JP2018197329A - Room temperature-curable composition - Google Patents

Abstract

To provide a room temperature-curable composition that contains a hydrolyzable silicon group, and gives a cured product having excellent water-resistant adhesion particularly to concrete (mortar), wherein the curable composition has less load on the environment and human bodies.SOLUTION: A curable composition contains an organic polymer (A) having a hydrolyzable silicon group, and a cashew nutshell liquid derivative (B) having a phenolic hydroxyl group. In the curable composition, relative to 100 pts.wt. of the organic polymer (A), the cashew nutshell derivative (B) is 50-200 pts.wt. In the curable composition, the main chain of the organic polymer (A) is preferably a polyoxyalkylene (A1) and/or (meth) acrylate polymer (A2). There is also provided a structural adhesion body of the curable composition and mortar.EFFECT: The curable composition has water-resistant adhesion to concrete (mortar).SELECTED DRAWING: None

Description

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

  An organic polymer having at least one hydrolyzable silicon group in the molecule has a silyl group hydrolyzed by moisture or the like even at room temperature, and a siloxane bond is formed three-dimensionally by a condensation reaction. It is known that things can be obtained. Organic polymers do not contain compounds that are likely to affect the human body, and in recent years, they are also attracting attention as environmentally friendly technologies that have a low impact on the human body and the environment. Has been.

For example, polyoxyalkylene polymers having reactive silicon groups are widely used for applications such as sealing materials, adhesives, and paints. There are a wide variety of target substrates, but among them, porous substrates such as concrete (mortar) and wood are known as difficult-to-adhere substrates. As mentioned.
Here, it is known that non-mineral oils such as cardanol, cashew nut oil, cashew nut shell liquid and derivatives thereof can be used as organic extenders for siloxane blends (Patent Document 1). Further, it is known that a resin composition excellent in flexibility and bleed resistance is provided by blending a polyester resin with a derivative obtained by esterifying a phenolic hydroxyl group as a plasticizer (Patent Document 2). ). Furthermore, it is known to provide a curable composition having good adhesion to various substrates by blending an aromatic plasticizer with an organic polymer having a reactive silicon group. (Patent Document 3). However, the adhesion to the porous substrate has not been studied, and the problem of the decrease in adhesion after the water resistance test has not been solved.

Special table 2010-506034 gazette JP 2010-0664967 A JP 2004-323843 A

An object of the present invention is to provide a curable composition comprising an organic polymer having a hydrolyzable silicon group, which has good water-resistant adhesion to a porous substrate, particularly concrete (mortar). It is in.

The present inventors have found that it is effective for solving the above-mentioned problems to include a cashew nut shell liquid derivative (B) having a phenolic hydroxyl group in an organic polymer (A) having a hydrolyzable silicon group. .
That is, the present invention provides (1) a curable composition containing an organic polymer (A) having a hydrolyzable silicon group, and a cashew nut shell liquid derivative (B) having a phenolic hydroxyl group,
(2) The curable composition according to (1), wherein the component (B) is 50 to 200 parts by weight with respect to 100 parts by weight of the component (A),
(3) The main chain of the organic polymer of component (A) is polyoxyalkylene (A1) and / or (meth) acrylic acid ester polymer (A2), (1) or (2 ), The curable composition according to
(4) Adhesive structure of the curable composition according to any one of (1) to (3) and mortar,
About.

  The curable composition of the present invention has good water-resistant adhesion.

Hereinafter, the present invention will be described in detail.
There is no restriction | limiting in particular as an organic polymer which has a hydrolyzable silicic group which is (A) component of this invention, For example, the main chain skeleton is generally known oxyalkylene type polymer, (meth) acrylic acid ester type Organic polymers such as polymers, saturated hydrocarbon polymers, and polyester polymers can be used. Of these, oxyalkylene polymers are particularly preferred because of their low temperature characteristics, flexibility, and compatibility with other components. In the following explanation of polymer (A), oxyalkylene polymers are used as representative examples. Describe what is considered a case.

The reactive silicon group-containing polyoxyalkylene polymer has a reactive silicon group represented by the following general formula (1).
-SiR ¹ _a X _3-a (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group. A represents 0 or 1.).

