JP6371049B2 - Curable composition - Google Patents

Description

  The present invention relates to a polymer having a crosslinkable silyl group and a curable composition containing an air oxidation curable compound.

  A polymer containing a crosslinkable silyl group can be a liquid polymer and is cured at room temperature with moisture or the like to produce a rubber-like cured product. For this reason, it is used for the elastic sealant of a building, an adhesive agent, etc.

  Examples of the main chain of the polymer containing the crosslinkable silyl group include polyoxyalkylene polymers, (meth) acrylic acid ester polymers, saturated hydrocarbon polymers, and the like. It is used for applications suitable for In particular, polyoxyalkylene polymers are often used as sealants that require a low elastic modulus.

  When the above-mentioned polymer containing a crosslinkable silyl group is used as an elastic sealant for a building, the surface of the sealant after curing may become sticky, resulting in dust adhesion and a decrease in weather resistance. Therefore, by adding an air oxidation curable compound, stickiness is suppressed and the weather resistance of the surface is improved (Patent Documents 1 to 5).

  As the air oxidation curable compound, a liquid diene compound which is cured by oxygen, natural drying oil such as paulownia oil and linseed oil, and the like are used.

Japanese Patent Laid-Open No. 05-065407 JP 2011-219554 A JP 2002-179904 A WO2005 / 071015 Japanese Patent Laid-Open No. 02-132150

  An object of the present invention is to obtain a curable composition having good storage stability even if moisture is contained in a curable composition containing a crosslinkable silyl group and an air oxidation curable compound. To do.

As a result of intensive studies to solve the above problems, it has been clarified that the storage stability is improved by setting the acid value of the air oxidation curable compound to 4.0 or less.
That is, the present invention relates to a curable composition containing (A) a polymer having a crosslinkable silyl group and (B) an air oxidation curable compound having an acid value of 4.0 mgKOH / g or less.
The air oxidation curable compound (B) is preferably a natural drying oil and / or a modified product thereof.
The natural drying oil is preferably tung oil and / or linseed oil.
(B) It is preferable that the acid value of a component is 3.5 mgKOH / g or less.
It is preferable that the polymer of the component (A) is a polyoxyalkylene polymer.
It is preferable that a crosslinkable silyl group is General formula (1).
-SiR ¹ _3-a Z _a (1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, 3)
Said curable composition can be used suitably for a sealing material and an adhesive agent.
A cured product can be obtained by curing the curable composition.

  Even if moisture is contained in the curable composition containing a polymer having a crosslinkable silyl group and an air oxidation curable compound, a curable composition having good storage stability can be obtained.

  The present invention is a curable composition containing (A) a polymer having a crosslinkable silyl group and (B) an air oxidation curable compound having an acid value of 4.0 mgKOH / g or less.

<< (A) component >>
In the present invention, a polymer having a crosslinkable silyl group is used as the component (A). The main chain skeleton of the polymer (A) having a crosslinkable silyl group used in the present invention is not particularly limited, and those having various main chain skeletons can be used.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. 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 A copolymer of acrylonitrile and styrene, etc., a hydrocarbon polymer such as a hydrogenated polyolefin polymer obtained by hydrogenating these polyolefin polymers; a dibasic acid such as adipic acid and a glycol; Polyester polymers obtained by condensation or ring-opening polymerization of lactones; (meth) acrylic acid ester polymers obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate; (Meth) acrylic acid ester monomers, vinyl polymers obtained by radical polymerization of monomers such as vinyl acetate, acrylonitrile, styrene, etc .; graft polymers obtained by polymerizing vinyl monomers in the organic polymers; polysulfides Polymer: Nylon 6 by ring-opening polymerization of ε-caprolactam, nylon 6.6 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 6.10 by condensation polymerization of hexamethylenediamine and sebacic acid, ε-aminoundecanoic acid Nylon 11, ε-aminolaurolacta by condensation polymerization A polyamide polymer such as nylon 12 by ring-opening polymerization of the above, a copolymer nylon having two or more components among the above-mentioned nylons; for example, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl Examples thereof include phthalate polymers. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene and hydrogenated polybutadiene, polyoxyalkylene polymers, and (meth) acrylic acid ester polymers have a relatively low glass transition temperature, and the resulting cured product Is more preferable because of its excellent cold resistance.

  Polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because of their high moisture permeability and excellent deep-part curability when used in a one-part composition, and also excellent adhesion. Alkylene polymers are most preferred.

<Crosslinkable silyl group>
The crosslinkable silyl group contained in the polymer having a crosslinkable silyl group has a hydroxyl group or hydrolyzable group bonded to a silicon atom, and forms a siloxane bond by a reaction accelerated by a silanol condensation catalyst. It is a group capable of crosslinking. As the crosslinkable silyl group, the general formula (1):
-SiR ¹ _3-a Z _a (1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, and 3).

  It does not specifically limit as a hydrolysable group, What is necessary is just a conventionally well-known hydrolysable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable. Particularly preferred.

  Hydrolyzable groups and hydroxyl groups can be bonded to the silicon atom in the range of 1 to 3, and when two or more bonds are bonded to the silicon group, they may be the same or different. Good.

