as a method for producing an isobutylene polymer using the living polymerization method, an inifer polymerization (JP Kennedy et al.) Found by Kennedy et al. J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843).

  In this polymerization method, it is known that various functional groups can be introduced into the molecular terminals, and the resulting isobutylene polymer has a molecular weight distribution of 1.5 or less and a molecular weight of about 500 to 100,000.

  The method for producing the saturated hydrocarbon polymer having a reactive silicon group is not particularly limited, and examples thereof include known methods. For example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, and Japanese Patent Application Laid-Open No. Sho 63-63. Examples thereof include methods disclosed in Japanese Patent No. 254149, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Application Laid-Open No. 1-197509, Japanese Patent No. 2539445, Japanese Patent No. 2873395, Japanese Patent Application Laid-Open No. 7-53882, and the like.

  When the saturated hydrocarbon polymer having a reactive silicon group is blended in the curable composition, only one kind may be blended or a plurality of kinds may be blended in combination.

  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- (methacryloyloxypropyl) trimethoxysilane, γ- (methacryloyloxypropyl) dimethoxymethylsilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoro 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 trimethoxy silane and vinyl triethoxy silane. 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.

  When used for general building applications, the curable composition is required to have low viscosity, and the obtained cured product is required to have low modulus, high elongation, weather resistance, heat resistance, and the like.

  More preferably, the main chain skeleton of the organic polymer (A) is composed of a butyl acrylate compound to satisfy these requirements.

  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, as the ratio of butyl acrylate increases, its good oil resistance tends to be impaired. Therefore, when used in applications where oil resistance is required, the ratio is preferably 40% or less, Furthermore, it is more preferable to make it 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 (5):
^{_{-CH 2 -C (R 5) (}} COOR 6) - (5)
(R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an alkyl group having 1 to 8 carbon atoms), and a repeating unit having an alkyl group having 1 to 8 carbon atoms,
General formula (6):
—CH ₂ —C (R ⁵ ) (COOR ⁷ ) — (6)
(R ⁵ is the same as in the general formula (5), R ⁷ 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 Can be given.

R ⁶ in the general formula (5) 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, and an alkyl group having 1 or 2 carbon atoms is more preferable. Incidentally, R ⁶ contained in the copolymer is not necessarily limited to one kind of alkyl group.

R ⁷ described in the general formula (6) 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 ⁷ 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 (5) and the general formula (6). Here, “substantially” means that the total proportion of the repeating units described in the general formulas (5) and (6) in the copolymer exceeds 50% by weight, and occupies the copolymer. The total proportion of the repeating units described in the general formulas (5) and (6) is preferably 70% by weight or more.

The ratio of the repeating units of the general formulas (5) and (6) present in the copolymer is preferably 95: 5 to 40:60 in a weight ratio (general formula (5): general formula (6)). 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 (5) and (6) 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 (7):
—NR ⁸ —C (═O) — (7)
(R ⁸ 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 of an active hydrogen in a urethane group, a urea group, and a thiourethane group with 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 (8):
_{^{W-R 9 -SiR 10 3-}} c X 2 c (8)
(R ⁹ is a divalent organic group, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. (3-c) R ¹⁰ is a hydrogen atom or an organic group, and c Each X ² is a hydroxyl group or a hydrolyzable group, and c is an integer of 1 to ^3. W is selected from the 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)).

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 (9):
_{^{O = C = N-R 9}} -SiR 10 3-c X 2 c (9)
(R ⁹ , R ¹⁰ , X ² , and c are the same as those in the general formula (8).) 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 described in the general formula (8) is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and γ- (N-phenyl). ) Having amino groups such as aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Silane compounds; silane compounds having a hydroxy group such as γ-hydroxypropyltrimethoxysilane; silane compounds having a mercapto group such as γ-mercaptopropyltrimethoxysilane;

  Furthermore, as the silicon compound described in the general formula (8), 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 (9) 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 (9), a silicon compound described in the general formula (8) disclosed in JP-A No. 2000-119365 (US Pat. No. 6,046,270), an excessive amount Examples include reaction products of polyisocyanate compounds.

  The hydrolyzable group represented by X in the general formula (3) is not particularly limited, and examples thereof include known hydrolyzable groups such as a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, and a ketoximate group. Amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. 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. preferable.

  A hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and when two or more hydrolyzable groups or hydroxyl groups are bonded to a silicon atom in a reactive silicon group. They may be the same or different.

In addition, R ³ described in the general formula (3) is not particularly limited, and examples thereof include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and benzyl groups. And aralkyl groups, and the like. Among these, a methyl group is preferable.

  The reactive silicon group described in the general formula (3) is not particularly limited, and for example, a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diiso Examples thereof include a propoxymethylsilyl group, a methoxydimethylsilyl group, and an ethoxydimethylsilyl group. Of these, a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable, and a trimethoxysilyl group is more preferable because of high activity and good curability.

  In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of good curability and storage stability of the curable composition. A triethoxysilyl group is particularly preferable because the alcohol generated in the hydrolysis reaction of the reactive silicon group is ethanol with high safety.

The method for introducing the reactive silicon group is not particularly limited, and examples thereof include known methods, and examples thereof include the following methods (a) to (c).
(I). A polymer having a functional group such as a hydroxyl group in the molecule is reacted with an organic compound having an active group and an unsaturated group that are reactive with the functional group to obtain a polymer having an unsaturated group. Alternatively, a polymer having an unsaturated group is obtained by copolymerization with an epoxy compound having an unsaturated group. Next, the reaction product obtained is hydrosilylated by allowing hydrosilane having a reactive silicon group to act.
(B). A method of reacting a compound having a mercapto group and a reactive silicon group with an organic polymer having an unsaturated group obtained in the same manner as in the method (a).
(C). A method of reacting an organic polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule with a compound having a reactive functional group and a reactive silicon group.

Among these methods, the method (a) or the method (c) in which the polymer having a hydroxyl group at the terminal is reacted with the compound having an isocyanate group and a reactive silicon group has a relatively short reaction time. Is preferable because a high conversion can be obtained. Moreover, the curable composition which has as a main component the organic polymer which has the reactive silicon group obtained by the method (a) is a curable composition whose main component is the organic polymer obtained by the method (c). The viscosity tends to be lower than that of the composition, and as a result, a curable composition with good workability can be obtained. Further, the organic polymer obtained by the method (b) Since the odor based on mercaptosilane is stronger than the obtained organic polymer, the method (A) is more preferable.
The hydrosilane compound used in the method (a) is not particularly limited. For example, halogenated hydrosilanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyl Alkoxysilanes such as diethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane; methyldiacetoxysilane, phenyl And acyloxyhydrosilanes such as diacetoxysilane; ketoximate hydrosilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoximate) methylsilane. Among these, halogenated hydrosilanes and alkoxyhydrosilanes are preferable, and the resulting curable composition mainly composed of the organic polymer (A) has a moderate hydrolyzability and is easy to handle. More preferred. Among the alkoxyhydrosilanes, it is easily available, and the properties of the curable composition and the cured product (curability, storage stability, elongation properties, tensile strength, etc.) mainly composed of the obtained organic polymer (A). ) Is preferred, methyldimethoxysilane is preferred.
The method for synthesizing (b) is not particularly limited. For example, a compound having a mercapto group and a reactive silicon group is converted into an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical source. Examples thereof include a method for introducing into an unsaturated binding site. The compound having a mercapto group and a reactive silicon group is not particularly limited. For example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldi Examples include ethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane.
The 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 of (c) is not particularly limited, and is disclosed in, for example, JP-A-3-47825. The method that is done. The compound having an isocyanate group and a reactive silicon group is not particularly limited. For example, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldi Examples include ethoxysilane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  A silane compound in which three hydrolyzable groups are bonded to one silicon atom, such as trimethoxysilane, may cause a disproportionation reaction to proceed rapidly. As the disproportionation reaction proceeds, dangerous compounds such as dimethoxysilane are formed.

  However, such disproportionation reaction does not proceed with γ-mercaptopropyltrimethoxysilane or γ-isocyanatopropyltrimethoxysilane. For this reason, when using a group in which three hydrolyzable groups are bonded to one silicon atom, such as a trimethoxysilyl group, it is preferable to use the synthesis method (b) or (c). .