Specific examples of R ¹ in the general formula (1) include, for example, an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl such as a benzyl group; A triorganosiloxy group represented by —OSi (R ′) _{3 in} which R ′ is a methyl group, a phenyl group or the like; a fluoroalkyl group such as a fluoromethyl group or a difluoromethyl group; a chloromethyl group, a 1-chloroethyl group Chloroalkyl groups such as; methoxymethyl group, ethoxymethyl group, phenoxymethyl group, 1-methoxyethyl group and other alkoxyalkyl groups; aminomethyl group, N-methylaminomethyl group, N, N-dimethylaminomethyl group and the like Aminoalkyl group; acetoxymethyl group, methyl carbamate group, 2-cyanoethyl group and the like. Among these, a methyl group is more preferable in view of availability of raw materials.

  Examples of the hydrolyzable group represented by X in the general formula (1) include known hydrolyzable groups. Specific examples include hydrogen, halogen, alkoxy groups, alkenyloxy groups, and aryloxy groups. Acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and the like. Among these, halogen, alkoxy group, alkenyloxy group, and acyloxy group are preferable because of their high activity, and alkoxy groups such as methoxy group and ethoxy group are more preferable because they are mildly hydrolyzable and easy to handle. The group is particularly preferred. In addition, the ethoxy group and the isopropenoxy group are preferably removed from the reaction by ethanol and acetone, respectively, from the viewpoint of safety.

Specific examples of the reactive silicon group represented by the general formula (1) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, a dimethoxymethylsilyl group, A diethoxymethylsilyl group, diisopropoxymethylsilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, and (ethoxymethyl) dimethoxysilyl group are preferred. Among these, dimethoxymethylsilyl group and trimethoxysilyl group are preferable because a cured product having high strength can be obtained.
The polyoxyalkylene polymer has a relatively low glass transition temperature, and the resulting cured product is excellent in cold resistance. In addition, when it is made into a one-component composition with high moisture permeability, it has a feature that it is excellent in deep part curability and further excellent in adhesiveness.

  Specifically, polyoxyalkylene heavy polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, etc. For example, coalescence.

  The main chain structure 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 sealants, adhesives, etc., an amorphous material is a polyoxypropylene polymer having a repeating unit of oxypropylene of 50% by weight or more, preferably 80% by weight or more of the polymer main chain structure. From the viewpoint of quality and relatively low viscosity.

  The main chain structure of the polymer may have a polymer structure other than the oxyalkylene structure as long as the effects of the invention are not impaired.

  The main chain structure of the polymer may be linear or may have a branched chain. When it is desired to obtain a cured product with higher strength, it is preferably a branched polymer. When it is desired to obtain a cured product having a higher elongation, it is preferably linear. When the polymer has a branched chain, the number of branched chains is preferably 1 to 4, and the number of branched chains is most preferably 1.

  The polyoxyalkylene polymer is preferably obtained by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.

  Examples of the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, it is particularly preferable to use propylene oxide because an amorphous and relatively low viscosity polyether polymer can be obtained.

  Specific examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol, Alcohols such as sorbitol; number average molecular weights of 300 to 4,000, and polyoxyalkylene polymers such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol .

  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 Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3,427,334, 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, can be mentioned, but not particularly limited, manufacturing cost and, because of such the polymer having a narrow molecular weight distribution is obtained, by the polymerization method is more preferred composite metal cyanide complex catalyst.

  The molecular weight distribution (Mw / Mn) of the polymer is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. preferable.

  The number average molecular weight of the polymer is preferably 8,000 or more, more preferably 9,000 or more, and particularly preferably 10,000 or more, in terms of polystyrene by GPC. The upper limit is preferably 50,000 or less, more preferably 35,000 or less, and particularly preferably 30,000 or less. When the number average molecular weight of the polymer is small, the viscosity is low, so that the workability when using the curable composition is improved. On the other hand, the hardened | cured material obtained becomes hard and there exists a tendency for an elongation characteristic to fall. If the molecular weight is too large, the reactive silicon group concentration may be too low, and the curing rate may be slow. Also, the viscosity tends to be too high and handling tends to be difficult.

  The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.

  (I) Hydrosilylation: First, an unsaturated bond is introduced into a raw material polymer (sometimes referred to as a precursor polymer), and a hydrosilane compound is added to the unsaturated bond by a hydrosilylation reaction. . Any method can be used for introducing the unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is allowed to react with a compound having reactivity with this functional group and a compound having an unsaturated group. There are a method for obtaining an unsaturated group-containing polymer and a method for copolymerizing a polymerizable monomer having an unsaturated bond.

  (Ii) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent: reacting with the precursor polymer having a reactive group such as a hydroxyl group, an amino group, or an unsaturated bond, and the reactive group. And a compound having both a group capable of forming a bond and a reactive silicon group (also called a silane coupling agent). As a combination of the reactive group of the precursor polymer and the reactive group of the silane coupling agent, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, Examples include, but are not limited to, Michael addition of amino group and acrylic structure, carboxylic acid group and epoxy group, unsaturated bond and mercapto group.