Specific examples of R ¹ 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, aralkyl groups such as a benzyl group, R ′ is a methyl group, Examples thereof include a triorganosiloxy group represented by (R ′) ₃ SiO— which is a phenyl group. Of these, a methyl group is particularly preferred.

  More specific examples of the crosslinkable silyl group include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, methoxydimethylsilyl. Group, ethoxydimethylsilyl group and the like. A trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are more preferable, and a trimethoxysilyl group is particularly preferable because of high activity and good curability. In addition, a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability. The triethoxysilyl group is particularly preferable because the alcohol produced in the hydrolysis reaction of the crosslinkable silyl group is ethanol and has higher safety.

  In addition, an organic polymer having a crosslinkable silyl group having three hydrolyzable groups on a silicon atom can provide high curability, and also has good restorability, durability, and creep resistance. This is preferable.

  The introduction of the crosslinkable silyl group may be performed by a known method. That is, for example, the following method can be mentioned.

  (B) An organic polymer having an unsaturated group is reacted with an organic polymer having a functional group such as a hydroxyl group in the molecule by reacting an organic compound having an active group and an unsaturated group reactive to the functional group. Get coalesced. Alternatively, an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound. Then, the resulting reaction product is hydrosilylated by allowing hydrosilane having a crosslinkable silyl group to act.

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

  (C) An organic polymer having a functional group such as a hydroxyl group, an epoxy group, or an isocyanate group in the molecule is reacted with a compound having a functional group reactive to the functional group and a crosslinkable silyl group.

  Among the above methods, the method (a) or the method (c) in which the organic polymer having a hydroxyl group at the terminal and the compound having an isocyanate group and a crosslinkable silyl group are reacted in a relatively short reaction time. It is preferable because a high conversion rate can be obtained. Furthermore, the organic polymer having a crosslinkable silyl group obtained by the method (a) becomes a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). The organic polymer obtained by the method (b) has a strong odor based on mercaptosilane, and therefore the method (a) is particularly preferred.

  Specific examples of the hydrosilane compound used in the method (a) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, and methyldiethoxysilane. Alkoxysilanes such as methyldimethoxysilane and phenyldimethoxysilane; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; bis (dimethylketoximate) methylsilane, bis (cyclohexylketoximate) methylsilane Examples thereof include, but are not limited to, ketoximate silanes. Among these, halogenated silanes and alkoxysilanes are particularly preferable, and alkoxysilanes are particularly preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle. Among the alkoxysilanes, methyldimethoxysilane is particularly preferable because it is easily available and the curable composition containing the obtained organic polymer has high curability, storage stability, elongation characteristics, and tensile strength.

  As a synthesis method of (b), for example, a compound having a mercapto group and a crosslinkable silyl group is converted into an unsaturated bond site of an organic polymer by a radical addition reaction in the presence of a radical initiator and / or a radical generation source. Although the method of introduce | transducing etc. is mentioned, it does not specifically limit. Specific examples of the compound having a mercapto group and a crosslinkable silyl group include, for example, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyldiethoxymethyl. Examples include, but are not limited to, silane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, and the like.

  As a method of reacting an organic polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silyl group in the synthesis method (c), for example, the method described in JP-A-3-47825 can be mentioned. However, it is not particularly limited. Specific examples of the compound having an isocyanate group and a crosslinkable silyl group include, for example, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatepropyldimethoxymethylsilane, γ-isocyanatepropyltriethoxysilane, and γ-isocyanatepropyldiethoxymethyl. Examples include, but are not limited to, silane, isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, and isocyanatemethyldiethoxymethylsilane.

  The polymer having a crosslinkable silyl group as the component (A) may have a straight chain or a branch, and the number average molecular weight is more than 6,000 and not more than 100,000 in terms of polystyrene in GPC. More preferably, it is 7,000-50,000, Most preferably, it is 9,000-30,000. If the number average molecular weight is 6,000 or less, there is an inconvenient tendency in terms of elongation characteristics of the cured product, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity.

  In the case where the component (A) is a polyoxyalkylene polymer having a crosslinkable silyl group having a reactive silicon group, the number average molecular weight of the polyoxyalkylene polymer is the organic polymer before introduction of the reactive silicon group. The precursor was directly measured for the end group concentration by titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method defined in JIS K 0070. The molecular weight (end group molecular weight) corresponding to the number average molecular weight determined in consideration of the structure (branching degree determined by the polymerization initiator used) is defined. (A) As a measuring method of the number average molecular weight of a component, the calibration curve of the polystyrene conversion number average molecular weight (GPC molecular weight) calculated | required by the general GPC measurement of an organic polymer precursor and the said terminal group molecular weight is created, ( It is also possible to obtain the GPC molecular weight of the component A) by converting it to a terminal group molecular weight.