On the other hand, general formula (10):
H- (SiR ¹¹ ₂ O) _n SiR ¹¹ ₂ -R ¹² -SiX ³ ₃ (10)
(Three X ³ are each independently a hydroxyl group or a hydrolyzable group. (2n + 2) R ¹¹ are each independently a hydrocarbon group. R ¹² is a divalent organic group. n is an integer of 0 to 19.), the disproportionation reaction does not proceed. Therefore, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (a), a silane compound represented by the general formula (10) may be used. preferable.

R ¹¹ described in the general formula (10) is not particularly limited as long as it is a hydrocarbon group, and among these, a hydrocarbon group having 1 to 20 carbon atoms is preferable from the viewpoint of availability and cost. A hydrocarbon group having 1 to 8 carbon atoms is more preferable, and a hydrocarbon group having 1 to 4 carbon atoms is particularly preferable.

R ¹² described in the general formula (10) is not particularly limited as long as it is a divalent organic group, and among these, a divalent carbon atom having 1 to 12 carbon atoms from the viewpoint of availability and cost. A hydrogen group is preferable, a divalent hydrocarbon group having 2 to 8 carbon atoms is more preferable, and a divalent hydrocarbon group having 2 carbon atoms is particularly preferable.

  N described in the general formula (10) is an integer of 0 to 19, and among these, 1 is preferable from the viewpoint of availability and cost.

  Examples of the silane compound described in the general formula (10) include 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) propyl]. Examples include -1,1,3,3-tetramethyldisiloxane and 1- [2- (trimethoxysilyl) hexyl] -1,1,3,3-tetramethyldisiloxane.

  As the organic polymer (A) having a reactive silicon group, any polymer having a linear or branched structure in the molecule can be used, and the number average molecular weight is measured by GPC. Is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, particularly preferably from 3,000 to 30,000. If the number average molecular weight is less than 500, the resulting cured product tends to be inferior in elongation characteristics, and if it exceeds 100,000, the curable composition tends to have high viscosity and inferior workability.

  The number of reactive silicon groups contained in one molecule of the organic polymer (A) is preferably 1 or more, and preferably 1.1 to 5 as an average value. If the number of reactive silicon groups contained in the molecule is less than 1 on average, the curable composition tends to be inferior in curability, and the resulting cured product tends not to exhibit good rubber elastic behavior. There is.

  The reactive silicon group may be at the end of the main chain, at the end of the side chain, or at both. In particular, when the reactive silicon group is only at the end of the main chain, the effective network length of the organic polymer component contained in the resulting cured product is increased, so that the rubber exhibits high strength, high elongation, and low elastic modulus. It becomes easier to obtain a cured product.

  The curable composition of the present invention is a Lewis acid and / or Lewis acid guanidine compound (B) represented by the following general formula (1) as a curing catalyst for the organic polymer (A) having a reactive silicon group. It is used in combination with the complex (C), or the Lewis acid guanidine complex (D), which is a reaction product of the guanidine compound (B) and the Lewis acid and / or Lewis acid complex (C), is an essential component.

By using the above-mentioned curing catalyst, while being a non-organotin catalyst that is the subject of the present invention, it is excellent in curability, and the resulting cured product has suppressed surface stickiness, and also in mechanical strength. A curable composition having excellent characteristics can be obtained.
General formula (1):
R ¹ N = C (NR ¹ ₂ ) ₂ (1)
(One of the five R ¹ groups is an aryl group. The remaining R ¹ groups are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and a saturated hydrocarbon group. at least is one selected from the group consisting of.)
Four R ¹ described in the general formula (1) are a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or a saturated hydrocarbon group .

However, in order to obtain a curable composition having good curability, and a cured product obtained having high strength and no stickiness on the surface, 5 R described in the general formula (1) ^{At least one} of 1 needs to be an aryl group.

  The aryl group is not particularly limited, and examples thereof include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2,6-dimethylphenyl group, 2 , 4,6-trimethylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 2,4-dichlorophenyl group, 2,6-dichlorophenyl group, 2-hydroxyphenyl group, 4-hydroxyphenyl group, 2-aminophenyl group 4-aminophenyl group, 2,4-diaminophenyl group, 4- (dimethylamino) phenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 4-sulfonic acid phenyl group, 4-methoxyphenyl group, 4 -Ethoxyphenyl group, 4-benzyloxyphenyl group, 4-phenoxyphenyl group, 4-carboxypheny Group, 4-acetoxyphenyl group, 4-benzoylphenyl group, 4- (ethoxycarbonyl) phenyl group, 4- (phenoxycarbonyl) phenyl group, 4-guanidinophenyl group, 2,4-diguanidinophenyl group, 4- ( Acetylamino) phenyl group, 4- (benzoylamino) phenyl group, 4- (dimethylaminosulfonyl) phenyl group, 2-methyl-4-methoxyphenyl group, 2-methyl-4-nitrophenyl group, 2-methoxy-4 -Guanidinophenyl group, 2-methoxy-4- (acetylamino) phenyl group, naphthyl group, biphenyl group and the like.

  Among these, the phenyl group, the 2-methylphenyl group, 3 because it is easily available, increases the curability of the organic polymer (A), and has a great effect of suppressing stickiness of the surface of the resulting cured product. -A methylphenyl group, 4-methylphenyl group, 4-aminophenyl group or 4-guanidinophenyl group is preferable, and a phenyl group or 2-methylphenyl group is more preferable. Furthermore, for the same reason as described above, the guanidine compound (B) is preferably a compound represented by the following general formula (2).

(The four R ^{1 s} are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or a saturated hydrocarbon group. A R ^{2 s} are a hydrogen atom or a halogen atom. , Hydroxy group, amino group, nitro group, cyano group, sulfonic acid group, or at least one selected from the group consisting of organic groups, a is an integer of 1 to 4.)
Four R ¹ described in the general formula (2) are a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or a saturated hydrocarbon group .

When R ¹ described in the general formula (1) or the general formula (2) is other than an aryl group, the organic polymer (A) is improved in curability, so that a hydrogen atom, an amino group, or a saturated hydrocarbon is used. group rather preferable, hydrogen atom or a hydrocarbon group saturation is particularly preferred. When R ¹ is a saturated hydrocarbon group, it is easily available, and therefore the number of carbon atoms is preferably 1 to 20, and more preferably 1 to 10.

As described above, the guanidine compound (B) needs to be substituted with one aryl group on the guanidyl group . With increase in the number of substitution by an aryl group, since the curability improvement on the organic polymer (A) decreases, you are preferable that the number of aryl groups substituted on the guanidyl group is one.

In general formula (1) or general formula (2) guanidine compounds described, when ^{R 1} is an organic group represented by the ^{-C (= NR 13) -NR 13} 2, called biguanide compounds.

Examples of a R ² described in the general formula (2) include a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, or an organic group. When R ² is an organic group, the organic group is not particularly limited, for example, a saturated or unsaturated hydrocarbon group; one or more hydrogen atoms in the hydrocarbon group are a nitrogen atom, an oxygen atom, sulfur An organic group substituted with a functional group containing one or more selected from atoms; an alkoxy group, a carboxy group, an acyl group, a carbonyl group, an imino group, a sulfonyl group, and the like.

Among these, from the viewpoint of enhancing the curability of the organic polymer (A), a hydrogen atom, an amino group, or an organic group is preferable, a hydrogen atom or a hydrocarbon group is more preferable, and a hydrogen atom or a saturated hydrocarbon group is preferable. Particularly preferred. In the case where R ² is an organic group, the number of carbon atoms is preferably 1 to 20 and more preferably 1 to 10 because it is easily available.

  The number of carbon atoms contained in the guanidine compound (B) is preferably 2 or more, more preferably 6 or more, and particularly preferably 7 or more. When the number of carbon atoms is as small as less than 2 (small molecular weight), the volatility of the compound increases and the working environment tends to deteriorate. The upper limit of the number of carbon atoms contained in the guanidine compound (B) is not particularly required, but is generally preferably 10,000 or less. The molecular weight of the guanidine compound (B) is preferably 60 or more, more preferably 120 or more, and particularly preferably 130 or more for the same reason as described above. The upper limit of the molecular weight is not particularly required, but is generally preferably 100,000 or less.