  The method (i) is preferable because the reaction is simple, the adjustment of the amount of reactive silicon groups introduced, and the physical properties of the resulting reactive silicon group-containing polymer are stable. The method (ii) has many reaction options, and it is easy and preferable to increase the rate of introduction of reactive silicon groups.

  A part of hydrosilane compound used by the method of (i) is illustrated. Halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, trimethoxysilane, triethoxysilane, (chloromethyl) dimethoxysilane, (methoxymethyl) ) Alkoxysilanes such as dimethoxysilane; isopropenyloxysilanes (deacetone type) such as triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane, etc. .

  Examples of the silane coupling agent that can be used in the method (ii) include the following compounds. Mercaptosilanes that react with unsaturated bonds, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxymethylsilane; Reactive isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy, which reacts with hydroxyl, amino and carboxylic acid groups Epoxy silanes such as propyl dimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane; isocyanate group, thioisocyanate 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) propyltrimethoxysilane, 3- (2-aminoethyl) which react with groups Propyl dimethoxymethylsilane, 3- (2-aminoethyl) propyltriethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropi Triethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenyl Aminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, bis (3- (trimethoxysilyl) propyl) amine, etc. Aminosilanes; hydroxyalkylsilanes such as 3-hydroxypropyltrimethoxysilane and hydroxymethyltriethoxysilane; The above silane coupling agent is an example, and a silyl group can be introduced by utilizing or applying a similar reaction.

  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 a urethane bond component, The group (henceforth an amide segment) produced | generated by reaction with an isocyanate group and an active hydrogen group can be mentioned.

  A cured product obtained by curing a curable composition containing a polymer containing a urethane bond or an ester bond in the main chain has such effects as high hardness and improved strength due to the action of hydrogen bonds. May be. On the other hand, the urethane bond may be cleaved by heat or the like. For the purpose of imparting such characteristics to the curable composition of the present invention, an amide segment can be introduced into the polymer, or the amide segment can be excluded. A polyoxyalkylene polymer having an amide segment tends to have a high viscosity. In addition, the polyoxyalkylene polymer having an amide segment may be improved in curability.

The amide segment has the general formula (2):
-NR < ³ > -C (= O)-(2)
(R ³ represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

  Specifically, as the amide segment, a urethane group formed by a reaction between an isocyanate group and a hydroxy group or a reaction between an amino group and a carbonate; a urea group formed by a reaction between an isocyanate group and an amino group; And a thiourethane group generated by the reaction of a group and a mercapto group. In the present invention, groups generated by the reaction of the active hydrogen in the urethane group, urea group, and thiourethane group with an isocyanate group are also included in the group of the general formula (2).

An example of an industrially easy production method of a polyoxyalkylene polymer having an amide segment and a reactive silicon group is illustrated by reacting an excess polyisocyanate compound with a polyoxyalkylene polymer having an active hydrogen-containing group at the terminal. Or a polymer having an isocyanate group at the terminal of the polyurethane main chain, or at the same time, all or part of the isocyanate group is represented by the general formula (3):
Z—R ⁴ —SiR ¹ _a X _3-a (3)
(R ¹ , X, and a are the same as described above. R ⁴ is a divalent organic group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxy group, a carboxy group, or a mercapto group. And an amino group (which is an active hydrogen-containing group selected from primary or secondary)) and those produced by a method of reacting a Z group of a silicon compound.

Further, the polyoxyalkylene polymer having an active hydrogen-containing group at the terminal is represented by the general formula (4):
^{O = C = N-R 4} -SiR 1 a X 3-a (4)
(R ⁴ , R ¹ , X, and a are the same as described above), and those produced by reacting with a reactive silicon group-containing isocyanate compound.

  Although there is no limitation in particular as a silicon compound of General formula (3), when it illustrates concretely, (gamma) -aminopropyl dimethoxymethylsilane, (gamma) -aminopropyl trimethoxysilane, N-((beta) -aminoethyl) -gamma-amino Amino group-containing silane such as propyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyldimethoxymethylsilane, (N-phenyl) -γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane Hydroxy group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; 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 products of various α, β-unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds, The Michael addition reaction product of can also be used as the silicon compound of general formula (3).

  The reactive silicon group-containing isocyanate compound represented by the general formula (4) is not particularly limited, but specific examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, and γ-methyldimethoxysilylpropyl isocyanate. , Γ-methyldiethoxysilylpropyl isocyanate, γ- (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl ) Dimethoxysilylmethyl isocyanate and the like.