  In order to obtain a rubber-like cured product having high strength, high elongation, and low elastic modulus, at least one crosslinkable silyl group contained in component (A) is averaged in one molecule of the polymer, preferably It should be 1.1-5. When the number of crosslinkable silyl groups contained in the molecule is less than 1 on average, curability becomes insufficient, and good rubber elasticity behavior is hardly exhibited. The crosslinkable silyl group may be at the end of the main chain of the organic polymer molecular chain, at the end of the side chain, or at both ends. In particular, when the crosslinkable silyl group is at the end of the main chain of the molecular chain, the effective network length of the polymer component contained in the finally formed cured product is increased, so that the strength and elongation are high, and the low It becomes easy to obtain a rubber-like cured product exhibiting an elastic modulus.

<Polyoxyalkylene polymer>
The polyoxyalkylene polymer essentially has the general formula (2):
-R ² -O- ⁽²⁾
(Wherein R ² is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ² in the general formula (2) is the number of carbon atoms. 1 to 14, more preferably 2 to 4, linear or branched alkylene groups are preferred. Specific examples of the repeating unit represented by the general formula (2) include

Etc. The main chain skeleton of the polyoxyalkylene polymer may consist of only one type of repeating unit, or may consist of two or more types of repeating units. In particular, when used in a sealant or the like, a polymer comprising a propylene oxide polymer as a main component is preferred because it is amorphous or has a relatively low viscosity.

  Examples of the method for synthesizing the polyoxyalkylene polymer include a polymerization method using an alkali catalyst such as KOH, and a complex obtained by reacting an organoaluminum compound and porphyrin as disclosed in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Patent 3,278,457, US Patent 3,278,458, US Patent 3,278,459, US Patent 3,427,256, US Patent 3,427,334, Polymerization method using double metal cyanide complex catalyst as shown in U.S. Pat. No. 3,427,335, polymerization method using catalyst comprising polyphosphazene salt exemplified in JP-A-10-273512, phosphazene exemplified in JP-A-11-060722 Using a compound catalyst Polymerization method, and the like, but not particularly limited.

  A method for producing a polyoxyalkylene polymer having a crosslinkable silyl group is disclosed in JP-B Nos. 45-36319, 46-12154, JP-A Nos. 50-156599, 54-6096, and 55-13767. JP-A-55-13468, JP-A-57-16123, JP-B-3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345,053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc. -197631, 61-215622, 61-215623, 61-218632, JP-A-3-72527, JP-A-3-47825, and JP-A-8-231707. Polyoxya with a narrow molecular weight distribution with a high molecular weight with a number average molecular weight of 6,000 or more and Mw / Mn of 1.6 or less Killen polymer can be exemplified, but not particularly limited thereto.

  The above polyoxyalkylene polymers having a crosslinkable silyl group may be used alone or in combination of two or more.

<Saturated hydrocarbon polymer>
The saturated hydrocarbon polymer is a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring, and the polymer constituting the skeleton thereof is (1) ethylene, propylene, 1-butene, isobutylene, etc. The main monomer is an olefin compound having 2 to 6 carbon atoms, or (2) a diene compound such as butadiene or isoprene is homopolymerized, or is copolymerized with the olefin compound. After that, it can be obtained by a method such as hydrogenation. However, isobutylene-based polymers and hydrogenated polybutadiene-based polymers can easily introduce functional groups at the terminals, easily control the molecular weight, The number can be increased, and an isobutylene polymer is particularly preferable.

  Those whose main chain skeleton is a saturated hydrocarbon polymer have characteristics of excellent heat resistance, weather resistance, durability, and moisture barrier properties.

  In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, or may be a copolymer with other monomers, but the repeating unit derived from isobutylene is 50 from the viewpoint of rubber properties. What contains more than weight% is preferable, What contains 80 weight% or more is more preferable, What contains 90 to 99 weight% is especially preferable.

  As a method for synthesizing a saturated hydrocarbon polymer, various polymerization methods have been reported so far, but in particular, many so-called living polymerizations have been developed in recent years. In the case of saturated hydrocarbon polymers, particularly isobutylene polymers, the inifer polymerization found by Kennedy et al. (JP Kennedy et al., J. Polymer Sci., Polymer Chem. Ed. 1997, 15, 2843). It is known that a molecular weight of about 500 to 100,000 can be polymerized with a molecular weight distribution of 1.5 or less, and various functional groups can be introduced at the molecular ends.

  Examples of the method for producing a saturated hydrocarbon polymer having a crosslinkable silyl group include Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 63-254149, Japanese Patent Publication No. 64-22904, Although described in each specification of Kaihei 1-197509, Japanese Patent Publication No. 2539445, Japanese Patent Publication No. 2873395, and Japanese Patent Application Laid-Open No. 7-53882, it is not particularly limited thereto.

The saturated hydrocarbon polymer having a crosslinkable silyl group may be used alone or in combination of two or more.
<(Meth) acrylic acid ester polymer>
It does not specifically limit as a (meth) acrylic-ester type monomer which comprises the principal chain of the said (meth) acrylic-ester type polymer, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 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, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxy) propyltrimethoxysilane, γ- (methacryloyloxy) propyldimethoxymethylsilane, methacryloyloxymethyltrimethoxysilane, methacryloyloxymethyltriethoxysilane, methacryloyloxymethyldimethoxymethylsilane, methacryloyloxymethyldiethoxymethylsilane, (Meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethyl methyl, (meth) acrylic acid 2-trifluoromethyl ethyl, (meth) acrylic acid 2- -Fluoroethylethyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoro) (meth) acrylate Methyl) methyl, (meth) acrylic acid 2-trifluoromethyl-2-perfluoroethylethyl, (meth) acrylic acid 2-perfluorohexylethyl, (meth) acrylic acid 2-perfluorodecylethyl, (meth) acrylic Examples include (meth) acrylic acid monomers such as 2-perfluorohexadecylethyl acid.