The guanidine compound (B) is not particularly limited, and examples thereof include 1-phenylguanidine, 1- (o-tolyl) guanidine, 1- (3-methylphenyl) guanidine, 1- (4-methylphenyl) guanidine, 1 -(2-chlorophenyl) guanidine, 1- (4-chlorophenyl) guanidine, 1- (2,3-xylyl) guanidine, 1- (2,6-xylyl) guanidine, 1- (1-naphthyl) guanidine , 1- Phenyl-1-methylguanidine, 1- (4-chlorophenyl) -3- (1-methylethyl) guanidine , 1- (3,4-dichlorophenyl) -3- (1-methylethyl) guanidine, 1- (4- Methylphenyl) -3-octylguanidine, 1,1′-hexamethylenebis [3- (4-chlorophenyl) guanidine], 1- ( -Methoxyphenyl) guanidine, 1,1 '-[4- (dodecyloxy) -m-phenylene] bisguanidine, 1- (4-nitrophenyl) guanidine, 4-guanidinobenzoic acid, 1- (4-chlorophenyl)- 2-cyanoguanidine, 2- (phenylimino) imidazolidine, 2- (5,6,7,8-tetrahydronaphthalen-1-ylamino) -2-imidazoline, N- (2-imidazolin-2-yl) -2 , 3-xylidine, N-(2-imidazolin-2-yl) -1-naphthalenamine, 1,1 '- etc. [methylenebis (p- phenylene)] guanidine bis guanidine compounds.

  These guanidine compounds may be blended in one kind when blended into the curable composition, or may be blended in combination of two or more kinds.

  Among the guanidine compounds, 1-phenylguanidine and 1- (o-tolyl) are easily available, increase the curability of the organic polymer (A), and have a great effect of suppressing stickiness of the cured product surface. Guanidine compounds such as guanidine, 1-phenylbiguanide and 1- (o-tolyl) biguanide are preferred.

  As a compounding quantity of a guanidine compound (B), 0.1-30 weight part is preferable with respect to 100 weight part of organic polymers (A), and 0.1-12 weight part is more preferable. When the blending amount of the guanidine compound (B) is 0.1 to 30 parts by weight, the curable composition has more excellent curability and has an appropriate curing time, and therefore has excellent workability. Become.

  The Lewis acid and / or Lewis acid complex (C) used in combination and / or in combination with the guanidine compound (B) as a curing catalyst is superior to the organic polymer (A) of the guanidine compound (B). It is useful when the curable composition of the present invention is used for an application that has a function of further improving curability and particularly requires fast curability. Furthermore, there is an advantage that the blending amount of the curing catalyst can be reduced.

  The Lewis acid is not particularly limited. For example, titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, copper chloride, antimony chloride, gallium chloride, indium chloride, titanium bromide, tin bromide, Metal halides such as zirconium bromide, aluminum bromide, iron bromide, zinc bromide, copper bromide; and boron halides such as boron trifluoride, boron trichloride, boron tribromide, boron triiodide Metal triflate compounds such as trimethylsilyl trifluoromethanesulfonate, scandium triflate, yttrium triflate, zinc triflate, and the like.

  Among the Lewis acids, titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, and boron trifluoride are preferable because they are easily available and easy to handle. Titanium chloride, zirconium chloride, iron chloride Boron trifluoride is more preferable.

  In addition, the Lewis acid complex is not particularly limited, and examples thereof include the above-mentioned complexes containing Lewis acids, and more specifically, Lewis acid amine complexes, alcohol complexes, ether complexes, and water complexes. .

  The amine compound constituting the amine complex of Lewis acid is not particularly limited, and examples thereof include ammonia, monoethylamine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), pyridine, Examples include piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, and triethanolamine.

  The alcohols constituting the Lewis acid alcohol complex are not particularly limited, and examples thereof include methanol, ethanol, propanol, n-butanol, isopropanol, and 2-butanol.

  Ethers constituting the Lewis acid ether complex are not particularly limited, and examples thereof include dimethyl ether, diethyl ether, n-dibutyl ether, and tetrahydrofuran.

  Among the Lewis acid complexes, boron trifluoride amine complex, boron trifluoride alcohol complex, and boron trifluoride ether complex are preferable because they are easily available and easy to handle. Boron trifluoride ethylamine Complex, boron trifluoride piperidine complex, boron trifluoride methanol complex, boron trifluoride ethanol complex, boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex are more preferred, boron trifluoride diethyl ether complex is particularly preferred preferable.

  The blending amount of the Lewis acid and / or Lewis acid complex (C) is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 12 parts by weight with respect to 100 parts by weight of the organic polymer (A). preferable. When the blending amount of the Lewis acid and / or Lewis acid complex (C) is 0.1 to 30 parts by weight, the curable composition has excellent curability and has an appropriate curing time. Excellent in properties.

  Further, since the effect of suppressing stickiness of the cured product surface is large and the adhesiveness of the cured product is good, the guanidine compound (B) contained in the composition, Lewis acid and / or Lewis acid complex (C) The molar ratio of ((B) :( C)) is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, and 70:30 to 50: 50 is particularly preferred.

  The curable composition of the present invention is a Lewis polymer obtained by previously reacting a guanidine compound (B) with a Lewis acid and / or a Lewis acid complex (C) as a curing catalyst for an organic polymer (A) having a reactive silicon group. It is also desirable to use an acid guanidine complex (D).

  The Lewis acid guanidine complex (D) is formed by reacting the guanidine compound (B) having the specific structure shown above with the Lewis acid and / or Lewis acid complex (C). Specifically, when a guanidine compound is allowed to act on boron trifluoride diethyl ether complex or the like, the boron ether trifluoride guanidine complex is easily formed by the elimination of diethyl ether, and the curing catalyst according to the present invention is formed. Can be obtained.

  If the reactivity of boron trifluoride and other guanidine compounds is poor, or if you want to increase the reactivity, add or add organic solvent such as diethyl ether, methanol, ethanol, hexane, toluene, methylcyclohexane. It is preferable to react by heating. It should be noted that unreacted substances and desorbed substances (such as diethyl ether) remaining in the curing catalyst after completion of the reaction need not be positively removed because they have little influence on the catalyst performance. However, when it is desired to increase the purity of the curing catalyst, it is preferable to remove unreacted and desorbed substances by means such as distillation under reduced pressure.

  Since the effect of suppressing stickiness on the surface of the cured product is large and the adhesiveness of the cured product is good, the guanidine compound (B) and Lewis acid and / or Lewis acid complex (C) for obtaining the Lewis acid guanidine complex (D) ) In terms of molar ratio ((B) :( C)) is preferably 90:10 to 30:70, more preferably 80:20 to 40:60, and 70:30 to Particularly preferred is 50:50.

  Moreover, 0.1-30 weight part is preferable with respect to 100 weight part of organic polymers (A), and, as for the compounding quantity as a Lewis' acid guanidine complex (D), 0.1-12 weight part is more preferable. When the blending amount of the Lewis acid guanidine complex (D) is 0.1 to 30 parts by weight, the curable composition has excellent curability and has an appropriate curing time, and therefore has excellent workability. It becomes.

  The curable composition of the present invention uses a guanidine compound (B) in combination with a Lewis acid and / or Lewis acid complex (C) as a curing catalyst, or a guanidine compound (B) and a Lewis acid and The Lewis acid guanidine complex (D), which is a reaction product of the Lewis acid complex (C), is used. If necessary, other curing catalysts can be added to the extent that the effects of the present invention are not impaired.

  The curing catalyst other than the guanidine compound (B), Lewis acid and / or Lewis acid complex (C), or Lewis acid guanidine complex (D) is not particularly limited. For example, tin carboxylate, lead carboxylate, Bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, carboxylic acid Carboxylic acid metal salts such as cerium; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate), etc. Tan compounds; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyl Tin bis (butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dioctyl tin bis (ethyl maleate), Dioctyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetate) Organic tin compounds such as a reaction product of dibutyltin oxide and silicate compound, a reaction product of dibutyltin oxide and phthalate ester; aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diiso Aluminum compounds such as propoxyaluminum ethyl acetoacetate; Zirconium compounds such as zirconium tetrakis (acetylacetonate); Various metal alkoxides such as tetrabutoxyhafnium; Organic acidic phosphates; Organic sulfonic acids such as trifluoromethanesulfonic acid Inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid;

  When these curing catalysts are used in combination with a guanidine compound (B), a Lewis acid and / or Lewis acid complex (C), or a Lewis acid guanidine complex (D), the catalytic activity is increased, and the curable composition is obtained. It is expected that the deep curability, thin layer curability, and adhesion of the resulting cured product will be improved.

