JP2014001358A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which is particularly useful for an adhesive for asphalt roofing material and provides excellent adhesion to a modified asphalt sheet of poorly adhesive material.SOLUTION: The curable composition contains a polyoxyalkylene polymer (A) having a reactive silicon group, and a terpene resin (B).

Description

  In the present invention, an organic heavy group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silicon group capable of forming a crosslink by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). The present invention relates to a curable composition containing a coalescence and a terpene resin.

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

  As these organic polymers having a reactive silicon group, organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer have already been industrially produced, such as sealing materials, adhesives, paints, etc. Widely used in applications (Patent Document 1) and (Patent Document 2).

  Asphalt is widely used in road paving materials, roofing materials, sealing materials, adhesives, waterway lining materials, vibration damping materials, soundproofing materials, etc. because it is excellent in tackiness, processability, waterproofness and is inexpensive. .

  In the case of using asphalt as a roofing material, a so-called asphalt waterproof thermal construction method in which a waterproof layer is formed by laminating a plurality of asphalt sheets is adopted as a mainstream of waterproof construction. This method is very reliable in waterproofing, but when melting asphalt, the smoke and odor of molten asphalt significantly contaminates the surrounding environment, so it is avoided in densely populated areas and in the city center. There was a trend. In order to solve these problems, the self-adhesion method, which is a room temperature method, is being established in this field. However, a large amount of release paper peeled off during construction is generated as a waste material. In order to solve these problems, a method of laminating asphalt sheets using an adhesive composition has attracted attention. However, there was a problem in securing adhesiveness with the asphalt sheet.

JP-A-52-73998 JP-A 63-6041

  An object of the present invention is to provide a curable composition that is particularly useful for an adhesive for asphalt roofing materials and is excellent in adhesion to a modified asphalt sheet that is a difficult-to-adhere substrate.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyoxyalkylene polymer (A) having a reactive silicon group as a polymer component and a terpene resin (B) -containing curing. The present invention has been completed by finding that the composition can be improved by using an adhesive composition.

In other words, the present invention
(1). A curable composition containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1), and a terpene resin (B);
-SiR ¹ _a X _3-a (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom on the 1st to 3rd carbon atoms may be substituted with a heteroatom. X is a hydroxyl group or hydrolysis. And a represents a condition satisfying a condition of 0 or 1. When a plurality of Xs are present, they may be the same or different.
(2). The curable composition according to (1), wherein the reactive silicon group equivalent of the polyoxyalkylene polymer (A) is 0.15 mmol / g or less,
(3). The curable composition according to (1) or (2), wherein the terpene resin as the component (B) is a terpene phenol resin,
(4). The curable composition according to (3), wherein the terpene phenol resin as the component (B) has a hydroxyl value of 1.4 mmol / g or more,
(5). The curable composition according to any one of (1) to (4), wherein the polyoxyalkylene polymer as the component (A) is a polyoxypropylene polymer,
(6). The curing according to any one of (1) to (5), comprising a (meth) acrylic acid ester polymer (C) having a reactive silicon represented by the general formula (1). Sex composition,
(7). The curable composition according to any one of (1) to (6), which comprises a polyether plasticizer,
(8). An adhesive comprising the curable composition according to any one of (1) to (7) as a component;
(9). A non-contact adhesive containing the curable composition according to any one of (1) to (7) as a component;
(10). An adhesive for asphalt roofing materials comprising the curable composition according to any one of (1) to (7) as a component;
(11). (1) to an adhesive for asphalt roofing materials using a modified asphalt containing as a component the curable composition according to any one of (7),
(12). A sealing agent comprising the curable composition according to any one of (1) to (7) as a component;
About.

  The curable composition containing the polyoxyalkylene polymer (A) having a reactive silicon group and the terpene resin (B) of the present invention is particularly suitable as an adhesive for asphalt roofing materials.

Hereinafter, the present invention will be described in detail.
<Reactive silicon group-containing polyoxyalkylene polymer (A)>
The reactive silicon group-containing polyoxyalkylene polymer (A) of the present invention has a reactive silicon group represented by the following general formula (1).
-SiR ¹ _a X _3-a (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom on the 1st to 3rd carbon atoms may be substituted with a heteroatom. X is a hydroxyl group or hydrolysis. A represents a sex group, a satisfies the condition of 0 or 1. When a plurality of X are present, they may be the same or different.

R ¹ in the general formula (1) is independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms, each of which may be independently substituted with a heteroatom. Or a triorganosiloxy group represented by —OSi (R ′) ₃ (three R ′ are each independently a hydrocarbon group having 1 to 20 carbon atoms). They may be the same or different.