  When the main chain skeleton of the polymer contains an amide segment, the average number of amide segments per molecule is preferably 1 to 10, more preferably 1.5 to 5, and particularly preferably 2 to 3. When the number is less than 1, the curability may not be sufficient. When the number is more than 10, the polymer may have a high viscosity and may be difficult to handle.

  For the purpose of reducing the viscosity of the curable composition or improving workability, it is preferable that the polymer does not substantially contain an amide segment.

  The polymer may contain two or more reactive silicon groups at one terminal site. For a specific production method, it is possible to refer to a patent document (WO2013 / 18020).

  The lower limit of the average number of reactive silicon groups in the polymer per molecule is preferably 1.2 or more, more preferably 1.3 or more, and most preferably 1.5 or more. The upper limit is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less. If the number of reactive silicon groups is 1.2 or less, a high-strength cured product may not be obtained. If the number of reactive silicon groups is 6.0 or more, a cured product having a high elongation may not be obtained, which is not preferable.

The average number of reactive silicon groups in the polymer is defined as the average number obtained by a method of quantifying protons on carbon directly bonded with reactive silicon groups by high resolution ¹ H-NMR measurement. In the calculation of the average number of reactive silicon groups in the polymer in the present invention, when the reactive silicon group is introduced into the precursor polymer, the precursor polymer and side reaction in which no reactive silicon group is introduced. When calculating the average number of reactive silicon groups in one molecule, the resulting polymer without a reactive silicon group is regarded as a part of the polymer component having the same main chain structure. The calculation is included in the parameter (number of molecules).

  The polymer of the present invention may be used alone or in combination of two or more.

In the present invention, by adding the cashew nut shell liquid derivative (B) having a phenolic hydroxyl group having a phenolic hydroxyl group, the water-resistant adhesion of the cured product to concrete (mortar) can be dramatically improved.
Cashew nut shell liquid is also called cashew nut shell oil or cashew nut oil. An oily liquid contained in the shell of cashew nut tree (Anacardium accidentale L., Ursiaceae). There are a solvent extraction method and a heating method as a method for collecting cashew nut shell liquid from the husks of peanut tree (Anacardium accidentale L., Ursiaceae), and the heating method is mainly used in the production area. That is, the cashew nut shell liquid can be obtained by dry distillation of the cashew nut shell or by solvent extraction directly from the cashew nut shell. As components of cashew nut shell liquid, anacardic acid and cardol are the main components in the extraction method, and cardanol and cardol are the main components in the heating method.

  Component (B) is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight, and particularly preferably 50 to 200 parts by weight per 100 parts by weight of component (A). (B) When there are few components, the water-resistant adhesiveness of the hardened | cured material obtained becomes inadequate, and conversely when too large, the elasticity modulus of hardened | cured material becomes small too much and adhesive strength falls, or hardening time There is a case where a problem such as a slowdown occurs.

  In the curable composition of the present invention, a curing catalyst for the polymer (A) having a reactive silicon group is used.

  As the curing catalyst, known ones can be arbitrarily used. For example, tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate , Metal carboxylates such as hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate; tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate) , Titanium compounds such as bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibuty Tin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate) , Dibutyltin bis (tridecyl maleate), dibutyltin bis (benzyl maleate), dibutyltin diacetate, dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dibutyltin dimethoxide, dibutyltin bis (Nonylphenoxide), dibutenyl tin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), monobutyltin tridibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, dioctyl Organotin compounds such as bis (neodecanoate), dioctyltin dilaurate, reaction product of dibutyltin oxide and phthalate, reaction product of dioctyltin salt and normal ethyl silicate; aluminum tris (acetylacetonate), aluminum tris ( Aluminum compounds such as ethyl acetoacetate) and diisopropoxy aluminum ethyl acetoacetate; Zirconium compounds such as zirconium tetrakis (acetylacetonate); Various metal alkoxides such as tetrabutoxyhafnium; Organic acidic phosphates; Trifluoromethane Organic sulfonic acids such as sulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid and boronic acid; and amidine compounds such as DBU and guanidine.

  When the curable composition of the present invention is cured by heat curing, a known heat-curable catalyst can be used. Monobutyltin tris (2-ethylhexanoate) (trade name: SCAT24 (Nitto Kasei) ), Tetrabutylammonium acetate (trade name: Catana N416 (manufactured by SACHEM), etc.) and tetrabutylphosphonium acetate (trade name: Catana N563 (manufactured by SACHEM), etc.), onium salts, zirconium tris (2- By using a catalyst such as ethylhexanoate), a good cured product with a good balance between storage stability at room temperature and curing activity at high temperature and with less mixing of bubbles can be obtained.

