JP6383158B2 - Curable composition and cured product thereof - Google Patents

Description

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

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

  Among organic polymers having a reactive silicon group, an organic polymer whose main chain skeleton is a polyoxyalkylene polymer, a polyisobutylene polymer, or a (meth) acrylic acid ester polymer is used as a sealing material or an adhesive. It is widely used for agent applications. Although this sealing material and adhesive have low viscosity at room temperature and excellent workability, there is room for improvement in the hardness, tensile strength, and adhesive strength of the cured product.

  On the other hand, among organic polymers with reactive silicon groups, organic polymers with reactive silicon groups introduced into prepolymers obtained by reacting polyester polyols with isocyanate monomers are mainly used as urethane resin adhesives. Has been. However, a urethane resin adhesive synthesized from a polyester polyol is generally excellent in hardness, tensile strength, and adhesive strength of a cured product, but has poor workability because heating is required during use.

  For example, Patent Document 1 discloses that by using a urethane resin synthesized from a polyester polyol and a vinyl polymer in combination, the bonding time is long and the performance of expressing the adhesiveness immediately after bonding is excellent. However, there is room for improvement in workability because heating is required. Patent Document 2 discloses a method of bonding a gas impermeable material using a hot melt adhesive using a polymer in which a silicon group is introduced at the end of a urethane prepolymer obtained by reacting a polyester diol and a diisocyanate. However, this also required heating and was difficult to work with.

JP 2003-193019 A JP 7-278320 A

  The present invention provides a curable composition containing an organic polymer having a reactive silicon group, which does not necessarily require heating, and is excellent in workability, tensile strength, and adhesive strength. Objective.

  As a result of various studies to solve the above-mentioned problems, the present inventors are excellent in workability, tensile strength, and adhesive strength by mixing several organic polymers having reactive silicic groups having different structures and properties. It was found that a curable composition was obtained, and the present invention was completed.

That is, the present invention
(I). (A) An organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, the main chain skeleton of which is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, a (meth) acrylic ester heavy polymer An organic polymer that is at least one selected from the group consisting of a polymer, (B) an organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, wherein the main chain skeleton is a polyester-based polymer, A crystalline organic polymer that is at least one selected from the group consisting of polyamide-based polymers, (C) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, A curable composition comprising a non-crystalline organic polymer, wherein the case is at least one selected from the group consisting of polyester polymers and polycarbonate polymers
(II). The organic polymer (B) and / or the organic polymer (C) is an organic polymer obtained by reacting a silicon compound having at least one of a hydrosilyl group, an isocyanate group and a thiol group (I ) Curable composition according to
(III). The curable composition according to (I) or (II), wherein the organic polymer (B) and / or the organic polymer (C) is an organic polymer containing no main chain skeleton obtained by reacting a diisocyanate compound. ,
(IV). The curable composition according to any one of (I) to (III), wherein the main chain skeleton of the organic polymer (B) and / or the organic polymer (C) is a polyester polymer,
(V). The curable composition according to any one of (I) to (IV), wherein the organic polymer (A) is a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer,
(VI). The curable composition according to any one of (I) to (V), wherein the crosslinkable silicon group of the organic polymer (A) is a trialkoxysilyl group,
(VII). The curable composition according to any one of (I) to (VI), wherein the crosslinkable silicon group of the organic polymer (B) and / or the organic polymer (C) is a trialkoxysilyl group,
(VIII). Curing according to any one of (I) to (VII), wherein at least one selected from the group consisting of organic tin, titanium compounds, carboxylic acids, carboxylic acid metal salts, and amine compounds is used as the curing catalyst (D). Sex composition,
(IX). Furthermore, the plasticizer (E) is contained, and the amount of the plasticizer (E) used is 30 parts by weight or less with respect to 100 parts by weight of the total amount of the organic polymers (A) to (C). ) The curable composition according to any one of
(X). (I) to (IX) a sealing material using the curable composition according to any one of
(XI). An adhesive comprising the curable composition according to any one of (I) to (IX);
(XII). A coating material comprising the curable composition according to any one of (I) to (IX),
(XIII). A cured product obtained by curing the curable composition according to any one of (I) to (IX),
About.

  The curable composition of the present invention does not necessarily require heating, and is excellent in workability, tensile strength, and adhesive strength.

The present invention will be described in detail below.
The curable composition of the present invention has a reactive silicon group, and the main chain skeleton is selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylate polymer. And at least one organic polymer (A) 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 (1):
-SiR ¹ _a X ¹ _3-a (1)
(A R ^{1 s} are each 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.) (3-a) X ¹ groups selected from the group consisting of triorganosiloxy groups. Are each independently a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 3.).

  The curable composition of the present invention uses an organic polymer (A) having a reactive silicon group as a main component. However, the curable composition of the present invention has a higher organic weight than that using an inorganic polymer such as polydimethylsiloxane as a main component. Since the compatibility and dispersibility with the polymer (B) and the organic polymer (C) are good, it has the characteristics of excellent curability and adhesion.

  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 a polyoxyalkylene polymer, a saturated hydrocarbon polymer, or a (meth) acrylic acid ester polymer. For example, polyoxyalkylene polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer; ethylene -Propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or copolymer of butadiene and acrylonitrile and / or styrene, polybutadiene, isoprene or butadiene and acrylonitrile and Copolymers with styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; ethyl (meth) acrylate, (Meth) acrylic acid ester polymer obtained by radical polymerization of a compound such as chill (meth) acrylate; obtained by radical polymerization of a compound such as (meth) acrylic acid ester compound, vinyl acetate, acrylonitrile, styrene Organic polymers such as vinyl polymers; graft polymers obtained by polymerizing vinyl compounds in the aforementioned polymers; polysulfide 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 a coating material, 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 (2):
-R ² -O- ⁽²⁾
(R ² is a linear or branched alkylene group having 1 to 14 carbon atoms).

R ² described in the general formula (2) 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 linear chain having 2 to 4 carbon atoms. A branched or branched alkylene group is preferred.

The repeating unit of the general formula (2) wherein, 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- (methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, ethylene oxide adduct of (meth) acrylic acid, trifluoro (meth) acrylic acid Methylmethyl, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, (meth) acrylic acid Perfluoroethyl, (meth) a Trifluoromethyl laurate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, ( Examples include (meth) acrylic acid compounds such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate.

  The (meth) acrylic acid ester polymer includes a copolymer of a (meth) acrylic acid ester compound and a vinyl compound copolymerizable therewith.

  The vinyl compound is not particularly limited, and for example, styrene compounds such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and salts thereof; silicon groups such as vinyl 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 (3):
—CH ₂ —C (R ³ ) (COOR ⁴ ) — (3)
A repeating unit having an alkyl group having 1 to 8 carbon atoms represented by (R ³ is a hydrogen atom or a methyl group, and R ⁴ is an alkyl group having 1 to 8 carbon atoms);
General formula (4):
—CH ₂ —C (R ³ ) (COOR ⁵ ) — (4)
(R ³ is the same as in the general formula (3), R ⁵ 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 ⁴ described in the general formula (3) 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 ⁴ contained in the copolymer is not necessarily limited to one kind of alkyl group.

R ⁵ described in the general formula (4) 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 ⁵ is not necessarily limited to one kind of the alkyl group contained in the copolymer.

  The (meth) acrylic ester copolymer is substantially composed of repeating units described in the general formula (3) and the general formula (4). Here, “substantially” means that the total proportion of the repeating units described in the general formulas (3) and (4) in the copolymer exceeds 50% by weight, and occupies the copolymer. The total proportion of the repeating units described in the general formulas (3) and (4) is preferably 70% by weight or more.

  Further, the ratio of the repeating units of the general formulas (3) and (4) present in the copolymer is preferably 95: 5 to 40:60 in weight ratio (general formula (3): general formula (4)). 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 (3) and (4) 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 the general formula (5):
—NR ⁶ —C (═O) — (5)
(R ⁶ 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 end of the polyurethane main chain, or at the same time, all or part of the isocyanate group in the polymer and the general formula (6):
_{^{W-R 7 -SiR 8 3-}} b X 2 b (6)
(R ⁷ is a divalent organic group, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. (3-b) R ⁸ is a hydrogen atom or an organic group, b X ² is a hydroxyl group or a hydrolyzable group, and b 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 (7):
_{^{O = C = N-R 7}} -SiR 8 3-b X 2 b (7)
(R ⁷ , R ⁸ , X ² , and b are the same as those in the general formula (6)). 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.