  However, when the organic tin compound is used in combination, the addition of the organic tin compound tends to increase the toxicity of the curable composition, so that the addition amount of the organic tin compound is preferably small. More specifically, the metal tin is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, still more preferably 0.05 parts by weight or less, substantially 100 parts by weight of the organic polymer (A). Most preferably it is not contained.

  The curable composition of the present invention is preferably a non-organotin curable composition for the same reason as described above. In the present invention, the non-organotin-based curable composition is defined as the amount of the organic tin compound added is 50% by weight or less of the total amount of the compound acting as a silanol condensation catalyst. % Or less, more preferably 10% by weight or less, still more preferably 1% by weight or less, and most preferably not contained.

  In addition, when a metal compound other than organic tin is used in combination, it is preferable that the addition amount is small in consideration of the environmental load, and more specifically, 5 parts per 100 parts by weight of the organic polymer (A). The amount is preferably not more than parts by weight, more preferably not more than 2 parts by weight, and particularly preferably substantially not contained.

  The curable composition of the present invention is preferably a non-organotin curable composition, but substantially contains a tin compound such as an organic tin compound or tin carboxylate from the viewpoint of toxicity or environmental load. Non-tin-based curable compositions are more preferable, non-organic tin and non-carboxylic acid metal salt-based curable compositions substantially free of organic tin compounds and various carboxylic acid metal salts are more preferable, Particularly preferred are non-metallic catalyst-based curable compositions that substantially do not contain the metal element-containing curing catalyst such as acid metal salts, titanium compounds, organotin compounds, organoaluminum compounds, and zirconium compounds.

  Moreover, in the curable composition of this invention, a carboxylic acid is added as a co-catalyst as needed so that the effect of invention may not be reduced.

  The carboxylic acid used as a co-catalyst is not particularly limited. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid, undecane. Acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and laxelic acid Saturated fatty acids; Undecylenic acid, Linderic acid, Tuzic acid, Fizeteric acid, Myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-Hexadecenoic acid, Palmitoleic acid, Petroceric acid, Oleic acid, Elaidic acid, Asclepic acid , Vaccenic acid, gadoleic acid, gondoic acid Mono-unsaturated fatty acids such as cetoleic acid, erucic acid, brassic acid, ceracoleic acid, ximenoic acid, lumenic acid, acrylic acid, methacrylic acid, angelic acid, crotonic acid, isocrotonic acid, 10-undecenoic acid; linoelaidic acid, linol Acid, 10,12-octadecadienoic acid, hiragoic acid, α-eleostearic acid, β-eleostearic acid, punicic acid, linolenic acid, 8,11,14-eicosatrienoic acid, 7,10,13 -Docosatrienoic acid, 4,8,11,14-hexadecatetraenoic acid, moloctic acid, stearidonic acid, arachidonic acid, 8,12,16,19-docosatetraenoic acid, 4,8,12,15,18- Polyene unsaturated fatty acids such as eicosapentaenoic acid, sardine acid, nisinic acid, docosahexaenoic acid; 1-methylbutyric acid Isobutyric acid, 2-ethylbutyric acid, isovaleric acid, tuberculostearic 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-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5 -Branched fatty acids such as dimethylhexanoic acid, neodecanoic acid and versatic acid; fatty acids having triple bonds such as propiolic acid, talylic acid, stearolic acid, crepenic acid, ximenic acid and 7-hexadesinic acid; naphthenic acid, Malvalic acid, sterlic acid, hydnocarbic acid, scholmooglic acid, gollulinic acid, 1-methylcyclopentanecarboxylic acid, 1-methylcyclohexane Sun carboxylic acid, 2-methylbicyclo [2.2.1] -5-heptene-2-carboxylic acid, 1-adamantanecarboxylic acid, bicyclo [2.2.1] heptane-1-carboxylic acid, bicyclo [2. 2.2] Alicyclic carboxylic acids such as 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, uniperic acid, ambretoleic acid, aleurit acid, 2-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 18-hydroxyoctadecanoic acid, 9,10- Dihydroxyoctadecanoic acid, ricinoleic acid, camlorenic acid, ricanoic acid, Oxygenated fatty acids such as ferronic acid, cerebronic acid, 2-methyl-7-oxabicyclo [2.2.1] -5-heptene-2-carboxylic acid; chloroacetic acid, 2-chloroacrylic acid, chlorobenzoic acid, etc. And halogen-substituted products of monocarboxylic acids.

  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 cocatalysts together, the catalytic activity of the curing agent is increased, and improvement effects such as curability and deep curability of the curable composition are expected.

  The addition amount of the carboxylic acid 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 polymer (A).

  A silane coupling agent is added to the curable composition of this invention as needed. Here, the silane coupling agent is a compound having a hydrolyzable silicon group and other functional groups in the molecule, and by blending it in the curable composition, adhesion of the resulting cured product to various adherends It shows the effect of improving the property, or the effect of removing (dehydrating) water contained in the curable composition. The silane coupling agent is a compound that can function as a physical property modifier, an inorganic filler dispersibility improving agent, and the like in addition to the above-described effects.

Examples of the hydrolyzable silicon groups present in the silane coupling agent, the general formula (3): - those ^{_{SiR 3 b X 1 3-b}} X 1 described in is a hydrolyzable group, and specific Specifically, the groups already exemplified as the hydrolyzable group can be mentioned. Among these, a methoxy group, an ethoxy group, and the like are preferable because they have an appropriate hydrolysis rate. The number of hydrolyzable groups contained in one molecule of the silane coupling agent is preferably 2 or more, particularly 3 or more.

  Examples of functional groups other than hydrolyzable silicon groups present in silane coupling agents include substituted or unsubstituted amino groups, mercapto groups, epoxy groups, carboxyl groups, vinyl groups, isocyanate groups, isocyanurates, halogens, etc. it can. Among these, a silane coupling agent having a substituted or unsubstituted amino group is particularly preferable in terms of enhancing the adhesion between the obtained cured product and the adherend.

  Furthermore, the curable composition obtained by adding the above-mentioned silane coupling agent to the organic polymer (A) having a reactive silicon group can be stored for a long time in a good state with suppressed increase in viscosity over time. .

  The silane coupling agent is not particularly limited. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Methyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- ( 6-aminohexyl) aminop Pyrtrimethoxysilane, 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-aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylamino Aminosilanes such as methyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N Ketimine type silanes such as-(1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyl Isocyanate silanes such as methyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane; γ-mercaptopropyltrimethoxy Mercaptosilanes such as lan, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane; γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Epoxysilanes such as triethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-amino Carboxysilanes such as propyltrimethoxysilane; vinyl type unsaturation such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane Group-containing silanes; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate; Moreover, the reaction product of the said aminosilanes and epoxysilanes, the reaction product of aminosilanes and isocyanate silanes, etc. can be used. Condensates obtained by partially condensing the silanes can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives of these, can also be used as silane coupling agents. .

  Among the silane coupling agents, γ-aminopropyltrimethoxysilane is particularly preferable from the viewpoint of compatibility, transparency, and availability.

  Only one type of silane coupling agent may be added to the curable composition, or a plurality of types may be added in combination. When selecting a silane coupling agent, the hydrolyzability having the same structure as the hydrolyzable group of the organic polymer (A) is used for the purpose of preventing the surface curability of the curable composition from changing during storage. It is preferable to use one having a group. That is, when the hydrolyzable silyl group of the organic polymer (A) is a methoxysilyl group, the silane coupling agent also has a methoxysilyl group structure, and the hydrolyzable silyl group of the organic polymer (A) is ethoxysilyl. In the case of a group, a silane coupling agent having an ethoxysilyl group structure is also selected.