A plasticizer may be added to the curable composition of the present invention. By adding a plasticizer, the viscosity, slump property of the curable composition, and mechanical properties such as hardness, tensile strength, and elongation of the cured product obtained by curing the curable composition can be adjusted. Specific examples of the plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate and the like; bis (2-ethylhexyl) ) Terephthalic acid ester compounds such as 1,4-benzenedicarboxylate (specifically, trade name: EASTMAN 168 (manufactured by EASTMAN CHEMICAL)); non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester ( Specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, tributy acetyl citrate Aliphatic carboxylic acid ester compounds such as; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetyl ricinoleate; alkylsulfonic acid phenyl esters (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as zil phosphate and tributyl phosphate; Trimellitic ester compounds; Chlorinated paraffins; Hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; Process oils; Epoxidized soybean oil, Epoxy benzyl stearate, etc. Epoxy plasticizers; sulfonic acid amide plasticizers (trade names: Ketjenflex (manufactured by Axentive), topsizer (manufactured by Fuji Ad Chemical)), and the like.
The curable composition of the present invention can also be obtained by heat curing. In that case, by using a sulfonic acid amide plasticizer, foaming of the cured product is suppressed, and the curability is promoted. be able to.

  Polymer plasticizers can also be used. When a high molecular plasticizer is used, the initial physical properties can be maintained over a long period of time compared to the case where a low molecular plasticizer is used. Furthermore, the drying property (paintability) when an alkyd paint is applied to the cured product 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, 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; number average molecular weight of 500 or more Furthermore, more than 1,000 polyether polyols such as polyethylene glycol polypropylene glycol and polytetramethylene glycol, or the hydroxy group of these polyether polyols are esterified Polyethers such as derivatives converted to ether groups; polystyrenes such as polystyrene and poly-α-methylstyrene; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene, and the like. It is not something.

  The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, and particularly preferably 20 to 100 parts by weight with respect to 100 parts by weight of the 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. 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.

  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.

In the curable 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 such silane coupling agents include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4- Epoxy group-containing silanes such as epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyl Methyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl- γ-aminopropyltriethoxy N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylaminomethyl) trimethoxysilane, bis (3 -Trimethoxysilylpropyl) amine-containing amino group-containing silane coupling agent; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanate Isocyanate group-containing silanes such as anatepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyl Mercapto group-containing silanes such as methyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) silane, N-β- (carboxymethyl) Carboxysilanes such as aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Lan, vinyl-type unsaturated group-containing silanes such as γ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate Carbamate silanes such as methyl (N-dimethoxymethylsilylmethyl) carbamate, methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate; Alkoxy group-containing silanes such as (methoxymethyl) dimethoxymethylsilane, (methoxymethyl) trimethoxysilane, (ethoxymethyl) trimethoxysilane, (phenoxymethyl) trimethoxysilane; 3- ( Can be exemplified trimethoxy silyl) propyl succinic anhydride, 3- (acid anhydride-containing silane such as triethoxy silyl) propyl succinic anhydride and the like. In addition, these partial condensates and derivatives thereof, such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent. These silane coupling agents may be used alone or in combination. As the reaction product of the silane coupling agent, a reaction product of isocyanate silane and a hydroxyl group-containing compound, an amino group-containing compound; a Michael addition reaction product of aminosilane; a reaction product of an aminosilane and an epoxy group-containing compound, an epoxy silane and a carboxylic acid group Examples thereof include a reaction product with a containing compound and an amino group-containing compound.

  0.1-20 weight part is preferable with respect to 100 weight part of (A) component, and, as for the usage-amount of a silane coupling agent, 0.5-10 weight part is especially preferable.

  Specific examples of the adhesion-imparting agent 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.

  Moreover, a silicate can be added to 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 obtained from the curable 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 and alkylalkoxysilane or partial hydrolysis condensates thereof can be used.

  Specific examples of the silicate include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, and tetra-n-butoxy. Examples thereof include tetraalkoxysilanes (tetraalkyl silicates) such as silane, 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 partially hydrolyzed condensate of tetraalkoxysilane include those obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis. 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.).

  When using a silicate, the usage-amount is 0.1-20 weight part with respect to 100 weight part of (A) component, Preferably it is 0.5-10 weight part.