  In the present invention, the main chain skeleton of the component (A) is at least one selected from the group consisting of a polyoxyalkylene polymer, a saturated hydrocarbon polymer, and a (meth) acrylic acid ester polymer, Preferably, it is at least one selected from the group consisting of a polyoxyalkylene polymer or a (meth) acrylic acid ester polymer. Particularly preferably, a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer are used in combination. It is particularly preferable to use both of these because adhesiveness is improved with respect to a substrate that is difficult to bond.

  The silicon compound described in the general formula (6) 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 (6), 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 (7) 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 (7), an excessive amount of the silicon compound described in the general formula (6) disclosed in JP 2000-119365 A (US Pat. No. 6,046,270) Examples include reaction products of polyisocyanate compounds.

The hydrolyzable group represented by X ¹ in the general formula (1) 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 ¹ described in the general formula (1) 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 (1) 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.

  Further, a dimethoxymethylsilyl group is particularly preferred 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. Furthermore, the organic polymer obtained by the method (b) can be 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 (8):
^{_{H- (SiR 9 2 O) n}} SiR 9 2 -R 10 -SiX 3 3 (8)
(Three X ³ are each independently a hydroxyl group or a hydrolyzable group. (2n + 2) R ^9s are each independently a hydrocarbon group. R ¹⁰ 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 (8) may be used. preferable.

R ⁹ in the general formula (8) 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 ¹⁰ described in the general formula (8) is not particularly limited as long as it is a divalent organic group. Among these, divalent carbonization 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 (8) 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 (8) 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 1.1 to 5 as an average value, more preferably 1.2 to 4.5, and 1.4 to 4 Is particularly preferred. If the number of reactive silicon groups contained in the molecule is less than 1.1 on average, the curable composition tends to be inferior in curability, and the resulting cured product is less likely to exhibit good rubber elastic behavior. Tend to be. On the other hand, when the number exceeds 5, the cured product tends to be brittle and the strength tends to be weak.

  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 comprises at least one crystalline organic polymer (B) having a reactive silicon group and a main chain skeleton selected from a polyester polymer and a polyamide polymer, and a reactive property. At least one amorphous organic polymer (C) having a silicon group and having a main chain skeleton selected from a polyester polymer and a polycarbonate polymer is included.

  The organic polymer (B) has crystallinity at room temperature, and the organic polymer (C) has non-crystallinity. The crystallinity in the present invention is evaluated in terms of crystallinity by the X-ray diffraction method (Luland method) of a polymer cooled and solidified at a cooling rate of 10 ° C./min from the molten state (for example, “ X-ray diffraction of polymer ", by LE Alexander, edited by Ichiro Sakurada, Kagaku Dojin, 1972, p125), crystallinity of 30% or more, preferably 40% or more, particularly preferably 50% or more. On the other hand, non-crystallinity is outside the above definition.

  In the present invention, the polymer in which the reactive silicon group is introduced into the crystalline polyester corresponds to the component (B), and the polymer in which the reactive silicon group is introduced into the amorphous polyester and / or the liquid polyester corresponds to the component (C).

  Similar to the organic polymer (A), the organic polymer (B) and the organic polymer (C) have one or more reactive silicon groups on average per molecule. Examples of the reactive silicon group include a group represented by the general formula (1). The organic polymer (B) is obtained by introducing a reactive silicon group into one or more polyol compounds selected from polyester polyols and polyamide polyols. On the other hand, the organic polymer (C) is obtained by introducing a reactive silicon group into one or more polyol compounds selected from polyester polyols and polycarbonates.

The raw material polyester resin used in the components (B) and (C) of the present invention can be obtained by a known method such as condensation of a dibasic acid such as adipic acid and a diol, or ring-opening polymerization of lactones. Examples of the dibasic acid that can be used include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3 , 3-diethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,20-eicosanedicarboxylic acid, etc. Saturated aliphatic dicarboxylic acids; maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentenedioic acid, methylene succinic acid, aqua Unsaturated dicarboxylic acids such as rilmalonic acid, isopropylidene succinic acid, 2,4-hexadiene diacid, acetylenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; Phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxy Aromatic dicarboxylic such as diacetic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid An acid; etc. are mentioned, It can use suitably. Of these, succinic acid, suberic acid, adipic acid, sebacic acid, and dodecanedioic acid are more preferably used. These dibasic acids may be used alone or in combination of two or more. Furthermore, you may use together polyvalent carboxylic acid, such as trimellitic acid, trimesic acid, and pyromellitic acid. Among these, 1,12-dodecanedicarboxylic acid, sebacic acid, adipic acid, and succinic acid are preferable as raw materials suitable for the component (B) having crystallinity because the crystallinity is increased. On the other hand, an aromatic dicarboxylic acid such as phthalic acid is preferable as a raw material suitable for the non-crystalline (C) component.

  Examples of the diol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3- Methyl-1,3-butanediol, 2-methyl-1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1, 5-heptanediol, 1,7-heptanediol, 3,4-heptanediol, 3,5-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,2 -Decanediol, 1,10-decanediol, 1,12-dodecanediol, 1,16-hexadecanediol, 1, 8-octadecanediol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclododecanediol, polyethylene glycol, Examples thereof include diols having 2 to 20 methylene groups such as polypropylene glycol, polytetramethylene glycol and polycaprolactone diol, and diols having 2 to 10 are particularly suitable from the viewpoint of availability and workability. In addition, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-bis (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxyethoxyphenyl) in which carbon atoms are partially substituted with oxygen atoms or aromatic rings It may be propane, etc. Among them, ethylene glycol, 1,6-hexanediol and butanediol are easily available and effective in improving crystallinity, and are suitably used as a raw material for component (B). May be used alone or in combination of two or more.

  A polyester resin having hydroxyl groups at both ends of the molecule can be obtained by carrying out an ordinary polycondensation reaction using these dibasic acids and diols. Usually, the equivalent ratio (hydroxyl group / carboxyl group) of the hydroxyl group of the aliphatic diol or aliphatic polyol and the carboxyl group of the aliphatic dicarboxylic acid and / or aromatic polycarboxylic acid (and / or its derivative) is 1.02. -1.5 is preferable and 1.05-1.3 is more preferable. Specifically, a predetermined amount of aliphatic dicarboxylic acid and aliphatic diol or aromatic polycarboxylic acid and aliphatic polyol are added in the presence or absence of a catalyst at a temperature range of about 150 to 250 ° C. for 1 to 50 hours. Esterification or transesterification is performed by polycondensation to a certain extent.

  As a catalyst in this case, for example, it is preferable to carry out in the presence of a titanium-based catalyst such as titanium tetrabutoxide and a tin-based catalyst such as dibutyltin oxide, in order to promote polycondensation. The catalyst may be charged together with an aliphatic diol and an aliphatic dicarboxylic acid, or an aliphatic polyol and an aromatic polycarboxylic acid, or may be added after the prepolymerization has progressed without a catalyst. In the production of polyester polyols, it is desirable that both ends are almost hydroxyl groups and carboxylic acid ends are not formed. For this purpose, it is particularly effective to add the above-mentioned catalyst after prepolymerization. Is preferable.

  Although the polyester resin to be used is not particularly limited, the number average molecular weight thereof is preferably 500 to 30,000, more preferably 1000 to 20,000, in terms of the GPC measurement value converted to polystyrene. 2000 to 10,000 are more preferable, and 2000 to 4500 are particularly preferable. If the number average molecular weight of the polyester resin is less than 500, the bondable time of the resulting curable composition may be shortened, or the elasticity after moisture curing may be poor. Conversely, the number average molecular weight of the polyester resin is 30. If it exceeds 1,000, the strength and heat resistance after moisture curing of the resulting curable composition may be insufficient.

  In the polycondensation reaction, when the number of moles of dicarboxylic acid charged is n, a crystalline polyester resin having hydroxyl groups at both molecular ends can be obtained by setting the number of moles of diol charged to n + 1. Moreover, the crystalline polyester resin which has the said preferable number average molecular weight can be obtained by adjusting the number of n or n + 1.