  When the silane coupling agent is added, the addition amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the organic polymer (A). 7 parts by weight is particularly preferred. When the compounding quantity of a silane coupling agent is less than 0.01 weight part, there exists a tendency for the storage stability of a curable composition to be inferior, and there exists a tendency for the adhesiveness of the hardened | cured material obtained to be inferior. On the other hand, if the blending amount exceeds 20 parts by weight, there is a tendency that practical deep part curability cannot be obtained.

  In the curable composition of this invention, a plasticizer is added as needed. 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.

  The plasticizer is not particularly limited. For example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, bis (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate Non-aromatic dibasic acid esters such as; aliphatic esters such as butyl oleate and methyl acetylricinoleate; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; chlorinated paraffin Hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  In addition, the initial characteristics of the obtained cured product can be maintained over a long period of time, and the drying property (also referred to as paintability) when an alkyd paint is applied to the obtained cured product can be improved. It is preferable to add a polymeric plasticizer. The polymer plasticizer is not particularly limited. For example, vinyl polymers obtained by polymerizing vinyl monomers by various methods; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Esters of polyesters: 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; molecular weight 500 or more, more than 1000 polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like, or these polyether polyols Polystyrenes such as polystyrene and polymethyl -α- methyl styrene; polyethers derivatives hydroxyl group was substituted such as an ester group and an ether group in polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, etc. polychloroprene and the like.

  Among these polymer plasticizers, those having high compatibility with the organic polymer (A) are preferable, and examples thereof include polyethers and vinyl polymers. In addition, polyethers are more preferable because the surface curable property and deep-part curable property of the curable composition are good and the curing delay after storage does not occur. Specifically, polypropylene glycol is particularly preferable.

  In addition, a vinyl polymer is preferred because of high compatibility with the organic polymer (A) and good weather resistance and heat resistance of the resulting cured product. Among them, an acrylic polymer and / or a methacrylic polymer are preferred. Are more preferable, and acrylic polymers such as polyacrylic acid alkyl esters are particularly preferable.

  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 from 500 to 15000 and from 800 to 10,000, more preferably from 1000 to 8000, particularly preferably from 1000 to 5000, and most preferably from 1000 to 3000. 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 plasticizer may be added, or multiple 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).

  When adding a plasticizer, as the addition amount, 5-150 weight part is preferable with respect to 100 weight part of organic polymers (A), 10-120 weight part is more preferable, 20-100 weight part is especially preferable. . 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.

  In the curable composition of the present invention, for example, an epoxy resin, a phenol resin, sulfur, an alkyl titanate, an aromatic polyisocyanate, or the like is added in order to give an adhesion-imparting effect. Only one kind of these may be added, or a plurality of kinds may be added in combination. However, since the epoxy resin tends to decrease the catalytic activity of the guanidine compound (B) as the addition amount increases, the addition amount of the epoxy resin is preferably small. When the epoxy resin is added, the addition amount is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially contains 100 parts by weight of the organic polymer (A). It is particularly preferred not to.

  In the curable composition of this invention, a filler is added as needed. The filler is not particularly limited. For example, reinforcing filler such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate , Colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass micro Examples include balloons, organic microballoons of phenolic resins and vinylidene chloride resins, organic powders such as PVC powder and PMMA powder; and fibrous fillers such as asbestos, glass fibers and filaments.

  When adding a filler, the addition amount is preferably 1 to 250 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the organic polymer (A).

  When the curable composition is used for a one-pack type adhesive and a sealing material, in order to obtain good storage stability, the filler is disclosed in JP-A No. 2001-181532, After uniformly mixing with a dehydrating agent such as calcium oxide, it is preferably added after being dehydrated and dried in advance by enclosing it in a bag made of an airtight material and leaving it for an appropriate time.

  In addition, when the obtained cured product is used for an application requiring transparency, the filler added is a polymer made of a polymer such as methyl methacrylate disclosed in JP-A-11-302527. Powder, amorphous silica and the like are preferable, and hydrophobic silica disclosed in JP 2000-38560 A and the like are more preferable.

  Here, the hydrophobic silica is defined as (-SiO-hydrophobic group) by treating the surface of silicon dioxide fine powder generally occupied by silanol groups (-SiOH) with organosilicon halides or alcohols. Say things. Hydrophobic silica is not particularly limited. For example, silanol groups present on the surface of fine silicon dioxide powder were treated with dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, and the like. Things can be raised. The untreated silicon dioxide fine powder whose surface is occupied by silanol groups (—SiOH) is called hydrophilic silica fine powder.

  Further, when the obtained cured product is used for an application where high strength is required, the filler to be added includes fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, Silicon compounds such as hydrous silicic acid; carbon black, surface-treated fine calcium carbonate, calcined clay, clay, activated zinc white and the like are preferable, and the addition amount is 1 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A). Is preferred.

  Further, when the obtained cured product is used for an application requiring low strength and high elongation, the added filler is calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc. Ferric oxide, zinc oxide, shirasu balloon and the like are preferable, and the addition amount is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A).

  In addition, when adding calcium carbonate, the tendency for improvement in breaking strength, breaking elongation, and adhesiveness of a cured product obtained as the specific surface area increases is increased. One type of these fillers may be added, or a plurality of types may be added in combination.

  Examples of adding a plurality of additives are not particularly limited, and the combined use of calcium carbonate having a large particle size such as surface-treated fine calcium carbonate and heavy calcium carbonate has excellent physical properties of the resulting cured product. This is preferable.

  As the surface-treated fine calcium carbonate, those having a particle diameter of 0.5 μm or less and the particle surface being treated with a fatty acid or a fatty acid salt are preferable.

  Moreover, as calcium carbonate with a large particle size, the particle size is preferably 1 μm or more and the particle surface is not treated.

  When workability (such as sharpness) is required as the curable composition, or when the surface of the resulting cured product is required to be matte, the filler added is preferably an organic balloon or an inorganic balloon. These fillers may be added with or without surface treatment, and only one kind may be added, or a plurality of fillers may be mixed and added. The particle diameter of the balloon is preferably 0.1 mm or less for the purpose of improving workability (such as sharpness), and preferably 5 to 300 μm for the purpose of matting the surface of the cured product.

  The curable composition of the present invention is suitable for ceramics and other siding boards, seals for exterior wall tiles and exterior tiles, adhesives, etc., because the resulting cured product has excellent chemical resistance. used.

  When used in such applications, the resulting cured product is present in portions that appear on the surface, such as joints, so it is desirable that the design of the outer wall and the design of the cured product harmonize. Particularly in recent years, high-quality outer walls such as spatter coating and colored aggregates have been used, and the importance of the design of cured products has increased.

  In order to obtain a high-quality design, a scaly or granular substance is added to the curable composition of the present invention. Here, when a granular substance is added, the surface becomes sandy or sandstone-like rough, and when a scaly substance is added, it becomes an uneven surface due to scaly.

  In addition, since the obtained hardened | cured material is in harmony with a high-quality outer wall and is excellent in chemical resistance, the appearance with a high-class feeling has the characteristic of lasting for a long time.

  The scale-like or granular substance is not particularly limited, and examples thereof include those disclosed in JP-A-9-53063. The diameter is appropriately selected according to the material and pattern of the outer wall, but is 0.1 mm. The above is preferable, and 0.1 to 5.0 mm is more preferable. In the case of a scaly substance, the thickness is preferably 1/10 to 1/5 (0.01 to 1.00 mm) of the diameter.

  The addition amount of the scaly or granular substance is appropriately selected depending on the size of the scaly or granular substance, the material of the outer wall, the pattern, etc., but is 1 to 200 weights with respect to 100 parts by weight of the curable composition. Part is preferred.

  The material of the scaly or granular substance is not particularly limited, and examples thereof include natural products such as silica sand and mica, and inorganic materials such as synthetic rubber, synthetic resin, and alumina, which are filled in joints and the like. In order to improve the designability at the time, it may be appropriately colored in accordance with the material and pattern of the outer wall.

  A preferable finishing method is disclosed in JP-A-9-53063.

  The scaly or granular substance may be mixed in advance in the curable composition, or may be mixed with the curable composition at the time of use.