  In the curable composition of the present invention, various fillers can be blended in addition to the component (C). As fillers, reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, aluminum hydroxide, and carbon black; heavy calcium carbonate, Filler like resin powder such as colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, titanium oxide, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, PVC powder, PMMA powder; asbestos And fibrous fillers such as glass fibers and filaments.

  As described in Japanese Patent Application Laid-Open No. 2001-181532, the filler is uniformly mixed with a dehydrating agent such as calcium oxide, and then sealed in a bag made of an airtight material and left for an appropriate time. It is also possible to dehydrate and dry in advance. By using this low water content filler, storage stability can be improved particularly when a one-component composition is used.

  When you want to obtain a cured product with high strength by using these fillers, fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, hydroxylation A filler selected from aluminum, surface-treated fine calcium carbonate, activated zinc white and the like is preferable, and the amount used is preferably 1 to 200 parts by weight per 100 parts by weight of component (A).

  If you want to obtain a cured product with low strength and high elongation at break, mainly from calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, ferric oxide, zinc oxide, and Shirasu balloon When the selected filler is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the component (A), 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. 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. Surface treatment agents for producing surface-treated calcium carbonate powder include palmitic acid, caprylic acid, capric acid, lauric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, etc. Carboxylic acids such as fatty acids and unsaturated fatty acids, rosin acid compounds and esters thereof, silane compounds such as hexamethyldisilazane, chlorosilane, and aminosilane, paraffin compounds, and the like. I don't mean. Especially, when a surface treating agent is carboxylic acid, when it is set as a curable silicone type resin composition, since it becomes difficult to produce hardening delay further, it is preferable. Further, among the carboxylic acids, saturated fatty acids or unsaturated fatty acids are particularly preferred because they are much less likely to cause curing delay. Of course, these fillers may be used alone or in combination of two or more. Fatty acid surface-treated colloidal calcium carbonate and heavy calcium carbonate that has not been surface-treated such as calcium carbonate having a particle size of 1 μm or more can be used in combination.

  The amount of the filler used is preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, based on 100 parts by weight of component (A).

  An organic balloon or an inorganic balloon may be added in order to improve the workability (such as sharpness) of the composition and to make the surface of the cured product matt. 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, 5-300 μm is preferable.

An anti-sagging agent may be added to the curable composition of the present invention as necessary to prevent sagging and improve workability. The sagging inhibitor 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 anti-sagging agents may be used alone or in combination of two or more.
The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight per 100 parts by weight of component (A).

  An antioxidant (antiaging agent) can be used in the curable composition of the present invention. If an antioxidant is used, the weather resistance of the cured product can be increased. Examples of the antioxidant include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by Ciba Japan Co., Ltd.); All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) Hindered amine light stabilizers can also be used. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.

  0.1-10 weight part is preferable with respect to 100 weight part of (A) component, and, as for the usage-amount of antioxidant, 0.2-5 weight part is especially preferable.

  A light stabilizer can be used in the curable composition of the present invention. Use of a light stabilizer can prevent photooxidation degradation of the cured product. Examples of the light stabilizer include benzotriazole, hindered amine, and benzoate compounds, with hindered amines being particularly preferred.

  0.1-10 weight part is preferable with respect to 100 weight part of (A) component, and, as for the usage-amount of a light stabilizer, 0.2-5 weight part is especially preferable.

  When a photocurable substance is blended in the curable composition of the present invention, particularly when an unsaturated acrylic compound is used, a tertiary amine is used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a contained hindered amine light stabilizer for improving the storage stability of the composition. As tertiary amine-containing hindered amine light stabilizers, Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all are manufactured by Ciba Japan Co., Ltd.); Adeka Stub LA-57, LA-62, LA-67, LA-63 (all above) Light stabilizers such as SANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).

An ultraviolet absorber can be used for the curable composition of the present invention. When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based and metal chelate-based compounds, and oxanilide-based compounds commercially available as SABO STAB UV312 (manufactured by SABO). Triazole type is preferable, and commercially available names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (above, manufactured by BASF) are mentioned. 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred. Furthermore, it is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.
0.1-10 weight part is preferable with respect to 100 weight part of (A) component, and, as for the usage-amount of a ultraviolet absorber, 0.2-5 weight part is especially preferable.
The antioxidant, light stabilizer, and ultraviolet absorber can be appropriately selected according to the use temperature, exposure environment, transparency requirements, and the like.

  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 modifier, For example, alkyl alkoxysilanes, such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Arylalkoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane, and other alkylisopropenoxysilanes; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as silyl) borate; 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 polyoxyalkylene 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.