  In the (meth) acrylic acid ester polymer, the following vinyl monomer can be copolymerized together with the (meth) acrylic acid ester monomer. Examples of the vinyl monomer include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid, and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, Methyl maleimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, cyclohex Maleimide monomers such as lumaleimide; Nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, cinnamon Examples thereof include vinyl esters such as vinyl acid; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol.

  These may be used alone or a plurality of these may be copolymerized. Especially, the polymer which consists of a styrene-type monomer and a (meth) acrylic-acid type monomer from the physical property of a product etc. is preferable. More preferred is a (meth) acrylic polymer comprising an acrylate monomer and a methacrylic acid ester monomer, and particularly preferred is an acrylic polymer comprising an acrylate monomer.

  It does not specifically limit as a synthesis method of a (meth) acrylic acid ester type polymer, What is necessary is just to carry out by a well-known method. However, a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity is increased. Yes. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. It is preferable to use a living radical polymerization method.

  Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing a (meth) acrylate monomer using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, In addition to the characteristics of the “living radical polymerization method”, it has a halogen or the like that is relatively advantageous for functional group conversion reaction, and has a specific functional group because it has a large degree of freedom in designing initiators and catalysts ( The method for producing a (meth) acrylic acid ester polymer is more preferable. Examples of this atom transfer radical polymerization method include Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614.

  Examples of the method for producing a (meth) acrylic acid ester-based polymer having a crosslinkable silyl group include chain transfer in JP-B-3-14068, JP-B-4-55444, JP-A-6-221922, and the like. A production method using a free radical polymerization method using an agent is disclosed. Japanese Patent Application Laid-Open No. 9-272714 discloses a production method using an atom transfer radical polymerization method, but is not particularly limited thereto.

  The (meth) acrylic acid ester polymer having a crosslinkable silyl group may be used alone or in combination of two or more.

<Polymer blend>
The above polymers having a crosslinkable silyl group may be used alone or in combination of two or more. Specifically, a group consisting of a polyoxyalkylene polymer having a crosslinkable silyl group, a saturated hydrocarbon polymer having a crosslinkable silyl group, and a (meth) acrylic acid ester polymer having a crosslinkable silyl group. A polymer obtained by blending two or more selected from the above can also be used.

<Polymer containing urethane bond component>
On the other hand, the main chain skeleton of the polymer may contain other components such as a urethane bond component as long as the effects of the present invention are not significantly impaired.

  Although it does not specifically limit as said urethane bond component, The group (henceforth an amide segment) produced | generated by reaction of an isocyanate group and an active hydrogen group can be mentioned.

The amide segment has the general formula (3):
-NR < ³ > -C (= O)-(3)
(R ³ represents a hydrogen atom or a substituted or unsubstituted organic group).

Specifically, the amide segment includes a urethane group formed by a reaction between an isocyanate group and a hydroxyl group; a urea group formed by a reaction between the isocyanate group and an amino group; a thiol formed by a reaction between the isocyanate group and a mercapto group. A urethane group etc. can be mentioned. Moreover, in this invention, the group which the active hydrogen in the said urethane group, urea group, and thiourethane group reacts with an isocyanate group and also produces | generates is also contained in group of General formula (3). An example of an industrially easy method for producing a polymer having an amide segment and a crosslinkable silyl group is as follows. An excess polyisocyanate compound is reacted with a polymer having an active hydrogen-containing group at a terminal to form a polyurethane main chain. After the polymer having an isocyanate group at the end or simultaneously, all or a part of the isocyanate group is represented by the general formula (4)
W-R ⁴ -SiR ¹ _3-a Z _a (4)
(In the formula, R ¹ , Z and a are the same as above. R ⁴ is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms. W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an unsubstituted or monosubstituted amino group. Things can be mentioned. Examples of known production methods for organic polymers related to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557), Japanese Patent Application Laid-Open No. 58-109529 (US Pat. No. 4,374,237), Japanese Patent Application Laid-Open No. Sho 62. 13430 (US Pat. No. 4,645,816), JP-A-8-53528 (EP0676403), JP-A-10-204144 (EP0831108), JP 2003-508561 (US Pat. No. 6,1979,912), JP-A-6-21879 (US) (Japanese Patent No. 5364955), Japanese Patent Laid-Open No. 10-53637 (US Pat. No. 5,757,751), Japanese Patent Laid-Open No. 11-100197, Japanese Patent Laid-Open No. 2000-169544, Japanese Patent Laid-Open No. 2000-169415, Japanese Patent Laid-Open No. 2002-212415, and Japanese Patent No. 3313360 , US Pat. No. 4,067,844, US Pat. No. 37 No. 1445, JP 2001-323040, and the like.