  For the same purpose, a balloon (preferably having an average particle diameter of 0.1 mm or more) can be added to the curable composition, and the resulting curing agent has a sanding tone or sandstone tone. It becomes a certain surface and can achieve weight reduction. The balloon is a spherical filler with a hollow inside.

  The balloon is not particularly limited. For example, JP-A-10-251618, JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113073. , JP-A-9-53063, JP-A-2000-154368, JP-A-2001-164237, WO97 / 05201, and the like.

  Examples of the material of the balloon include inorganic materials such as glass, shirasu, and silica; and organic materials such as phenol resin, urea resin, polystyrene, and saran. In addition, a composite material of an inorganic material and an organic material; a laminated material including a plurality of layers can be given. These may use only 1 type and may add in combination of multiple types.

  In addition, as balloons, those whose surfaces are coated and those treated with various surface treatment agents can be used. As specific examples, organic balloons are made of calcium carbonate, talc, titanium oxide or the like. Examples thereof include a coated one, and an inorganic balloon surface-treated with an adhesion-imparting agent.

  Furthermore, the particle size of the balloon is preferably 0.1 mm or more, more preferably 0.2 mm to 5.0 mm, and particularly preferably 0.5 mm to 5.0 mm. If it is less than 0.1 mm, even if it is added in a large amount, only the viscosity of the composition is increased, and the obtained cured product may not exhibit a rough feeling.

  In the case of adding a balloon, the amount added can be appropriately selected depending on the intended design, but a volume concentration of 5 to 25 vol% in a curable composition is used when the particle size is 0.1 mm or more. It is preferable to add so that it may become, and it is more preferable to add so that it may become 8-22 vol%. When the volume concentration of the balloon is less than 5 vol%, the feeling of roughness tends to be lost, and when it exceeds 25 vol%, the viscosity of the curable composition tends to increase and workability tends to deteriorate. Moreover, the modulus of the cured product obtained is increased, and the basic performance of the sealing material and the adhesive tends to be impaired.

  When adding the balloon, the anti-slip agent as disclosed in JP-A-2000-154368, the surface of the resulting cured product as disclosed in JP-A-2001-164237 is added, It can be added in combination with a matte amine compound. The amine compound is preferably a primary and / or secondary amine having a melting point of 35 ° C. or higher.

  In addition, as a balloon, the thermally expansible fine particle hollow body currently disclosed by Unexamined-Japanese-Patent No. 2004-51701 or 2004-66749 etc. can also be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylidene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape.

  By adding a thermally expandable fine hollow body to the curable composition of the present invention, it can be easily peeled off without destroying the adherend when it is no longer needed, and an organic solvent. An adhesive composition that can be removed by heating without using any is obtained. This is because the gas pressure in the shell of the thermally expandable fine hollow body increases by heating the adhesive part, and the polymer outer shell material softens and expands dramatically, thereby peeling the adhesive interface. .

  Even when the sealing material cured product particles are included in the curable composition of the present invention, the obtained cured product can form irregularities on the surface and improve the design. A preferable diameter, blending amount, material, and the like of the cured sealant particles are disclosed in JP-A No. 2001-115142, and the diameter is preferably 0.1 mm to 1 mm, more preferably 0.2 to 0.5 mm. 5-100 weight part is preferable with respect to 100 weight part of curable compositions, and, as for the compounding quantity, 20-50 weight part is more preferable. The material is not particularly limited as long as it is used for a sealing material, and examples thereof include urethane resin, silicone, modified silicone, and polysulfide rubber. Among these, modified silicone-based sealant cured particles are preferable.

  A silicate is added to the curable composition of this invention as needed. The silicate acts as a crosslinking agent for the organic polymer (A), and as a result, has a function of improving the restorability, durability, and creep resistance of the resulting 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.

  Furthermore, 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 kind as the hydrolyzable group therein. 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.

  In addition, the initial characteristics of the obtained cured product can be maintained over a long period of time, and the drying property (also referred to as paintability) when an alkyd paint is applied to the obtained cured product can be improved. It is preferable to add a polymeric plasticizer.

  The polymer plasticizer is not particularly limited. For example, vinyl polymers obtained by polymerizing vinyl monomers by various methods; polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester. Esters of polyesters: 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; molecular weight 500 or more, more than 1000 polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or the like, or these polyether polyols Polystyrenes such as polystyrene and polymethyl -α- methyl styrene; polyethers derivatives hydroxyl group was substituted such as an ester group and an ether group in polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, etc. polychloroprene and the like.

  In the curable composition of this invention, a tackifier is added as needed. 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. That. 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 this invention, a solvent or a diluent is added as needed. 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.

  In the curable composition of this invention, a physical property modifier is added 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. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  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).

  In the curable composition of the present invention, a thixotropic agent (anti-sagging agent) is added as necessary. 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, the compound which has an epoxy group in 1 molecule is added 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. However, since the epoxy compound tends to decrease the catalytic activity of the guanidine compound (B) as the addition amount increases, the addition amount of the epoxy compound is preferably small.

  When an epoxy compound is added, the amount added is preferably 50 parts by weight or less, more preferably 5 parts by weight or less, and substantially no content with respect to 100 parts by weight of the organic polymer (A). Particularly preferred.

  In the curable composition of this invention, a photocurable substance is added 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, a 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 substance is 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 be the main component, and further each of them 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.

  In the curable composition of this invention, antioxidant is added 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. Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all manufactured by Ciba Specialty Chemicals Co., Ltd.); (All are manufactured by ADEKA Corp.); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all are Sankyo Life Tech 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.

  In the curable composition of this invention, a light stabilizer is added as needed. 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, CHIMASSORB119FL (all of these are manufactured by Ciba Specialty Chemicals); ADK STAB LA-57, LA- 62, LA-67, LA-63 (all manufactured by ADEKA Corporation); Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of these are Sankyo Lifetech Co., Ltd.) Manufactured).

  In the curable composition of this invention, the surface weather resistance of the obtained hardened | cured material improves by addition of the ultraviolet absorber with which an ultraviolet absorber is added as needed.

  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 an ultraviolet absorber, 0.1-10 weight part is preferable with respect to 100 weight part of organic polymers (A), and its 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 the absorbent.

  An epoxy resin is added to the curable composition of the present invention as necessary. Addition of the epoxy resin improves the adhesiveness of the obtained cured product, and the curable composition to which the epoxy resin is added is preferably used as an adhesive, particularly as an adhesive for exterior wall tiles.

  The epoxy resin is not particularly limited. For example, an epichlorohydrin-bisphenol A type epoxy resin, an epichlorohydrin-bisphenol F type epoxy resin, a flame retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, a novolac type epoxy resin, or a hydrogenated bisphenol. A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various Alicyclic epoxy resin, N, N-diglycidyl aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycerin Lumpur diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, such as epoxidized unsaturated polymer such as petroleum resins.

  Among these, those having at least two epoxy groups in one molecule are preferable because they increase the reactivity of the curable composition and the resulting cured product easily forms a three-dimensional network structure. A type epoxy resin or novolac type epoxy resin is more preferable.

  When adding an epoxy resin, the amount of addition varies depending on the use application of the curable composition, for example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin, It is preferable to add 1 to 100 parts by weight of the organic polymer (A) with respect to 100 parts by weight of the epoxy resin, and it is more preferable to add 5 to 100 parts by weight. On the other hand, when improving the intensity | strength of the hardened | cured material of an organic polymer (A), it is preferable to add 1-200 weight part of epoxy resins with respect to 100 weight part of organic polymers (A), and 5-100 weight. It is more preferable to add a part. However, since the epoxy resin tends to decrease the catalytic activity of the guanidine compound (B) as the addition amount increases, the addition amount of the epoxy resin is preferably small. The addition amount of the epoxy resin is preferably 50 parts by weight or less, more preferably 5 parts by weight or less, and particularly preferably substantially not contained with respect to 100 parts by weight of the organic polymer (A).

  When an epoxy resin is added to the curable composition of the present invention, it is preferable to add a curing agent for the epoxy resin.