  The dicarboxylic acid and diol of the present invention may be used alone or in combination. Furthermore, there is no problem even if it is a mixture of the polyester polyol obtained above.

  The raw material polyamide polymer used in the component (B) of the present invention is a polymer formed by bonding a large number of monomers by amide bonds. The polyamide polymer can be obtained by polycondensation of diamine and dibasic acid, polycondensation of aminocarboxylic acid, polycondensation from lactam, polycondensation of diamine with dimerized fatty acid, and the like.

  In the case of general polycondensation of diamine and dibasic acid, the above-mentioned dibasic acid can be used.

  Examples of the diamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9- Nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl- Aliphatic diamines such as 1,6-hexanediamine, 2-methyl-1,8-octanediamine and 5-methyl-1,9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine, p -Phenylenediamine, m-phenylenediamine, o-phenylenediamine, - xylylenediamine, m- xylylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, aromatic diamines such as 4,4'-diaminodiphenyl ether; and the like. These diamines may be used alone or in combination of two or more.

  The polyamide resin can be produced by any method known as a method for producing polyamide. From the viewpoint of high molecular weight and productivity, a diamine and a dibasic acid are mixed batchwise or continuously. It is preferable to produce by condensation reaction.

  Other methods include, for example, polyamide 6 by ring-opening polymerization of ε-caprolactam, polyamide 11 by polycondensation of ε-aminoundecanoic acid, polyamide 12 by ring-opening polymerization of ε-aminolaurolactam, and a plurality of the above polyamides. Polymerized polyamides can also be mentioned.

  The polyamide resin to be used is not particularly limited, but the number average molecular weight is preferably 500 to 30,000, more preferably 1000 to 20,000, in terms of the GPC measurement value converted to polystyrene. 2000 to 10,000 are particularly preferred. If the number average molecular weight of the polyamide-based resin is less than 500, the bondable time of the resulting curable composition may be shortened or the elasticity after moisture curing may be poor. Conversely, the number average molecular weight of the polyamide resin may be When it exceeds 30,000, the strength and heat resistance after moisture curing of the resulting curable composition may be insufficient.

  Any method can be used as a method for introducing a reactive silicon group into the polyamide resin. For example, it may be obtained by preparing a polymer having a terminal carboxyl group using an excess of basic acid compared to amine, reacting an isocyanate group-containing compound, and reacting an amino group and a silicon-containing compound.

  (B) The compounding quantity of a component has preferable 1-200 weight part with respect to 100 weight part of organic polymers of (A) component, Furthermore, 3-100 weight part is preferable, and 5-50 weight part is more preferable. When the blending amount of the component (B) is less than 1 part by weight, the compatibility of the curable composition of the present invention is low, and problems such as separation may occur during long-term storage. On the other hand, when the amount of component (B) exceeds 200 parts by weight, the elongation of the cured product is undesirably reduced.

  Polycarbonate diol is used as a raw material for the reactive silicon group-containing polycarbonate polymer of component (C) of the present invention. Polycarbonate diol has a long-chain glycol structure in which alkylene is linked by a carbonate bond and hydroxyl groups are present at both ends. Using diol and ethylene carbonate as raw materials, it is polymerized by transesterification and condensation reaction while distilling ethylene glycol in a high-temperature vacuum state. Further, it may be obtained by condensation of polyol and phosgene, chloroformate ester, dialkyl carbonate or diaryl carbonate without using ethylene carbonate. As the diol, those described above can be used, and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and the like are preferable from the viewpoint of availability and melting point, and in particular, 1,6-hexane. Diols are particularly preferred. These diols may be used alone or in combination of two or more. Further, these polycarbonate polyols may be random or block copolymerized.

  The number average molecular weight of the polycarbonate diol to be used is preferably 200 to 20,000, more preferably 300 to 10,000, and particularly preferably 500 to 5,000. When the number average molecular weight is less than 200, the bondable time of the resulting curable composition may be shortened or the elasticity after moisture curing may be poor. Conversely, when the number average molecular weight of the polycarbonate diol exceeds 10,000, the strength and heat resistance after moisture curing of the resulting curable composition may be insufficient.

  In the present invention, the component (B) and / or the component (C) is preferably a polymer containing no main chain skeleton obtained by reacting a diisocyanate compound. A so-called urethane prepolymer obtained by reacting a diol compound and a diisocyanate compound is not preferable because the viscosity of the polymer tends to be high and workability is lowered.

  As a method for introducing a reactive silicon group into the component (B) and the component (C), the method described in the explanation of the component (A) can be used. In particular, it is preferable to react a reactive silicon compound having at least one of a hydrosilyl group, an isocyanate group, and a thiol group.

  When the hydrosilylation method (a) described above is used, the polyester main chain may be hydrolyzed when subjected to an alkaline condition in the step of introducing an unsaturated group into the polymer terminal. In such a case, the method (c) is preferable. That is, a method in which an organic polymer having a functional group such as a hydroxyl group, an epoxy group, an isocyanate group, or a thiol group in the molecule is reacted with a compound having a reactive functional group and a reactive silicon group. It is. In particular, it is preferable to use 3-isocyanatopropyltriethoxysilane or 3-isocyanatopropyltrimethoxysilane and react with a hydroxyl-terminated polymer. In this case, it is preferable to use a catalyst in combination in order to facilitate the reaction. For example, mercaptotin is particularly preferable because it is effective when added in a small amount.

  When the reactive silicon group is introduced into the component (B) and the component (C), they may be mixed after reacting separately, or the reactive silicon group may be added to the premixed material and reacted. Also good. When the polymer of the component (B) has a high melting point, it is preferable to introduce the reactive silicon group after mixing the component (C) in advance because it is easy to handle. As the reactive silicon group, the same silicon group as described in the description of the component (A) can be used, but the same component may be used for the component (B) and the component (C), or different ones may be used. May be. Moreover, when introducing a reactive silicon group, you may blend and use 2 or more types. Of the reactive silicon groups, a trialkoxysilyl group is particularly preferred because of its high reactivity. Specifically, a trimethoxylylyl group or a triethoxysilyl group can be preferably used.

  A crystalline organic polymer (B) containing a reactive silicon group and having a main chain skeleton selected from the group consisting of a polyester polymer and a polyamide polymer is used in combination with the component (A). However, although there is no effect for improving mechanical properties such as strength improvement, it is excellent in compatibility with the component (A). On the other hand, the non-crystalline organic polymer (C) which has a reactive silicon group and the main chain skeleton is at least one selected from the group consisting of polyester polymers and polycarbonate polymers, When used in combination, there is an effect of improving the strength of the cured product, but the compatibility with the component (A) is poor, and the mixture of (A) and (C) is turbid or separated. By using the three components (A), (B), and (C) in combination, the compatibility of the mixture is good and the strength of the cured product can be improved.

  The amount of component (C) is preferably 3 to 200 parts by weight, more preferably 5 to 150 parts by weight, and even more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the organic polymer of component (A). When the blending amount of the component (C) is less than 3 parts by weight, the effect of improving the shear strength and tensile strength of the curable composition of the present invention is insufficient. On the other hand, when the amount of component (C) exceeds 200 parts by weight, the elongation of the cured product is lowered, which is not preferable.

  In the present invention, the curing catalyst (D) is used as a silanol condensation catalyst for the components (A), (B) and (C). Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dimethyltin diacetate, dimethyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate) , Dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis (benzyl maleate) Dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibutyltin bis (acetylacetate) Natto), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin bis (acetyl) Tetravalent organotin compounds such as acetonate); organics such as aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate Aluminum compounds; zirconium compounds such as zirconium tetrakis (acetylacetonate) and the like. Moreover, carboxylic acid and / or carboxylic acid metal salt can also be used as a curing catalyst. Moreover, an amidine compound as described in WO2008 / 078654 can also be used. Examples of amidine compounds include 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,5,7-triazabicyclo [4.4. .0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1,8-diazabicyclo [5.4.0] -7-. Although undecene (DBU) etc. can be mentioned, it is not restricted to these. Some amidines are solid at room temperature, but if there is a problem that they are difficult to disperse, use a means to disperse or dissolve in advance using a solvent or plasticizer suitable for each compound. Can do. Considering the working environment, a high boiling point solvent is preferable.