  In the present invention, a tackifying resin can be added for the purpose of enhancing the adhesion and adhesion to the substrate, or as necessary. The tackifying resin is not particularly limited, and those that are usually used can be used.

  Specific examples include terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols. Resin, cyclopentadiene-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, DCPD resin and the like. These may be used alone or in combination of two or more.

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

  Among these, a terpene-phenol resin is preferable because of high compatibility with the polymer and the plasticizer and high adhesion effect. On the other hand, when the color tone is important, a hydrocarbon resin is preferable.

  The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 5 to 30 parts by weight per 100 parts by weight of component (A). If the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion to the substrate, and if it exceeds 100 parts by weight, the viscosity of the curable composition may be too high and handling may be difficult.

  In the composition of the present invention, a compound containing an epoxy group 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 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 per 100 parts by weight of component (A).

  A photocurable material can be used in the composition of the present invention. 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) dimethacrylate and 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 M305 , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, Aronix M-400 (polyfunctional), etc. 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 component (A). When the amount is 20 parts by weight or more, the cured product tends to be too hard and tends to crack.

  An oxygen curable substance can be used in the composition of the present invention. Examples of the oxygen curable substance include unsaturated compounds that can react with oxygen in the air. The oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product. And prevents dust from adhering. Specific examples of the oxygen curable substance include drying oils typified by drill oil and linseed oil, various alkyd resins obtained by modifying the compounds; acrylic polymers and epoxy resins modified with drying oils , Silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid polymers, liquid copolymers such as NBR and SBR obtained by copolymerizing monomers such as acrylonitrile and styrene copolymerizable with these diene compounds so that the main component is a diene compound, Further, various modified products thereof (maleinized modified products, boiled oil modified products, etc.) and the like can be mentioned. These may be used alone or in combination of two or more. Of these, drill oil and liquid diene polymers are particularly preferable. Moreover, the effect may be enhanced if a catalyst for promoting the oxidative curing reaction or a metal dryer is used in combination. Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amidine compounds. The amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (A). If the amount used is less than 0.1 parts by weight, the improvement of the contamination is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen curable substance is preferably used in combination with a photocurable substance.

  An epoxy resin can be added to the composition of the present invention. A composition to which an epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles. Epoxy hydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A Glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether Examples include glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc., but are not limited to these, and generally used epoxies Resins can be used. Those containing at least two epoxy groups in the molecule are preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. More preferred are bisphenol A type epoxy resins or novolac type epoxy resins. The use ratio of these epoxy resins is in the range of polymer (A) / epoxy resin = 100/1 to 1/100 by weight ratio. When the ratio of the polymer (A) / epoxy resin is less than 1/100, the effect of improving the impact strength and toughness of the cured epoxy resin is hardly obtained, and the ratio of the polymer (A) / epoxy resin is 100. When the ratio exceeds / 1, the strength of the polymer cured product becomes insufficient. The preferred use ratio varies depending on the use of the curable resin composition and cannot be determined unconditionally. For example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of the cured epoxy resin The polymer is used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin. On the other hand, when improving the intensity | strength of hardened | cured material, it is good to use 1-200 weight part of epoxy resins with respect to 100 weight part of (A) component, More preferably, it is 5-100 weight part.

  When an epoxy resin is added, the composition of the present invention can naturally be used in combination with a curing agent that cures the epoxy resin. There is no restriction | limiting in particular as an epoxy resin hardening | curing agent which can be used, The epoxy resin hardening | curing agent generally used can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazole Dicyandiamides; boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc .; alcohols ; Fe Lumpur acids; carboxylic acids; but the compound of diketone complex compounds of aluminum or zirconium, or the like can be exemplified, but the invention is not limited thereto. Further, the curing agents may be used alone or in combination of two or more.

  When the epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Ketimine can be used as a curing agent for the epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into primary amines and ketones by moisture, and the resulting primary amine becomes a room temperature curable curing agent for the epoxy resin. When ketimine is used, a one-component composition can be obtained. Such a ketimine can be obtained by a condensation reaction between an amidine compound and a carbonyl compound.

  For the synthesis of ketimine, known amidine compounds and carbonyl compounds may be used. For example, as amidine compounds, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p, p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris (2-amino Polyethylamines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylenepolyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyl Triethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, N-(beta-aminoethyl)-.gamma.-aminopropyl aminosilane such as methyldimethoxysilane; and may be used. Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone and trimethylcyclohexanone; acetone , Aliphatic ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate , Β-dicarbonyl compounds such as diethyl malonate, methyl ethyl malonate, dibenzoylmethane And the like can be used.