  The curing agent for the epoxy resin is not particularly limited as long as it is a compound capable of curing the epoxy resin. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylene. Primary and secondary amines such as range amine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated polyethers; 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, etc. Tertiary amines and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; boron trifluoride complex compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl anhydride Alcohols; 珀酸, pyromellitic anhydride, carboxylic acids such as anhydrous Kuroren acid phenol; carboxylic acids; compounds such as diketone complex compounds of aluminum or zirconium are exemplified. Only one kind of these may be added, or a plurality of kinds may be added in combination.

  The addition amount of the epoxy resin curing agent is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Among the curing agents for epoxy resins, it is preferable to use a ketimine compound because a one-component curing composition is obtained. The ketimine compound exists stably in the absence of moisture, and is decomposed into a primary amine and a ketone by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. Examples of the ketimine compound include compounds obtained by a condensation reaction between an amine compound and a carbonyl compound.

  The amine compound and carbonyl compound used in the production of the ketimine compound are not particularly limited and include known compounds. Examples of the amine compound include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3- Diamines such as diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triamino Polyamines such as propane, triaminobenzene, tris (2-aminoethyl) amine, tetrakis (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, tetraethylenepentamine; Alkylene-based polyamines; aminosilanes such as γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane; Etc.

  Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane Compound; and the like.

  Ketimine compounds having an imino group include those obtained by reacting an imino group with styrene oxide; glycidyl ethers such as butyl glycidyl ether and allyl glycidyl ether; glycidyl esters and the like.

  These ketimine compounds may be added alone or in combination of two or more.

  When the ketimine compound is added, the amount added varies depending on the types of the epoxy resin and ketimine, but is usually preferably 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

  A flame retardant is added to the curable composition of this invention as needed. It does not specifically limit as a flame retardant, For example, flame retardants, such as phosphorus flame retardants, such as ammonium polyphosphate and tricresyl phosphate; Aluminum hydroxide, magnesium hydroxide, and thermally expansible graphite can be added. 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 (A), and 10-100 weight part is more preferable.

  In the curable composition of the present invention, various additives other than those described above are 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.

  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, it is not necessary to add a curing catalyst to the main component containing an organic polymer having a reactive silicon group, so that the curing proceeds even if the composition contains a small amount of water. Although there is little concern about (gelation), when long-term storage stability is required, it is preferable to dehydrate and dry.

  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.

  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 mold taking agent; a vibration-proofing material; a vibration-damping material; Among these uses, the obtained cured product is more excellent in flexibility and adhesiveness, so that it is more preferably used as a sealing material or an adhesive.

  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 multi-layer glass, sealing materials for SSG construction methods, or sealing materials for building working joints, 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 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.

  As a result, a polypropylene oxide having a number average molecular weight of about 19,000 having an allyl group at the end was obtained. 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 this unpurified allyl group-terminated polypropylene oxide, water was removed by centrifugation, and water 300 was added to the resulting hexane solution. Part by weight was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure to obtain a purified allyl group-terminated polypropylene oxide.

  To 100 parts by weight of the obtained allyl group-terminated polypropylene oxide, 150 ppm of a platinum vinylsiloxane complex isopropanol solution having a platinum content of 3 wt% was added as a catalyst, and reacted with 1.35 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours. Then, methyldimethoxysilyl group-terminated polypropylene oxide (A-1) was obtained.

As a result of measurement by ¹ H-NMR (measured in a CDCl ₃ solvent using JNM-LA400 manufactured by JEOL), the number of terminal methyldimethoxysilyl groups was about 1.7 on average per molecule.

(Synthesis Example 2)
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) Of polypropylene oxide was obtained. Subsequently, a methanol solution of 1.2 times equivalent NaOMe with respect to the hydroxyl group of the hydroxyl group-terminated polypropylene oxide was added to distill off the methanol, and further allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Unreacted allyl chloride was removed by vacuum devolatilization.

  After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene triol, 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.

To a 1 L autoclave, 100 parts by weight of the allyl-terminated trifunctional polypropylene oxide obtained above and 2 parts by weight of hexane were added, and azeotropic dehydration was performed at 90 ° C. The hexane was distilled off under reduced pressure, followed by nitrogen substitution. To this, 150 ppm of a platinum divinyldisiloxane complex isopropanol solution having a platinum content of 3 wt% was added as a catalyst and reacted with 1.28 parts by weight of trimethoxysilane at 90 ° C. for 5 hours to obtain a trimethoxysilyl-terminated polyoxypropylene polymer. (A-2) was obtained. As a result of measurement by ¹ H-NMR (the same method as in Synthesis Example 1), the number of terminal trimethoxysilyl groups was 1.8 on average per molecule.

(Synthesis and solution preparation of boron trifluoride 1-phenylguanidine complex)
Boron trifluoride diethyl was added to a cloudy mixture obtained by mixing 100 parts by weight of 1-phenylguanidine (manufactured by Nippon Carbide Industries Co., Ltd.) and 300 parts by weight of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). After 105 parts by weight of an ether complex (manufactured by Kanto Chemical Co., Inc.) was added dropwise, the reaction was allowed to proceed for 2 hours.

  The reaction mixture was concentrated under reduced pressure, and diethyl ether was removed to obtain 150 parts by weight of a white solid boron trifluoride 1-phenylguanidine complex. A solution of boron trifluoride 1-phenylguanidine complex was prepared by adding 150 parts by weight of methanol to this and dissolving it.

(Synthesis and solution preparation of boron trifluoride 1- (o-tolyl) biguanide complex)
To a cloudy mixture obtained by mixing 100 parts by weight of 1- (o-tolyl) biguanide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts by weight of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), After 74 parts by weight of boron fluoride diethyl ether complex (manufactured by Kanto Chemical Co., Inc.) was added dropwise, the mixture was reacted for 2 hours.

  The reaction mixture was concentrated under reduced pressure to remove diethyl ether, whereby 135 parts by weight of a white solid boron trifluoride 1- (o-tolyl) biguanide complex was obtained. A solution of boron trifluoride 1- (o-tolyl) biguanide complex was prepared by adding 135 parts by weight of methanol to this and dissolving it.

(Synthesis and solution preparation of boron trifluoride 1,5,7-triazabicyclo [4.4.0] dec-5-ene complex)
100 parts by weight of 1,5,7-triazabicyclo [4.4.0] dec-5-ene (manufactured by SIGMA-ALDRICH Corp.) and 300 parts by weight of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 102 parts by weight of boron trifluoride diethyl ether complex (manufactured by Kanto Chemical Co., Ltd.) was added dropwise to the cloudy mixture obtained by mixing, and the mixture was reacted for 2 hours. The reaction mixture was concentrated under reduced pressure to remove diethyl ether, thereby obtaining 149 parts by weight of boron trifluoride 1,5,7-triazabicyclo [4.4.0] dec-5-ene complex as a white solid. It was. A solution of boron trifluoride 1,5,7-triazabicyclo [4.4.0] dec-5-ene complex was prepared by adding and dissolving 149 parts by weight of methanol.

(Synthesis and solution preparation of boron trifluoride 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) complex)
100 parts by weight of 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) (manufactured by San Apro Co., Ltd.) and 300 parts by weight of diethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed. After adding 93 parts by weight of boron trifluoride diethyl ether complex (manufactured by Kanto Chemical Co., Inc.) to the cloudy mixed solution obtained above, the mixture was reacted for 2 hours. The reaction mixture was concentrated under reduced pressure to remove diethyl ether to obtain 145 parts by weight of a pale yellow, viscous liquid boron trifluoride DBU complex. A solution of boron trifluoride DBU complex was prepared by adding and dissolving 145 parts by weight of methanol.

(Solution preparation of boron trifluoride monoethylamine complex)
A solution of boron trifluoride monoethylamine complex was prepared by adding 100 parts by weight of methanol to 100 parts by weight of boron trifluoride monoethylamine complex (manufactured by Stella Chemifa Co., Ltd.) and dissolving it.

(Preparation of 1- (o-tolyl) biguanide solution)
To 100 parts by weight of 1- (o-tolyl) biguanide (manufactured by Tokyo Chemical Industry Co., Ltd.), 400 parts by weight of methanol was added and mixed, and then placed in a dryer at 50 ° C. for 30 minutes to give colorless and transparent 1- ( An o-tolyl) biguanide solution was obtained.