  Of the curing catalysts listed above, dibutyltin-based curing catalysts have a good balance of curability and adhesiveness and are most commonly used. In recent years, however, dibutyltin-based curing catalysts are concerned about adverse effects on the human body. In such cases, dioctyltin-based curing catalysts can be used. As the dioctyltin-based curing catalyst, dioctyltin dilaurate, dioctyltin bisacetylacetonate, and a reaction product of dioctyltin salt and ethyl silicate are industrially available and preferable. Moreover, since a titanium catalyst as a non-tin catalyst has high activity, it is preferable in the case of industrial adhesives and electrical / electronic adhesives that require rapid curing. Among the titanium catalysts, diisopropoxytitanium bis (ethyl acetocetate) is particularly preferable because of excellent curability and storage stability of the blend. This catalyst is sold under the trade name Tyzor PITA and is easily available and can be suitably used.

  As a compounding quantity of a curing catalyst, 0.01-20 weight part is preferable with respect to 100 weight part of total amounts of the organic polymer of (A)-(C) component, 0.05-15 weight part is further more preferable, 0.1 to 10 parts by weight is most preferred. When the blending amount of the curing catalyst is within this range, the curable composition has excellent curability, and has an appropriate curing time, and therefore has excellent workability.

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

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

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

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

  The blending amount of the plasticizer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less with respect to 100 parts by weight of the organic polymers (A) to (C). When the amount is more than 30 parts by weight, the strength and adhesiveness of the cured product tend to decrease.

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

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

  Among these polymer plasticizers, a vinyl polymer is preferable because of high compatibility with the organic polymers (A) to (C) and good weather resistance and heat resistance of the resulting cured product. Among them, acrylic polymers and / or methacrylic polymers 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 500 to 15,000, 800 to 10,000, more preferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, and 1,000 to Most preferred is 3,000. If the molecular weight of the polymer plasticizer is too low, the plasticizer will flow out from the cured product over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time, which may cause contamination due to dust adhesion. Yes, alkyd paintability tends to be inferior. On the other hand, if the molecular weight is too high, the viscosity of the curable composition tends to be high and workability tends to be poor.

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

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

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

  As the polymeric plasticizer having a reactive silicon group, the average number of reactive silicon groups per molecule is preferably 1 or less, and more preferably 0.8 or less.

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

  The amount of the polymer plasticizer added is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less with respect to 100 parts by weight of the organic polymers (A) to (C). If it exceeds 30 parts by weight, the mechanical strength of the cured product tends to be insufficient.

  Aminosilane can be added to the curable composition of the present invention. Aminosilane is a compound having a reactive silicon group and amino group in the molecule, and is usually referred to as an adhesion-imparting agent. By using this, various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc. When used, it exhibits a significant adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. In addition, it is a compound that can function as a physical property modifier, an inorganic filler dispersibility improver, and the like.

  Specific examples of the reactive silicon group of aminosilane include the groups already exemplified, but methoxy group, ethoxy group and the like are preferable from the viewpoint of hydrolysis rate. The number of hydrolyzable groups is preferably 2 or more, particularly 3 or more. Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ -(2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) amino Propylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) amino Propyltrimethoxysilane 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ -Aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2 -Aminoethyl) amino group-containing silanes such as aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) -3- ( Triethoxysilyl) -1- It may be mentioned ketimines type silanes such Ropan'amin.

  Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropylmethyldimethoxysilane are used. preferable. Only one type of aminosilane may be used, or two or more types may be used in combination. It has been pointed out that γ- (2-aminoethyl) aminopropyltrimethoxysilane is irritating compared to other aminosilanes, and instead of reducing this aminosilane, γ-aminopropyltrimethoxysilane should be used in combination. Can alleviate irritation.

  The amount of aminosilane is preferably about 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the organic polymer of the components (A) to (C). If the amount of aminosilane is less than 1 part by weight, sufficient adhesion may not be obtained. On the other hand, if the amount of aminosilane exceeds 20 parts by weight, the cured product becomes brittle and sufficient strength cannot be obtained, and the curing rate may be slow.

In the composition of the present invention, an adhesion-imparting agent other than aminosilane can be used.
Specific examples of the adhesion imparting agent other than aminosilane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxy Epoxy group-containing silanes such as cyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyl Isocyanate group-containing silanes such as diethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane; γ-mercaptopropi Mercapto group-containing silanes such as trimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltriethoxysilane; β-carboxyethyltriethoxysilane, Carboxysilanes such as β-carboxyethylphenylbis (2-methoxyethoxy) silane and N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ- Vinyl type unsaturated group-containing silanes such as methacryloyloxypropylmethyldimethoxysilane and γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing γ-chloropropyltrimethoxysilane and the like Orchids; can be exemplified tris isocyanurate silanes such as (trimethoxysilyl) isocyanurate. Moreover, the condensate which condensed the said silane partially 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. . The silane coupling agent used in the present invention is usually used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) to (C) components having a reactive silicon group. The In particular, it is preferably used in the range of 0.5 to 10 parts by weight.

  The effects of the silane coupling agent added to the curable composition of the present invention include various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, and mortar, vinyl chloride, acrylic, and polyester. When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., it exhibits a remarkable adhesive improvement effect under non-primer conditions or primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, and aromatic polyisocyanates. The adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesion-imparting agents, the adhesion to the adherend can be improved.

  Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane are preferred in order to ensure good adhesion.

  The amount of the adhesion-imparting agent used is preferably about 0.01 to 20 parts by weight, and about 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the organic polymers (A) to (C). More preferred is about 1 to 7 parts by weight. If the blending amount of the adhesiveness-imparting agent is below this range, sufficient adhesion may not be obtained. On the other hand, if the blending amount of the adhesion-imparting agent exceeds this range, practical deep curability may not be obtained.

  As the adhesiveness imparting agent, in addition to the adhesiveness imparting agent, the adhesiveness imparting agent is not particularly limited. For example, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like can be used. The adhesiveness-imparting agent may be used alone or in combination of two or more. However, since the epoxy resin may lower the catalytic activity depending on the addition amount, it is preferable that the addition amount of the epoxy resin is small in the curable composition of the present invention. The amount of the epoxy resin used is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less, and substantially no content with respect to 100 parts by weight of the total amount of the components (A) to (C). It is particularly preferred.

  An antioxidant (anti-aging agent) can be used in the composition obtained in the present invention. When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144, CHIMASORB 944LD, CHIMASSORB 119FL (all of these are manufactured by BASF Japan Ltd.); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all above Also manufactured by ADEKA Co., Ltd.); hindered amines shown by Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Corporation) A system light stabilizer can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the organic polymers (A) to (C) having a reactive silicon group. Preferably it is 0.2-5 weight part.

  A light stabilizer can be used in the composition obtained in the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the organic polymers (A) to (C) having a reactive silicon group. Preferably it is 0.2-5 weight part. Specific examples of the light stabilizer are also described in JP-A-9-194731.

  When a photocurable substance is used in combination with the composition obtained in the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition. Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144, CHIMASSORB119FL (all manufactured by BASF Japan Ltd.); MARK LA-57, LA-62, LA-67, LA-63 (all stocks) Examples include light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by BASF Japan Ltd.).

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

  A filler can be added to the composition of the present invention. Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, 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 microballoon, phenolic resin and vinylidene chloride Examples thereof include fillers such as resin powders such as resin organic microballoons, PVC powder, and PMMA powders; and fibrous fillers such as glass fibers and filaments. When the filler is used, the amount used is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (C).

  When you want to obtain a hardened product with high strength by using these fillers, mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment fine A filler selected from calcium carbonate, calcined clay, clay, activated zinc white and the like is preferable, and 1 to 200 weights per 100 weight parts of the total amount of the organic polymer (A) to (C) components having reactive silicon groups. If it is used within the range of parts, preferable results can be obtained. In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the organic polymer (A) to (C) components having a reactive silicon group, preferable results are obtained. In general, calcium carbonate has a greater effect of improving the breaking strength, breaking elongation, and adhesiveness of the cured product as the value of the specific surface area increases. Of course, these fillers may be used alone or in combination of two or more. When calcium carbonate is used, it is desirable to use a combination of surface treated fine calcium carbonate and heavy calcium carbonate such as heavy calcium carbonate. The particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 μm or less, and the surface treatment is preferably treated with a fatty acid or a fatty acid salt. Moreover, the particle size of calcium carbonate having a large particle size is preferably 1 μm or more, and an untreated surface can be used.