  To the curable composition of the present invention, a phosphorus-based flame retardant 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 400 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of component (A).
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 radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, solvents, fungicides, and the like. It is done. 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.

  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. As the dehydration and drying method, a heat drying method is preferable in the case of a solid substance such as a powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel or the like is preferable in the case of a liquid material. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. In addition to the dehydration drying method, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ -Storage stability is further improved by adding an alkoxysilane compound such as glycidoxypropyltrimethoxysilane.

  The amount of the silicon compound capable of reacting with water such as a dehydrating agent, particularly vinyltrimethoxysilane, is preferably 0.1 to 20 parts by weight, particularly 0.5 to 10 parts by weight per 100 parts by weight of component (A). Part is preferred.

  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 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 waterproofing coating film. Since the cured product obtained by curing the curable composition of the present invention has good water-resistant adhesion, among these, it is more preferable to use it as a sealing material or an adhesive.

  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, Can also be used.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples.

(Synthesis example)
Using a polyoxypropylene triol having a number average molecular weight of about 3,000 and a polyoxypropylene diol having a number of about 3,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 14,000. Of polyoxypropylene triol was obtained. Subsequently, a methanol solution of NaOMe equivalent to 1.2 times equivalent to the hydroxyl group of the hydroxyl-terminated polyoxypropylene triol was added to distill off the methanol, and 3-chloro-1-propene was further added to the hydroxyl group to 1.2%. An equivalent amount was added to convert the terminal hydroxyl group into an allyl group. Next, 50 μl of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) is added to 500 g of the allyl group-terminated polyoxypropylene obtained, and 6.7 g of DMS (dimethoxysilane) is slowly added while stirring. It was dripped. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted DMS is distilled off under reduced pressure, whereby a reactive silicon group-containing polyoxypropylene polymer having an average of 1.7 silicon groups per molecule is obtained. (A) was obtained.

   Using the obtained reactive silicon group-containing organic polymer, each component shown in Table 1 was weighed in the blending amount shown in the same table, and rotated 2300 times using a rotation and revolution type stirrer (trade name: SPEED MIXER DAC400FVZ). The mixture was stirred to obtain a curable composition. Using the curable composition thus obtained, physical properties were evaluated.

As shown in Table 1, by using a cashew nut shell liquid derivative having a phenolic hydroxyl group, it was possible to obtain a cured product having good mortar water resistance adhesion. In the case of using a cashew nut shell liquid derivative that does not have a phenolic hydroxyl group, such an effect cannot be obtained, and it is considered that the phenolic hydroxyl group contributes to improvement of water-resistant adhesion. The cause is considered to be that the affinity with mortar is improved by the phenolic hydroxyl group.

In Tables 1 to 3, each compounding agent is as follows.
Ultra LITE 2023: Cashew nut shell liquid derivative mainly composed of cardanol having a phenolic hydroxyl group manufactured by Cardolite.
LITE 2100R: Cashew nut shell liquid derivative mainly composed of a modified cardanol having a phenolic hydroxyl group and an alkyl substituent on the aromatic ring.
GX-5166: Cashew nut shell liquid derivative mainly composed of a modified cardanol in which the phenolic hydroxyl group is ethoxylated.
LITE 2020: Cashew nut shell liquid derivative mainly composed of modified cardanol in which the phenolic hydroxyl group is hydroxyethylated.
DINP: Diplusonyl phthalate manufactured by J-Plus Socal U1S2: Heavy calcium carbonate manufactured by Solvay RFK-2: Tranox titanium oxide Crayvallac SLX: Arkema amide wax tinuvin 770: BASF hindered amine light stabilizer Tinuvin 326: Benztriazole manufactured by BASF UV absorber VTMO: Evonik vinyltrimethoxysilane AMMO: Evonik aminopropyltrimethoxysilane DAMO: Evonik dimethylaminopropyltrimethoxysilane TIB KAT 223: TIB Chemical dioctyltin dicetylacetonate

Claims (4)

  A curable composition comprising an organic polymer (A) having a hydrolyzable silicon group and a cashew nut shell liquid derivative (B) having a phenolic hydroxyl group.   Component (B) is 50-200 weight part with respect to 100 weight part of component (A), The curable composition of Claim 1 characterized by the above-mentioned. The main chain of the organic polymer of component (A) is polyoxyalkylene (A1) and / or (meth) acrylic acid ester polymer (A2), curing according to claim 1 or 2 Sex composition. The adhesion structure of the curable composition and mortar in any one of Claims 1-3.