Example 1
4 parts by weight of a boron trifluoride 1-phenylguanidine complex solution was added to 100 parts by weight of the methyldimethoxysilyl group-terminated polyoxypropylene polymer (A-1) obtained in Synthesis Example 1, and a spatula was added. The resulting mixture was kneaded for 2 minutes to obtain a curable composition.
( Reference Example 2)
Instead of the boron trifluoride 1-phenylguanidine complex in Example 1, 5.1 parts by weight of a solution of boron trifluoride 1- (o-tolyl) biguanide complex was added. Thus, a curable composition was obtained.
(Example 3)
A curable composition was obtained in the same manner as in Example 1 except that instead of the organic polymer (A-1) in Example 1, the organic polymer (A-2) was changed.
( Reference Example 4)
Instead of the organic polymer (A-1) in Reference Example 2, except for changing the organic polymer (A-2), to obtain a curable composition in the same manner as in Reference Example 2.
(Comparative Example 1)
Instead of the boron trifluoride 1-phenylguanidine complex in Example 1, 4.1 parts by weight of a solution of boron trifluoride 1,5,7-triazabicyclo [4.4.0] dec-5-ene complex A curable composition was obtained in the same manner as in Example 1 except that was added.
(Comparative Example 2)
A curable composition was obtained in the same manner as in Example 1 except that 4.3 parts by weight of a boron trifluoride DBU complex solution was added instead of the boron trifluoride 1-phenylguanidine complex in Example 1. It was.
(Comparative Example 3)
A curable composition was prepared in the same manner as in Example 1, except that 4.4 parts by weight of a boron trifluoride monoethylamine complex solution was added instead of the boron trifluoride 1-phenylguanidine complex in Example 1. Obtained.
(Comparative Example 4)
The curable composition was the same as in Reference Example 2 except that 20 parts by weight of 1- (o-tolyl) biguanide solution was added instead of the boron trifluoride 1- (o-tolyl) biguanide complex in Reference Example 2. I got a thing.
(Curable)
The above curable composition was stretched with a spatula to a thickness of about 3 mm under conditions of 23 ° C. and 50% RH, and the surface of the curable composition was lightly touched over time using a microspatula. The time until the micro spatula was not reached was measured. As for curability, the shorter the time until the composition does not come into contact with the microspatula in terms of practical properties, the faster the cure and the better.
(Stickness of cured product surface)
When the above curable composition was stretched smoothly with a spatula to a thickness of about 3 mm under a condition of 23 ° C. and 50% RH for 1 hour, and the cured product surface was touched with a finger, The case where it did not feel was judged as ○, and the case where it felt sticky was judged as ×.

As is apparent from Table 1, as a curing catalyst, Example 1, 3 using boron trifluoride 1-phenyl-guanidine complex body, curing fast, I did not feel even more stickiness of the cured product surface. On the other hand, Comparative Example 1 using boron trifluoride 1,5,7-triazabicyclo [4.4.0] dec-5-ene complex felt stickiness on the surface of the cured product. Comparative Example 2 and Comparative Example 3 using boron trifluoride DBU complex and boron trifluoride monoethylamine complex are slow to cure, and Comparative Example 4 using 1- (o-tolyl) biguanide alone is also cured. It was late.
(Preparation of 1-phenylguanidine solution)
To 100 parts by weight of 1-phenylguanidine (manufactured by Nippon Carbide Industries Co., Ltd.), 150 parts by weight of polyoxypropylene diol (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Actol P-23) with a molecular weight of 3000 is added and mixed Then, it was placed in an 80 ° C. dryer for 1 hour to obtain a yellow transparent 1-phenylguanidine solution.
(Example 5)
Surface-treated colloidal calcium carbonate (product name: Hakujyo Hana CCR) manufactured by Shiraishi Kogyo Co., Ltd. with respect to 100 parts by weight of the methyldimethoxysilyl group-terminated polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 50.5 parts by weight of polypropylene glycol plasticizer with a molecular weight of 3000 (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Actol P-23), titanium oxide which is a white pigment (manufactured by Ishihara Sangyo Co., Ltd., product) Name: Typek R-820) 20 parts by weight, sagging inhibitor (manufactured by Enomoto Kasei Co., Ltd., trade name: Disparon 6500), 2 parts by weight, benzoate UV absorber (manufactured by Sumika Chemtex Co., Ltd., trade name: Sumisorb) 400) 1 part by weight, 1 part by weight of a hindered amine light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS-770) is weighed, mixed and charged After kneading for a minute, it was dispersed through three paint rolls.

  Thereafter, dehydration under reduced pressure at 120 ° C. for 2 hours, cooling to 50 ° C. or less, and 2 parts by weight of vinyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name: A-171) as a dehydrating agent, silane cup As a ring agent, 3 parts by weight of γ- (2-aminoethyl) aminopropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd., trade name: A-1120) was added and kneaded for 10 minutes, and then boron trifluoride. 2 parts by weight of diethyl ether complex (manufactured by Kanto Chemical Co., Inc.) was added and kneaded for 10 minutes.

  Further, 7.5 parts by weight of 1-phenylguanidine solution was added and kneaded for 10 minutes, and kneaded in a substantially moisture-free state, and then sealed in a cartridge that was a moisture-proof container, and the one-component curable composition Got.

(Example 6)
A curable composition was obtained in the same manner as in Example 5 except that the amount of boron trifluoride diethyl ether complex used in Example 5 was changed to 4 parts by weight.
(Example 7)
A curable composition was obtained in the same manner as in Example 5 except that the amount of Actol P-23 used in Example 5 was changed to 46 parts by weight and the amount of 1-phenylguanidine solution was changed to 15 parts by weight. It was.
(Curable)
The above curable composition was stretched with a spatula to a thickness of about 3 mm under conditions of 23 ° C. and 50% RH, and the surface of the curable composition was lightly touched over time using a microspatula. The time until the micro spatula was not reached was measured.
(Tensile property of cured product)
The curable composition was made into a sheet-like test body having a thickness of 3 mm, placed under conditions of 23 ° C. and 50% RH for 3 days, and further cured at 50 ° C. for 4 days for curing. After punching out into a No. 3 dumbbell shape, a tensile test was performed at a tensile speed of 200 mm / min using an autograph manufactured by Shimadzu Corporation to measure 100% tensile modulus, strength at break, and elongation at break.

  As shown in Table 2, Examples 5 to 7 in which 1-phenylguanidine was used in combination with boron trifluoride diethyl ether complex as a curing catalyst were fast cured, and the cured product had high tensile strength and was good. there were.

Claims (10)

An organic polymer (A) having a silicon group that can be crosslinked by forming a siloxane bond,
General formula (1):
R ¹ N = C (NR ¹ ₂ ) ₂ (1)
(One of the five R ¹ groups is an aryl group. The remaining R ¹ groups are each independently a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and a saturated hydrocarbon group. at least is one selected from the group consisting of.) represented by the guanidine compound (B),
And Lewis acid and / or Lewis acid complex (C),
A curable composition comprising: The guanidine compounds and (B) a Lewis acid and / or complex of a Lewis acid (C), the curable composition of claim 1 comprising a Lewis acid guanidine complex consisting (D). The guanidine compound (B) has the general formula (2):

(The four R ^{1 s} are each independently at least one selected from the group consisting of a hydrogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid, and a saturated hydrocarbon group. R ² in the formula is at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, an amino group, a nitro group, a cyano group, a sulfonic acid group, and an organic group, and a is an integer of 1 to 4. The curable composition according to claim 1, which is a guanidine compound represented by the formula: Guanidine compound (B) is 1-phenyl guanidine, or 1- (o-tolyl) guanidine down, curable composition according to any one of claims 1 to 3.   The curable composition according to any one of claims 1 to 4, wherein the Lewis acid and / or Lewis acid complex (C) comprises a metal halide or a boron halide.   The curable composition according to any one of claims 1 to 5, wherein the Lewis acid and / or the Lewis acid complex (C) contains boron trifluoride.   The main chain skeleton of the organic polymer (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. Item 7. The curable composition according to any one of Items 1 to 6.   The curable composition according to claim 7, wherein the polyoxyalkylene polymer is a polyoxypropylene polymer.   The sealing material which uses the curable composition of any one of Claims 1-8.   The adhesive agent using the curable composition of any one of Claims 1-8.