  In order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated, and may be used alone or in combination of two or more. In order to improve workability (such as sharpness), the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5 to 300 μm is preferable.

  The composition of the present invention is an adhesive for exterior wall joints, exterior wall tiles, and exterior wall tiles, such as sizing boards, especially ceramic sizing boards, because the cured product has good chemical resistance. However, it is desirable that the design of the outer wall and the design of the sealing material are harmonized. In particular, high-quality outer walls are used as outer walls due to the mixture of spatter coating, colored aggregates, and the like. When the composition of the present invention is blended with a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5.0 mm, the cured product is in harmony with such a high-quality outer wall. In addition, since the chemical resistance is excellent, the appearance of the cured product is an excellent composition that lasts for a long time. When a granular material is used, the surface becomes sandy or sandstone-like rough, and when a scaly material is used, the surface becomes uneven.

  As described in JP-A-9-53063, preferable diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows.

  The diameter is 0.1 mm or more, preferably about 0.1 to 5.0 mm, and those having an appropriate size are used according to the material and pattern of the outer wall. The thing of about 0.2 mm to 5.0 mm and about 0.5 mm to 5.0 mm can also be used. In the case of a scale-like substance, the thickness is about 1/10 to 1/5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed in the main sealing material at the construction site when used.

The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.
As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.

  Further, if a balloon (preferably having an average particle size of 0.1 mm or more) is used for the same purpose, the surface becomes sandy or sandstone-like, and the weight can be reduced. As described in JP-A-10-251618, preferred diameters, blending amounts, materials, and the like of the balloon are as follows.

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

  The balloon preferably has a particle size of 0.1 mm or more in order to obtain a surface having a sandy or sandstone texture. The thing of about 0.2 mm to 5.0 mm and about 0.5 mm to 5.0 mm can also be used. If it is less than 0.1 mm, even if it is blended in a large amount, it may only increase the viscosity of the composition and the rough feeling may not be exhibited. The blending amount of the balloon can be easily determined according to the desired degree of sanding tone or sandstone tone. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% in terms of volume concentration in the composition. When the volume concentration of the balloon is less than 5 vol%, there is no feeling of roughness, and when it exceeds 25 vol%, the viscosity of the sealing material and the adhesive becomes high, the workability is poor, the modulus of the cured product is also high, and the sealing material and bonding The basic performance of the agent tends to be impaired. The volume concentration with particularly preferable balance with the basic performance of the sealing material is 8 to 22 vol%.

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

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

  Even when the composition of the present invention contains particles of cured sealant, the cured product can form irregularities on the surface and improve the design. The preferable diameter, blending amount, material and the like of the cured sealant particles are as follows as described in JP-A-2001-115142. The diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm. The blending amount is preferably 5 to 100% by weight, more preferably 20 to 50% by weight in the curable composition. Examples of the material include urethane resin, silicone, modified silicone, polysulfide rubber and the like, and are not limited as long as they are used for the sealing material, but a modified silicone-based sealing material is preferable.

  Moreover, a silicate can be used for the composition of this invention. This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product of the composition of the present invention. Furthermore, it has the effect of improving adhesiveness, water-resistant adhesiveness, and adhesive durability under high temperature and high humidity conditions. As the silicate, tetraalkoxysilane or a partial hydrolysis condensate thereof can be used. When the silicate is used, the amount used is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the organic polymers (A) to (C).

  Specific examples of the silicate include, for example, tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n- Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as butoxysilane, tetra-i-butoxysilane, and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.

  The partial hydrolysis-condensation product of tetraalkoxysilane is more preferable because the restoring effect, durability, and creep resistance improvement effect of the present invention are greater than those of tetraalkoxysilane.

  Examples of the partial hydrolysis-condensation product of tetraalkoxysilane include a product obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis by a conventional method. A commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).

  A tackifier can be added to the composition of the present invention. Although it does not specifically limit as tackifying resin, What is normally used regardless of solid and liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resins, xylene-phenolic resins, cyclohexane. Pentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester 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 and the like. These may be used alone or in combination of two or more. Styrene block copolymers and their hydrogenated products include styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), and styrene-ethylenebutylene-styrene block copolymers. (SEBS), styrene-ethylenepropylene-styrene block copolymer (SEPS), styrene-isobutylene-styrene block copolymer (SIBS), and the like. The tackifying resins may be used alone or in combination of two or more.

  The tackifying resin is used in the range of 5 to 1,000 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (C).

  A solvent or diluent can be added to the composition of the present invention. Although it does not specifically limit as a solvent and a diluent, Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used. When a solvent or diluent is used, the boiling point of the solvent is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher because of the problem of air pollution when the composition is used indoors. . The said solvent or diluent may be used independently and may be used together 2 or more types.

  You may add the physical property modifier which adjusts the tensile characteristic of the hardened | cured material produced | generated as needed to the curable composition of this invention. Although it does not specifically limit as a physical property regulator, For example, alkyl alkoxysilanes, such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxy Alkoxysilanes having a functional group such as a silane; silicone varnishes; polysiloxanes and the like. By using the physical property modifier, it is possible to increase the hardness when the composition of the present invention is cured, or to decrease the hardness and break elongation. The said physical property modifier may be used independently and may be used together 2 or more types.

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

The physical property modifier is used in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total amount of the organic polymers (A) to (C) having reactive silicon groups. Is done.
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The anti-sagging 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, when rubber powder having a particle size of 10 to 500 μm as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used, thixotropy is high. A composition having good workability can be obtained. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) to (C).

  In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis (2-ethylhexyl) -4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, Examples thereof include epoxy butyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight based on 100 parts by weight of the total amount of the organic polymer (A) to (C) components having a reactive silicon group.

  To the curable composition of the present invention, a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, a flame retardant such as aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added. The said flame retardant may be used independently and may be used together 2 or more types.

  The flame retardant is used in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the total amount of the components (A) to (C).

  In the composition of the present invention, a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability. The solvent is not particularly limited, and various compounds can be used. Specific examples include hydrocarbon solvents such as toluene, xylene, heptane, hexane, petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketone solvents, alcohol solvents such as methanol, ethanol and isopropyl alcohol, and silicone solvents such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane. These solvents may be used alone or in combination of two or more.

  However, when the amount of the solvent is large, toxicity to the human body may be increased, and volume shrinkage of the cured product may be observed. Accordingly, the blending amount of the solvent is preferably 3 parts by weight or less, more preferably 1 part by weight or less, and substantially the solvent with respect to 100 parts by weight of the total amount of the components (A) to (C). Most preferably, it is not contained.

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

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

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. When the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so gelation is possible even if some moisture is contained in the compounding agent. However, when long-term storage stability is required, dehydration and drying are preferable. For dehydration and drying methods, heat drying method or vacuum dehydration method for solid materials such as powders, dehydration method using vacuum zeolite or activated zeolite, silica gel, quick lime, magnesium oxide for liquid materials The method is preferred. In addition to the dehydration drying method, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- An alkoxysilane compound such as glycidoxypropyltrimethoxysilane may be added and reacted with water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Addition of an alkoxysilane compound, an oxazolidine compound, and an isocyanate compound improves storage stability.

  The amount of the silicon compound capable of reacting with water, such as a dehydrating agent, especially vinyltrimethoxysilane, is 0.1 with respect to 100 parts by weight of the total amount of the organic polymer (A) to (C) components having reactive silicon groups. To 20 parts by weight, preferably in the range of 0.5 to 10 parts by weight.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components may be employed.

  The curable composition of the present invention is preferably in a liquid state at normal temperature (23 ° C.), and forms a three-dimensional network structure by the action of moisture when exposed to the atmosphere, to a solid having rubbery elasticity. And cured.

  The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration-proof material, a vibration-damping material, a sound-proof material, a foam material, a paint, and a spray material. Can be used for etc. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among them, it can be used as a sealing material or an adhesive, particularly an adhesive that is not a hot melt adhesive. More preferred.

  Also, electrical and electronic parts materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, contact type adhesives, spray type sealing materials, crack repair materials, and tiles Adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical device sealing materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coating materials, primers, electromagnetic wave shielding Conductive materials, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and anti-rust / waterproof sealing materials for meshed glass and laminated glass end faces (cut parts), It can be used for various applications such as liquid sealants used in automobile parts, electrical parts, various machine parts and the like. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . 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, It can also be used as a waterproof material combined with asphalt.