Further, the organic polymer having an active hydrogen-containing group at the terminal is represented by the general formula (5)
O = C = N—R ⁴ —SiR ¹ _3-a Z _a (5)
(However, in the formula, R ¹ , R ⁴ , Z, and a are the same as described above.) A compound produced by reacting with a crosslinkable silyl group-containing isocyanate compound can be exemplified. Examples of known production methods of organic polymers related to this production method include JP-A-11-279249 (US Pat. No. 5,990,257), JP-A 2000-119365 (US Pat. No. 6,046,270), JP-A 58- No. 29818 (US Pat. No. 4,345,053), JP-A-3-47825 (US Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002-155145, JP-A-2002-249538, WO03 / 018658, WO03 / 059981. Etc.

  Examples of the polymer having an active hydrogen-containing group at the terminal include a polyoxyalkylene polymer having a hydroxyl group at the terminal (polyether polyol), a polyacryl polyol, a polyester polyol, and a saturated hydrocarbon polymer having a hydroxyl group at the terminal (polyolefin polyol). ), Polythiol compounds, polyamine compounds and the like. Among these, polyether polyol, polyacryl polyol, and polyolefin polyol are preferable because the obtained organic polymer has a relatively low glass transition temperature and the resulting cured product is excellent in cold resistance. In particular, the polyether polyol is particularly preferable because the resulting polymer has a low viscosity, good workability, and good deep part curability. Polyacryl polyols and saturated hydrocarbon polymers are more preferred because the resulting cured organic polymer has good weather resistance and heat resistance.

  As the polyether polyol, those produced by any production method can be used, but those having at least 0.7 hydroxyl groups per molecular terminal in terms of the total molecular average are preferred. Specifically, an initiator such as a polyoxyalkylene polymer produced using a conventional alkali metal catalyst, or a polyhydroxy compound having at least two hydroxyl groups in the presence of a double metal cyanide complex or cesium is used as an alkylene. Examples thereof include polyoxyalkylene polymers produced by reacting oxides.

  Among the above polymerization methods, a polymerization method using a double metal cyanide complex is a polyoxyalkylene having a lower degree of unsaturation, a narrower Mw / Mn, a lower viscosity, and a high acid resistance and high weather resistance. It is preferable because a polymer can be obtained.

  Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule. The polymer synthesis method is preferably a living radical polymerization method and more preferably an atom transfer radical polymerization method because the molecular weight distribution is narrow and viscosity can be lowered. Moreover, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer described in JP-A-2001-207157 at high temperature and high pressure. Specific examples include UH-2000 manufactured by Toagosei Co., Ltd.

  Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. .

  Although there is no limitation in particular as a silicon compound of General formula (4), when it illustrates specifically, (gamma) -aminopropyltrimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyltrimethoxysilane, (gamma)-( Amino such as N-phenyl) aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, etc. Group-containing silanes; hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane; and the like. 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), JP-A 2000-169544, JP-A 2000-169545. As described in the above, Michael addition reaction product of various α, β-unsaturated carbonyl compounds and amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds. Michael addition reactants can also be used as silicon compounds of general formula (4).

  The crosslinkable silyl group-containing isocyanate compound of the general formula (5) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate and the like. Further, as described in JP-A-2000-119365 (US Pat. No. 6,046,270), a compound obtained by reacting a silicon compound of the general formula (5) with an excess of the polyisocyanate compound is also represented by the general formula: It can be used as the crosslinkable silyl group-containing isocyanate compound (7).

<< (B) component >>
In the composition of the present invention, an oxygen curable compound is used as the component (B). An example of the oxygen curable compound (B) is an unsaturated compound that can react with oxygen in the air. The oxygen curable compound (B) reacts with oxygen in the air to form a cured film near the surface of the cured product. It works to prevent dust and dust from sticking to the surface. Specific examples of the oxygen curable compound (B) include natural drying oil typified by tung oil and linseed oil, and various alkyd resins obtained by modifying the compound; acrylic polymers modified with drying oil , Epoxy resins, silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene NBR, SBR, etc. obtained by copolymerizing a liquid diene polymer such as a polymer, a monomer such as acrylonitrile or styrene copolymerizable with these diene compounds so that the diene compound is the main component, etc. Liquid copolymers, and various modified products thereof (maleinized modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Of these, natural drying oils and liquid diene polymers are preferred, natural drying oils and modified products thereof are more preferred, tung oil and linseed oil are more preferred, and tung oil is most preferred.

In the present invention, the component (B) having an acid value of 4.0 mgKOH / g or less is used. The acid value of (B) component becomes like this. Preferably it is 3.5 mgKOH / g or less, More preferably, it is 3.0 mgKOH / g or less, Most preferably, it is 2.5 mgKOH / g or less. The acid value of the component (B) is preferably 0.01 mgKOH / g or more, more preferably 0.1 mgKOH / g or more. The acid value measured by JIS K 2501 is used for the acid value.
When the component (B) is a dry oil, the acid value may be 4.0 mgKOH / g or more. In this case, the acid value is 4.0 mgKOH / g or less or a preferable acid value or less by treating the drying oil.