  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)
A polyoxypropylene triol having a number average molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a number average molecular weight of 26,200 having a hydroxyl group at three terminals (liquid feeding) As a system, Tosoh HLC-8120GPC was used, TOS-GEL H type manufactured by Tosoh was used as a column, and a polyoxypropylene (P-1) having a polystyrene-equivalent molecular weight measured using THF as a solvent was obtained.

  1.2 times molar equivalent sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-1). After distilling off methanol by vacuum devolatilization, 2.0 mol equivalent of 3-chloro-1-propene was added to the hydroxyl group of the polymer (P-1) to convert the terminal hydroxyl group to 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 group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. As a result, polyoxypropylene (P-2) having a number average molecular weight of about 26,200 having one carbon-carbon unsaturated bond at the terminal was obtained. The polymer (P-2) was found to have an average of 1.0 carbon-carbon unsaturated bonds introduced at one terminal site.

  To 500 g of the polymer (P-2), 50 μl of platinum divinyldisiloxane complex solution was added, and 6.3 g of trimethoxysilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to obtain polyoxypropylene (P-3) having a number average molecular weight of about 26,200 having a trimethoxysilyl group at the terminal. . The polymer (P-3) was found to have an average of 2.0 trimethoxysilyl groups in one molecule.

  Polymerized into a mixture of 300 g of methyl methacrylate, 115 g of 2-ethylhexyl acrylate, 46 g of γ-methacryloxypropyltrimethoxysilane, 37 g of γ-mercaptopropyltrimethoxysilane, and 140 g of IBA in 200 g of isobutyl alcohol (IBA) heated to 105 ° C. A solution in which 11.5 g of azobis-2-methylbutyronitrile was dissolved as an initiator was added dropwise over 4 hours, followed by polymerization after 2 hours, a solid content concentration of 60%, a number average molecular weight of 2,200, A (meth) acrylic acid ester copolymer (P-4) having an average of 1.5 methoxysilyl groups in one molecule was obtained. Reactive silicon group-containing polyoxypropylene (P-3) 60 so that the polymer (P-4) is 40 parts by weight in solid content of the solution of the (meth) acrylic acid ester copolymer (P-4). The mixture was uniformly mixed with parts by weight, and isobutyl alcohol was distilled off with a rotary evaporator to obtain a polymer mixture (Polymer A).

(Synthesis Example 2)
Polyoxypropylene glycol having a number average molecular weight of about 2,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and a polyoxypropylene having a number average molecular weight of 28,500 having hydroxyl groups at both ends. (P-5) was obtained. Subsequently, 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of this hydroxyl group-terminated polyoxypropylene (P-5). After distilling off methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the polymer (P-5) and reacted at 130 ° C. for 2 hours. Thereafter, 0.28 molar equivalent of sodium methoxide in methanol was added to remove the methanol, and 1.79 molar equivalent of 3-chloro-1-propene was added to convert the terminal hydroxyl group to 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 group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. As described above, polyoxypropylene (P-6) having a number average molecular weight of about 28,500 having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. The polymer (P-6) was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

  To 500 g of the obtained polymer (P-6), 10 g of trimethyl orthoacetate and 50 μl of platinum divinyldisiloxane complex solution were added, and 10.3 g of trimethoxysilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure, and a polyoxypropylene having a number average molecular weight of about 28,500 having a terminal structure having two or more trimethoxysilyl groups (polymer) B) was obtained. The polymer (Polymer B) was found to have an average of 1.6 trimethoxysilyl groups at one end and an average of 3.2 per molecule.

(Synthesis Example 3)
A polyoxypropylene diol having a number average molecular weight of about 3,000 is used as an initiator, and propylene oxide is polymerized by a zinc hexacyanocobaltate glyme complex catalyst, and a polyoxy having a number average molecular weight of 14,500 having hydroxyl groups at two ends. Propylene (P-7) was obtained.

  1.2 times molar equivalent sodium methoxide was added as a 28% methanol solution with respect to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene (P-7). After distilling off methanol by vacuum devolatilization, 2.0 molar equivalent of 3-chloro-1-propene was added to the hydroxyl group of the polymer (P-7) to convert the terminal hydroxyl group to 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 group-terminated polyoxypropylene, water was removed by centrifugation, and the resulting hexane solution was added. Further, 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by devolatilization under reduced pressure. Thus, polyoxypropylene (P-8) having a number average molecular weight of about 14,500 having a carbon-carbon unsaturated bond at the terminal was obtained.

  To 500 g of the polymer (P-8), 50 μl of platinum divinyldisiloxane complex solution was added, and 8.9 g of dimethoxymethylsilane was slowly added dropwise with stirring. After reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to obtain polyoxypropylene (P-9) having a number average molecular weight of about 14,500 having a dimethoxymethylsilyl group at the terminal. . The polymer (P-9) was found to have an average of 1.5 dimethoxymethylsilyl groups in one molecule.

  A mixture of 360 g of methyl methacrylate, 30 g of butyl acrylate, 70 g of stearyl methacrylate, 30 g of γ-methacryloxypropyldimethoxymethylsilane, 40 g of γ-mercaptopropyldimethoxymethylsilane, and 140 g of IBA in 200 g of isobutyl alcohol (IBA) heated to 105 ° C. A solution containing 15.0 g of azobis-2-methylbutyronitrile as a polymerization initiator was added dropwise over 4 hours, followed by polymerization after 2 hours, a solid content concentration of 60%, and a number average molecular weight of 2,000. A (meth) acrylic acid ester copolymer (P-10) having an average of 1.4 dimethoxymethylsilyl groups in one molecule was obtained.

Reactive silicon group-containing polyoxypropylene (P-) in the solution of the obtained (meth) acrylic acid ester copolymer (P-10) so that the polymer (P-10) has a solid content of 40 parts by weight. 9) The mixture was uniformly mixed with 60 parts by weight, and isobutyl alcohol was distilled off with a rotary evaporator to obtain a polymer mixture (Polymer C).
(Synthesis Example 4)
Polyoxypropylene diol having a number average molecular weight of about 2,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene having a number average molecular weight of about 28,500 (P-11). Got.

  A 28% methanol solution of 1.2 times molar equivalent sodium methoxide is added to the hydroxyl group of hydroxyl-terminated polyoxypropylene (P-11) to distill off the methanol, and further 1.3 times equivalent to the hydroxyl group. Allyl chloride was added to convert the terminal hydroxyl group into an allyl group. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified allyl-terminated polypropylene oxide, water was removed by centrifugation, and water was further added to the resulting hexane solution. After 300 parts by weight of the mixture were mixed and stirred, water was removed again by centrifugation, and then hexane was removed by devolatilization under reduced pressure. As a result, polyoxypropylene (P-12) having a number average molecular weight of about 28,500 having an allyl group at the end was obtained.

  100 parts by weight of the polymer (P-12) was reacted with 1.4 parts by weight of trimethoxysilane at 90 ° C. for 2 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst. A polyoxypropylene polymer having 6 trimethoxysilyl groups (Polymer D) was obtained.

(Synthesis Example 5)
3 parts by weight of toluene was added to 100 parts by weight of a crystalline polyester polyol (trade name: Dynacol 7331, melting point 110 ° C., molecular weight 3500, manufactured by Evonik), and azeotropic dehydration was performed at 110 ° C. under reduced pressure for 1.5 hours. After lowering the temperature to 90 ° C, 30 ppm of Neostan U-360 (manufactured by Nitto Kasei Co., Ltd.), a mercaptotin-based catalyst, is added, and 3-isocyanatopropyltriethoxysilane (manufactured by Momentive Performance Materials, Inc., product) Name: A-1310) 13.6 parts by weight were added and reacted. The disappearance of the peak of the isocyanate group (2272 cm ⁻¹ ) was confirmed by FT-IR, and the reaction was terminated to obtain a crystalline polyester polymer (b-1) having a triethoxysilyl group.

(Synthesis Example 6)
Except for using 11.3 parts by weight of 3-isocyanatopropyltrimethoxysilane (product name: Y-5187, manufactured by Momentive Performance Materials, Inc.) instead of 3-isocyanatopropyltriethoxysilane in Synthesis Example 5. In the same manner as in Synthesis Example 5, a crystalline polyester polymer (b-2) having a trimethoxysilyl group was obtained.