  The treatment method for reducing the acid value of the drying oil includes (1) a method of treating the drying oil with an alkaline treatment agent such as MgO, alumina, ion exchange resin, and (2) a carboxylic acid in the drying oil with alcohol. Examples of the method include esterification by reaction or reaction with an esterifying agent, and (3) deoxygenation by heating.

As the method (1), MgO, alumina and ion exchange resin are mixed with drying oil and mixed according to room temperature or heating conditions, or the drying oil alone or drying oil and solvent are mixed in a column packed with the ion exchange resin or the like. And a method of flowing a mixed solution.
As the esterification method (2), any known method may be used. Examples of the esterifying agent include alkyl orthoformate, alkyl orthoacetate, diazomethane, alkyl halide, bicycloaminoacetal (BAA) and the like, and a method using BAA is preferable. BAA includes 1-aza-4,6-dioxabicyclo [3.3.0] octane, 5-methyl-1-aza-4,6-dioxabicyclo [3.3.0] octane, 5- Ethyl-1-aza-4,6-dioxabicyclo [3.3.0] octane, 5-phenyl-1-aza-4,6-dioxabicyclo [3.3.0] octane, 5-ethyl- 3-methyl-1-aza-4,6-dioxabicyclo [3.3.0] octane, 3-allyloxymethyl-5-methyl-1-aza-4,6-dioxabicyclo [3.3. 0] octane, and the like.

  The amount of the oxygen curable compound (B) used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.8 to 100 parts by weight of the polymer (A) having a crosslinkable silyl group. 5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired.

<< Other additives >>
As other additives in the composition of the present invention, a filler, a curing catalyst, a plasticizer, a silane coupling agent, a physical property modifier, a thixotropic agent, an epoxy group-containing compound, a photocurable material, an oxidation agent An inhibitor, a light stabilizer, and an ultraviolet absorber can be added.

<Filler>
Fillers include reinforcing silica such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate Diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, inorganic balloon (glass, shirasu, silica, etc.), Examples thereof include a filler such as an organic microballoon of a phenol resin or a vinylidene chloride resin, a resin powder such as PVC powder or PMMA powder; a fibrous filler such as a glass fiber or a filament. When the filler is used, the amount used is 1 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the polymer of component (A).

<Curing catalyst>
In curing the composition of the present invention, a curing catalyst may or may not be used. When using a curing catalyst, conventionally known ones can be widely used. Specific examples include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin diethylhexanolate, dibutyltin dimethyl maleate, dibutyltin Diethyl maleate, dibutyltin dibutyl maleate, dibutyltin dioctyl maleate, dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin dinonyl Phenoxide, dibutenyl tin oxide, dibutyltin diacetyl Tetravalent tin compounds such as setonate, dibutyltin diethyl acetoacetonate, reaction product of dibutyltin oxide and phthalate; divalent tin compounds such as tin octylate, tin naphthenate and tin stearate; aluminum trisacetylacetonate , Organoaluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; zirconium compounds such as zirconium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, Triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylamino Propylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo ( 5,4,0) amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines Products of silane and epoxy compounds; silane coupling agents having amino groups such as γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropylmethyldimethoxysilane; silanol condensation catalysts such as Acid catalysts, basic catalysts, etc. Silanol condensation catalysts such knowledge can be mentioned. These catalysts may be used alone or in combination of two or more.

  The amount of these curing catalysts used is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight, based on 100 parts by weight of the polymer of component (A). If the amount of the curing catalyst used is too small, the curing rate is slow, and the curing reaction is not sufficiently progressed. On the other hand, if the amount of the curing catalyst used is too large, local heat generation and foaming occur during curing, and it becomes difficult to obtain a good cured product, which is not preferable.

In the curable composition of the present invention, in order to further increase the activity of the condensation catalyst, the general formula R _a Si (OR) _4-a (wherein R is independently substituted or non-substituted having 1 to 20 carbon atoms). A substituted hydrocarbon group, and a is any one of 0, 1, 2, and 3). The silicon compound is not limited, but R in the general formula such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, The aryl group having 6 to 20 aryl groups is preferable because the effect of accelerating the curing reaction of the composition is large. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are particularly preferable because of low cost and easy availability. The compounding amount of the silicon compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer of component (A). When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

<Plasticizer>
By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. Examples of plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate.