(Synthesis Example 7)
3 parts by weight of toluene was added to 100 parts by weight of a crystalline polyester polyol (trade name: Dynacol 7381, manufactured by Evonik Co., Ltd., melting point 65 ° C., molecular weight 3500), and azeotropic dehydration was performed at 110 ° C. under reduced pressure for 1.5 hours. After the temperature was lowered to 90 ° C., 30 ppm of Neostan U-360 was added, and 11.3 parts by weight of 3-isocyanatopropyltrimethoxysilane was added and reacted. The completion of the reaction was confirmed in the same manner as in Synthesis Example 5 to obtain a crystalline polyester polymer (b-3) having a trimethoxysilyl group.

(Synthesis Example 8)
3 parts by weight of toluene was added to 100 parts by weight of liquid polyester polyol (trade name: Dynacol 7255, product name: Dynacol 7255, molecular weight 3500) manufactured by Evonik, and azeotropic dehydration was performed at 110 ° C. under reduced pressure for 1.5 hours. After lowering the temperature to 90 ° C., 30 ppm of Neostan U-360 was added, and 14.0 parts by weight of 3-isocyanatopropyltriethoxysilane (made by Momentive Performance Materials, trade name: A-1310) was added. Reacted. The completion of the reaction was confirmed in the same manner as in Synthesis Example 5 to obtain a liquid polyester polymer (c-1) having a triethoxysilyl group.

(Synthesis Example 9)
3 parts by weight of toluene was added to 100 parts by weight of amorphous polyester polyol (Evonik, trade name: Dynacol 7131, melting point 76 ° C., molecular weight 3000), and azeotropic dehydration was performed at 110 ° C. under reduced pressure for 1.5 hours. After the temperature was lowered to 90 ° C., 30 ppm of Neostan U-360 was added, and 14.8 parts by weight of 3-isocyanatopropyltriethoxysilane was added and reacted. The completion of the reaction was confirmed in the same manner as in Synthesis Example 5 to obtain an amorphous polyester polymer (d-1) having a triethoxysilyl group.

(Synthesis Example 10)
An amorphous polyester having a trimethoxysilyl group in the same manner as in Synthesis Example 9 except that 9.4 parts by weight of 3-isocyanatopropyltrimethoxysilane was used instead of 3-isocyanatepropyltriethoxysilane in Synthesis Example 9. A system polymer (d-2) was obtained.

(Synthesis Example 11)
In the same manner as in Synthesis Example 10 except that 100 parts by weight of amorphous polyester polyol (trade name: Dynacol 7130, melting point 76 ° C., molecular weight 3000) manufactured by Evonik was used instead of Dynacor 7131 in Synthesis Example 10. An amorphous polyester polymer (d-3) having a trimethoxysilyl group was obtained.

Example 1
60 parts by weight of a mixture of a trimethoxysilyl group-containing polyoxypropylene polymer and a trimethoxysilyl group-containing (meth) acrylic acid ester copolymer (polymer A) obtained in Synthesis Example 1 and obtained in Synthesis Example 5 10 parts by weight of the triethoxysilyl group-containing crystalline polyester polymer (b-1) and 30 parts by weight of the triethoxysilyl group-containing liquid polyester polymer (c-1) obtained in Synthesis Example 8 were attached with a stirrer. The mixture was placed in a separate separable flask and stirred at 110 ° C. for 20 minutes. Thereafter, the temperature was lowered to 90 ° C., a small amount was taken out, placed in a vial, and allowed to stand at 23 ° C. for 24 hours, and the dispersibility was visually confirmed. After reducing the remaining polymer mixture to about 40 ° C., 5 parts by weight of an adhesion-imparting agent, 3-glycidoxypropyltrimethoxysilane (product name: A-187, manufactured by Momentive Performance Materials), 5 parts by weight of a titanium-based curing catalyst (manufactured by Dorf Ketal, trade name: Tyzor PITA) was added and kneaded to obtain a curable composition.

(Example 2)
Instead of the triethoxysilyl group-containing liquid polyester polymer (c-1) in Example 1, 30 parts by weight of the triethoxysilyl group-containing amorphous polyester polymer (d-1) obtained in Synthesis Example 9 was used. Except for this, a curable composition was obtained in the same manner as in Example 1.

(Example 3)
The amount of the triethoxysilyl group-containing liquid polyester polymer (c-1) used in Example 1 was changed to 10 parts by weight, and the triethoxysilyl group-containing amorphous polyester polymer (d) obtained in Synthesis Example 9 (d) -1) A curable composition was obtained in the same manner as in Example 1 except that 20 parts by weight was used.

Example 4
Instead of the mixture of trimethoxysilyl group-containing polyoxypropylene polymer and trimethoxysilyl group-containing (meth) acrylic acid ester copolymer (polymer A) in Example 2, trimethoxysilyl obtained in Synthesis Example 2 A curable composition was obtained in the same manner as in Example 2 except that 60 parts by weight of the group-containing polyoxypropylene polymer (Polymer B) was used.

(Example 5)
Instead of the mixture (polymer A) of the trimethoxysilyl group-containing polyoxypropylene-based polymer and the trimethoxysilyl group-containing (meth) acrylic acid ester copolymer in Example 2, dimethoxymethylsilyl obtained in Synthesis Example 3 A curable composition in the same manner as in Example 2 except that 60 parts by weight of a mixture (polymer C) of a group-containing polyoxypropylene polymer and a dimethoxymethylsilyl group-containing (meth) acrylic acid ester copolymer was used. Got.

(Comparative Example 1)
Without using the triethoxysilyl group-containing crystalline polyester polymer (b-1) and the triethoxysilyl group-containing liquid polyester polymer (c-1) in Example 1, a trimethoxysilyl group-containing polyoxypropylene system was used. A curable composition was obtained in the same manner as in Example 1 except that 100 parts by weight of a mixture of the polymer and a trimethoxysilyl group-containing (meth) acrylic acid ester copolymer (polymer A) was used.

(Comparative Example 2)
A curable composition was obtained in the same manner as in Comparative Example 1 except that 100 parts by weight of the polymer C obtained in Synthesis Example 3 was used instead of the polymer A in Comparative Example 1.

(Comparative Example 3)
The amount of the polymer C used in Comparative Example 2 was changed to 60 parts by weight, except that 40 parts by weight of the triethoxysilyl group-containing crystalline polyester polymer (b-1) obtained in Synthesis Example 5 was used. A curable composition was obtained in the same manner as in Comparative Example 2.

(Comparative Example 4)
Instead of using the triethoxysilyl group-containing crystalline polyester polymer (b-1) in Comparative Example 3, 10 weight of the triethoxysilyl group-containing liquid polyester polymer (c-1) obtained in Synthesis Example 8 A curable composition was obtained in the same manner as in Comparative Example 3 except that 30 parts by weight of the triethoxysilyl group-containing amorphous polyester polymer (d-1) obtained in Synthesis Example 9 was used.

(Comparative Example 5)
Instead of using the triethoxysilyl group-containing crystalline polyester polymer (b-1) in Comparative Example 3, 10 parts by weight of a liquid polyester polyol (trade name: Dynacol 7255, manufactured by Evonik), an amorphous polyester polyol (Evonik) A curable composition was obtained in the same manner as in Comparative Example 3, except that 30 parts by weight of a product manufactured by the company, trade name: Dynacol 7131) was used.

(Comparative Example 6)
Curing was carried out in the same manner as in Comparative Example 1, except that 100 parts by weight of the trioxysilyl group-containing polyoxypropylene polymer (Polymer D) obtained in Synthesis Example 4 was used instead of Polymer A in Comparative Example 1. Sex composition was obtained.

(Comparative Example 7)
Curing was conducted in the same manner as in Comparative Example 4 except that 60 parts by weight of the trioxysilyl group-containing polyoxypropylene polymer (Polymer D) obtained in Synthesis Example 4 was used instead of Polymer C in Comparative Example 4. Sex composition was obtained.

The compatibility and the shear tensile strength of the curable composition were evaluated by the following methods. The results are shown in Table 1.
(Compatibility)
Before adding the silane coupling agent A-187 and the curing catalyst, a small amount was put in a vial and allowed to stand at 23 ° C. for 24 hours, and then the dispersibility was visually confirmed.