  Moreover, a polymeric plasticizer can be used. When using a high-molecular plasticizer, compared to the case of using a low-molecular plasticizer that does not contain a polymer component in the molecule, the initial physical properties are maintained over a long period of time, and an alkyd paint is applied to the cured product. The dryness (also called paintability) can be improved. Specific examples of the polymer plasticizer include vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; sebacic acid and adipine Polyester plasticizers obtained from dibasic acids such as acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; molecular weight of 500 or more, and more than 1000 Polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, or derivatives such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc. Ethers; polystyrene and poly -α- polystyrenes methyl styrene and the like; polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, although polychloroprene, and the like, but is not limited thereto.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15000, more preferably 800 to 10000, still more preferably 1000 to 8000, and particularly preferably 1000 to 5000. Most preferably, it is 1000-3000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, the initial physical properties cannot be maintained over a long period of time, and the alkyd paintability cannot be improved. Moreover, when molecular weight is too high, a viscosity will become high and workability | operativity will worsen. The molecular weight distribution of the polymer plasticizer is not particularly limited, but is preferably narrow and is preferably less than 1.80. 1.70 or less is more preferable, 1.60 or less is more preferable, 1.50 or less is more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

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

  The polymer plasticizer may not have a crosslinkable silyl group, but may have a crosslinkable silyl group. When it has a crosslinkable silyl group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. In the case of having a crosslinkable silyl group, the average number per molecule is preferably 1 or less, more preferably 0.8 or less. When using a plasticizer having a crosslinkable silyl group, particularly a polyoxyalkylene polymer having a crosslinkable silyl group, the number average molecular weight must be lower than that of the polymer of component (A).

  A plasticizer may be used independently and may use 2 or more types together. Further, a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can also be blended at the time of polymer production.

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

<Silane coupling agent>
To the composition of the present invention, a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added as an adhesion promoter. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- ( 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ-ureido Amino group-containing silanes such as propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane Epoxy group-containing silanes such as lan; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane, etc. Carboxysilanes; vinyl-type unsaturated group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropylmethyltriethoxysilane; γ-chloropropyltrimethoxy Examples include halogen-containing silanes such as silane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate. In addition, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, and the like, which are derivatives of these, can also be used as silane coupling agents. . The silane coupling agent used for this invention is normally used in 0.1-20 weight part with respect to 100 weight part of polymers of (A) component. 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 are various adherends, that is, inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, vinyl chloride, acrylic, polyester, When used on organic substrates such as polyethylene, polypropylene, polycarbonate, etc., 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. 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.

<Physical property modifier>
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, and the like, which generate a silicon compound that generates 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 hydroxyl groups such as propane, glycerin, pentaerythritol, sorbitol, and the like, which generate silicon compounds that generate R ₃ SiOH such as trimethylsilanol by hydrolysis.

Further, there may be mentioned also compounds which produce a silicon compound that produces R ₃ SiOH such as trimethyl silanol a derivative of oxypropylene polymer as described in JP-A-7-258534 by hydrolyzing. Furthermore, a polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis as described in JP-A-6-279893 can also be used.

  The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer of component (A).

<Thixotropic agent (anti-sagging agent)>
A thixotropic agent (anti-sagging agent) may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging preventing agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer of component (A).

<Compound containing epoxy group>
When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof.

  Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate And epoxybutyl stearate. Of these, E-PS is particularly preferred. The epoxy compound is preferably used in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polymer of component (A).

<Photo-curing substance>
When a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is a substance in which the molecular structure undergoes a chemical change in a very short time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like. Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) acrylate or oligoesters having a molecular weight of 10,000 or less. Specifically, for example, special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (Multifunctional) Aronix M-400, etc., but especially contain acrylic functional groups In addition, a compound containing an average of 3 or more functional groups per molecule is preferable (all Aronix is a product of Toa Gosei Chemical Co., Ltd.).

  Examples of the polyvinyl cinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, and those obtained by esterifying polyvinyl alcohol with cinnamic acid, as well as many polyvinyl cinnamate derivatives. The azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972). There are detailed examples in Publishing, Publishing Society of Printing Press, page 93-, page 106-, page 117-), these may be used alone or in combination, and a sensitizer may be added as necessary. Can do. Note that the addition of a sensitizer such as ketones or nitro compounds or an accelerator such as amines may enhance the effect. The photocurable substance is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer of component (A), and 0.1 parts by weight or less. Then, there is no effect of increasing the weather resistance, and if it is 20 parts by weight or more, the cured product becomes too hard and cracks are generated, which is not preferable.

<Antioxidant>
If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all of these are manufactured by Ciba Geigy Japan); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARKLA-68 Adeka Argus Chemical Co., Ltd.); 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 Co., Ltd.) A hindered amine 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 antioxidant is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the component (A) polymer.

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred. The light stabilizer may be used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A). 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 of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. The use of a light stabilizer is preferred for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 119FL (all manufactured by Ciba Geigy Japan, Inc.); MARKLA-57, LA-62, LA-67, LA-63 (all above Adeka Argus Examples include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Corporation).

<Ultraviolet absorber>
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 ultraviolet absorber is used in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the polymer (A). It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber in combination.

<Application>
The curable composition of the present invention is also useful as an elastic sealant and an elastic adhesive, and can be used as a sealing material for buildings, ships, automobiles, roads and the like. In particular, it is useful as a sealing material for joints of exterior materials such as sizing boards that require weather resistance and workability. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal and resin moldings alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . In addition to a normal adhesive, it can be used as a contact adhesive. Furthermore, it is also useful as a food packaging material, cast rubber material, molding material, and paint.