(Shear tensile strength)
Hard vinyl chloride base material (manufactured by Nippon Tact Co., Ltd., JISK6745, size: 3 × 25 × 100 mm) and polycarbonate base material (manufactured by Nippon Tact Co., Ltd., JISK6735) Using a colorless and transparent, size: 3 × 25 × 100 mm, a test specimen for evaluating shear adhesion was prepared by setting the thickness of each curable composition to 30 μm and the bonding area to 25 mm × 25 mm. Tensile strength was measured at a rate of 50 mm / min according to JISK6850 after standard curing for 3 days at 23 ° C. and 50% RH, and after 4 days of standard curing for 50 days at 50 ° C. and further for 7 days in warm water at 50 ° C.

  As is clear from Table 1, Examples 1 to 5, which use the (A) component, the (B) component, and the (C) component in combination, have excellent compatibility and high shear tensile strength. It can be seen that this is superior in strength compared to Comparative Examples 1, 2, and 6 using only the component (A). Comparative Example 3 is an example in which the component (A) and the component (B) are used in combination, but the shear strength is lower than that in Comparative Example 2 in which only the component (A) is used. Comparative Example 4 and Comparative Example 7 are examples in which the (C) component is used in combination with the (A) component, but the shear strength is improved by the addition of the (C) component, but the compatibility is poor. Comparative Example 5 is an example using the polyester that does not introduce the silyl group of component (C) used in Comparative Example 4, but it can be seen that a polyester that does not contain a silyl group has no effect of imparting strength.

(Example 6)
60 parts by weight of a mixture (polymer A) of a trimethoxysilyl group-containing polyoxypropylene polymer and a trimethoxysilyl group-containing (meth) acrylic acid ester copolymer obtained in Synthesis Example 1 and obtained in Synthesis Example 6 10 parts by weight of the trimethoxysilyl group-containing crystalline polyester polymer (b-2) and 30 parts by weight of the trimethoxysilyl group-containing amorphous polyester polymer (d-2) obtained in Synthesis Example 10 were attached with a stirrer. The mixture was placed in a separate separable flask and stirred at 110 ° C. for 20 minutes. Thereafter, the temperature was lowered to 90 ° C., a small amount was taken out, placed in a vial, and allowed to stand at 23 ° C. for 24 hours, and the dispersibility was visually confirmed. After reducing the remaining polymer mixture to about 40 ° C., 3 parts by weight of vinyltrimethoxysilane (product name: A-171 manufactured by Momentive Performance Materials, Inc.) as a dehydrating agent, 3- Add 3 parts by weight of glycidoxypropyltrimethoxysilane (product name: A-187, manufactured by Momentive Performance Materials) and 3 parts by weight of titanium-based curing agent (product name: Tyzor PITA, manufactured by Dorf Ketal). By kneading, a one-component curable composition was obtained.

(Example 7)
Instead of using the trimethoxysilyl group-containing crystalline polyester polymer (b-2) and the trimethoxysilyl group-containing amorphous polyester polymer (d-2) in Example 6, the trimethoxysilyl group-containing amorphous polyester polymer (d-2) was used. Other than using 10 parts by weight of the methoxysilyl group-containing crystalline polyester polymer (b-3) and 30 parts by weight of the trimethoxysilyl group-containing amorphous polyester polymer (d-3) obtained in Synthesis Example 11. Obtained a one-component curable composition in the same manner as in Example 6.

(Example 8)
Instead of using 3-glycidoxypropyltrimethoxysilane and titanium-based curing agent in Example 7, γ- (2-aminoethyl) aminopropyltrimethoxysilane (manufactured by Momentive Performance Materials, trade name: A-1120) 3 parts by weight, same as Example 7 except that 0.15 parts by weight of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-100) which is a tin-based curing catalyst is used. Thus, a one-component curable composition was obtained.

(Comparative Example 8)
Instead of using the trimethoxysilyl group-containing crystalline polyester polymer (b-3) and the trimethoxysilyl group-containing amorphous polyester polymer (d-3) in Example 8, a trimethoxysilyl group-containing polyoxypropylene was used. A one-component curable composition was obtained in the same manner as in Example 8, except that 100 parts by weight of a mixture of a polymer and a trimethoxysilyl group-containing (meth) acrylic acid ester copolymer (polymer A) was used. It was.

Using the curable composition obtained above, the compatibility, surface curing time, and tensile strength of the film-like cured product were measured. Each physical property was evaluated by the following methods. The results are shown in Table 2.
(Surface curing time)
The curable composition was poured into a container so as to have 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. Was measured until the microspatula disappeared.

(Tensile property of cured product)
The curable composition was formed into a film having a thickness of about 1 mm, placed under conditions of 23 ° C. and 50% RH for 3 days, and further placed 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, and a 30% tensile modulus, strength at break, and elongation at break were measured.

As can be seen from Table 2, Examples 6 to 8 in which the (A) component, the (B) component, and the (C) component are used in combination are excellent in compatibility, have a fast surface curing time, and have a high tensile strength of the cured product. Are better. Example 8 and Comparative Example 8 are examples in which a tin-based curing catalyst is used, but compatibility is good by using the (B) component and the (C) component of the present invention together in the tin-based curing catalyst system. It can be seen that a composition having a high strength can be obtained.

Claims (14)

(A) An organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, the main chain skeleton of which is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, a (meth) acrylic ester heavy polymer An organic polymer that is at least one selected from the group consisting of a polymer, (B) an organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, wherein the main chain skeleton is a polyester-based polymer, A crystalline organic polymer that is at least one selected from the group consisting of polyamide polymers, (C) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, and a main chain skeleton There polyester polymers, noncrystalline organic polymer is at least one selected from the group consisting of polycarbonate-based polymer, only contains normal temperature (23 ° C. In the curable composition is a liquid.   The organic polymer (B) and / or the organic polymer (C) is an organic polymer obtained by reacting a silicon compound having at least one of a hydrosilyl group, an isocyanate group and a thiol group. The curable composition according to 1.   The curable composition according to claim 1, wherein the organic polymer (B) and / or the organic polymer (C) is an organic polymer not containing a main chain skeleton obtained by reacting a diisocyanate compound. object.   The curable composition according to any one of claims 1 to 3, wherein the main chain skeleton of the organic polymer (B) and / or the organic polymer (C) is a polyester polymer.   The curable composition according to any one of claims 1 to 4, wherein the organic polymer (A) is a polyoxyalkylene polymer and a (meth) acrylic acid ester polymer.   The curable composition according to any one of claims 1 to 5, wherein the crosslinkable silicon group of the organic polymer (A) is a trialkoxysilyl group.   The curable composition according to any one of claims 1 to 6, wherein the crosslinkable silicon group of the organic polymer (B) and / or the organic polymer (C) is a trialkoxysilyl group.   The curable composition according to any one of claims 1 to 7, wherein at least one selected from the group consisting of an organic tin compound, a titanium compound, a carboxylic acid, a carboxylic acid metal salt, and an amine compound is used as the curing catalyst (D). .   The plasticizer (E) is further contained, and the amount of the plasticizer (E) used is 30 parts by weight or less with respect to 100 parts by weight of the total amount of the organic polymers (A) to (C). The curable composition in any one. (A) An organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, the main chain skeleton of which is a polyoxyalkylene polymer, a saturated hydrocarbon polymer, a (meth) acrylic ester heavy polymer An organic polymer that is at least one selected from the group consisting of a polymer, (B) an organic polymer having a silicon group that can be cross-linked by forming a siloxane bond, wherein the main chain skeleton is a polyester-based polymer, A crystalline organic polymer that is at least one selected from the group consisting of polyamide polymers, (C) an organic polymer having a silicon group that can be crosslinked by forming a siloxane bond, and a main chain skeleton A non-crystalline organic polymer that is at least one selected from the group consisting of polyester-based polymers and polycarbonate-based polymers. Curable composition without ester copolymer. The sealing material which uses the curable composition in any one of Claims 1-10 . The adhesive agent using the curable composition in any one of Claims 1-10 . The coating material formed using the curable composition in any one of Claims 1-10 . A cured product obtained by curing the curable composition according to claim 10 .