The present invention will be specifically described below, but the present invention is not limited to these examples.
(Synthesis Example 1)
Polymerization of propylene oxide using a polyoxypropylene triol having a molecular weight of about 3,000 as an initiator, a zinc hexacyanocobaltate glyme complex catalyst, a number average molecular weight of about 26,000 determined by GPC, and a molecular weight distribution of 1.3 Polypropylene oxide was obtained. The end group molecular weight of polypropylene oxide was about 18,000. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polypropylene oxide to distill off the methanol, and a 1.2-fold equivalent of allyl chloride was added to remove the terminal hydroxyl group. Converted 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 polypropylene oxide, water was removed by centrifugation, and the resulting hexane solution was further added. 300 parts by weight of water was mixed and stirred, and after removing water again by centrifugation, hexane was removed by vacuum devolatilization. Thus, a trifunctional polypropylene oxide having a number average molecular weight of about 26,000 and having an allyl group at the end was obtained.

100 parts by weight of the obtained polymer was reacted with 1.1 parts by weight of methyldimethoxysilane at 90 ° C. for 5 hours using 150 ppm of an isopropanol solution having a platinum content of 3 wt% of a platinum vinylsiloxane complex as a catalyst to form a crosslinkable silyl group. A polymer having was obtained. Further, when the silyl group introduction rate was examined using ¹ H-NMR, the number of terminal methyldimethoxysilyl groups was 1.9 on average per molecule.
(Treatment of tung oil 1)
To a 200 ml flask, 1.5 g of MgO was added to 100 g of tung oil having an acid value of 4.61 mg KOH / g, and the mixture was stirred at 90 ° C. for 3 hours under a N ₂ stream. MgO was removed from the resulting solution by filtration to obtain treated tung oil a. The acid value of the obtained treated tung oil a was 1.52 mgKOH / g.

(Tung oil treatment 2)
In a 200 ml flask, 9 g of Al ₂ O ₃ was added to 100 g of tung oil having an acid value of 4.61, and the mixture was stirred at 90 ° C. for 3 hours under a N ₂ stream. Al ₂ O ₃ was removed from the resulting solution by filtration to obtain treated tung oil b. The acid value of the obtained treated tung oil b was 2.30 mgKOH / g.

(Tung oil treatment 3)
A 200 ml flask is charged with 70 g of tung oil having an acid value of 4.61 and 1 g of 5-methyl-1-aza-4,6-dioxabicyclo [3.3.0] octane, and stirred at 70 ° C. for 3 hours under a N ₂ stream. And processed tung oil c was obtained. The acid value of the obtained processed tung oil c was 1 mgKOH / g or less.

Example 1
100 parts by weight of the polymer having a crosslinkable silyl group obtained in Synthesis Example 1, 5 parts by weight of treated tung oil a obtained in treatment 1 of tung oil, and 200 ppm of water were mixed, and the resulting composition was sealed in a glass bottle. After measuring the viscosity before storage with an E-type viscometer, the viscosity after storing the glass bottle containing the mixture at 70 ° C. for 2 weeks and at 50 ° C. for 4 weeks was compared with the viscosity before storage. The results are shown in Table 1.

(Measurement method of viscosity)
Using an EHD viscometer manufactured by Tokyo Keiki Co., Ltd., a 23 ° C. viscosity was measured using an EHD type 1 ° 34 ′ × R24 cone.

(Example 2)
Except for using treated tung oil b obtained in tung oil treatment 2 as tung oil, the same operation as in Example 1 was performed, and the viscosity before storage was compared. The results are shown in Table 1.

(Example 3)
Except for using treated tung oil c obtained in tung oil treatment 3 as tung oil, the same operation as in Example 1 was performed, and the viscosity before storage was compared. The results are shown in Table 1.

(Comparative Example 1)
Except for using untreated tung oil (acid value 4.61 mgKOH / g) as tung oil, the same operation as in Example 1 was performed, and the viscosity before storage was compared. The results are shown in Table 1.

Claims (9)

  A curable composition comprising (A) a polymer having a crosslinkable silyl group and (B) an air oxidation curable compound having an acid value of 0.01 mgKOH / g or more and 4.0 mgKOH / g or less. The curable composition according to claim 1, wherein the air oxidation curable compound of component (B) is a natural drying oil and / or a modified product thereof. The curable composition according to claim 2 , wherein the natural drying oil is tung oil and / or linseed oil. (B) The upper limit of the acid value of a component is 3.5 mgKOH / g or less, The curable composition of any one of Claims 1-3 . (A) The polymer of a component is a polyoxyalkylene type polymer, The curable composition of any one of Claims 1-4 . Crosslinkable silyl group is General formula (1), The curable composition of any one of Claims 1-5 .
-SiR ¹ _3-a Z _a (1)
(In the formula, each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′) ₃ SiO— ( R ′ is each independently a triorganosiloxy group represented by a hydrocarbon group having 1 to 20 carbon atoms, and Z is each independently a hydroxyl group or a hydrolyzable group. , A is any one of 1, 2, 3) The sealing material containing the curable composition of any one of Claims 1-6 . The adhesive agent containing the curable composition of any one of Claims 1-6 . Hardened | cured material obtained by hardening the curable composition of any one of Claims 1-6 .