  X in the general formula (1) represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include known hydrolyzable groups. Specific examples thereof include hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, ketoximate group, amino group, and 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 dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, trimethoxysilyl group, triethoxysilyl group, tris ( Examples include, but are not limited to, 2-propenyloxy) silyl group, triacetoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, and the like. Among these, a dimethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group are preferable because they are easily available for production and exhibit good mechanical properties, and a dimethoxymethylsilyl group is most preferable. From the viewpoint of activity, a trimethoxysilyl group, a (chloromethyl) dimethoxysilyl group, and a (methoxymethyl) dimethoxysilyl group are more preferable. Since no halogen is contained, a trimethoxysilyl group and a (methoxymethyl) dimethoxysilyl group are Particularly preferred.
<Main chain structure of reactive silicon group-containing polyoxyalkylene polymer (A)>
As the main chain structure of the reactive silicon group-containing polyoxyalkylene polymer (A) of the present invention, those having a main chain structure having an ether bond can be used.

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

  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.

  The main chain structure of the polymer (A) of the present invention 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 (A) 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 polyoxyalkylene polymer (A) may be linear or may have a branched chain. In order to ensure adhesiveness with the asphalt sheet, it is preferably linear.

  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 (A) is not particularly limited, but is preferably 1.6 or less and particularly preferably 1.4 or less from the viewpoint of workability.

  The number average molecular weight of the polymer (A) is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and particularly preferably 5,000 to 25,000. When the number average molecular weight of the polyoxyalkylene polymer (A) 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 number average molecular weight of the polymer (A) is obtained by directly determining the end group concentration by titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the measurement method of iodine value defined in JIS K 0070. It is defined as the molecular weight (terminal molecular weight) corresponding to the number average molecular weight determined by taking into account the structure of the organic polymer (branching degree determined by the polymerization initiator used).

  The main chain structure of the polymer (A) is preferably a linear or branched structure having 2 to 8 terminal functional groups in the precursor polymer. Since a flexible cured product is obtained, the number of terminal functional groups is preferably 2 to 3.

  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 polymer (also referred to as a precursor polymer) that is a raw material of the polymer (A), and a hydrosilane compound is hydrosilylated with respect to the unsaturated bond. It is the method of adding by. 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, (chloromethyl) dichlorosilane, (methoxymethyl) dichlorosilane; dimethoxymethylsilane, trimethoxysilane, triethoxysilane, (chloromethyl) dimethoxysilane, ( Alkoxysilanes such as methoxymethyl) dimethoxysilane; isopropenyloxysilanes such as triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane (deacetone type), etc. can give.

  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 (A) 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 (A) or the amide segment can be excluded. The polyoxyalkylene polymer (A) having an amide segment tends to increase in viscosity. Further, the polyoxyalkylene polymer (A) having an amide segment may be improved in curability.

The amide segment has the general formula (2):
—NR ² —C (═O) — (2)
(R ² represents a C 1-10 organic group 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 3 -SiR 1 a X}} 3-a (3)
(R ¹ , X and a are the same as described above. R ³ 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 3} -SiR 1 a X 3-a (4)
(R ³ , R ¹ , X and a are the same as described above) can be 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 specifically, (gamma) -aminopropyltrimethoxysilane, N-((beta) -aminoethyl) -gamma-aminopropyltrimethoxysilane, (N- Phenyl) -γ-aminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, γ-aminopropyl (chloromethyl) dimethoxysilane, γ-aminopropyl (chloromethyl) diethoxysilane, γ-aminopropyl (methoxymethyl) ) Amino group-containing silanes such as dimethoxysilane, γ-aminopropyl (methoxymethyl) diethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane Gamma-hydroxy Hydroxy group-containing silane such as trimethoxy silane; .gamma.-mercaptopropyltrimethoxysilane, mercapto-containing silanes such as mercaptomethyl triethoxysilane; 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 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- (chloromethyl) dimethoxysilylpropyl isocyanate, γ- (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxysilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, Diethoxymethylsilylmethyl isocyanate, (chloromethyl) dimethoxysilylmethyl isocyanate, (methoxymethyl) dimethoxysilylme Le isocyanate, and the like.

  When the main chain skeleton of the polymer (A) includes 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.

  When aiming at reducing the viscosity of the curable composition or improving workability, it is preferable that the polymer (A) does not substantially contain an amide segment.

  In order to develop good adhesion, the reactive silicon group equivalent of the polyoxyalkylene polymer (A) is preferably 1.5 mmol / g or less, and more preferably 1.4 mmol / g or less. The lower limit is preferably 0.01 mmol / g or more, and more preferably 0.05 mmol / g or more.

  The average number of reactive silicon groups in the polyoxyalkylene polymer (A) is preferably 1.1 or more per molecule, and the upper limit is preferably less than 85% of the number of reactive groups in the precursor polymer. Specifically, for example, when the precursor polymer of the polyoxyalkylene polymer (A) has an average of two hydroxyl groups per molecule at the terminal, the reactivity of the polymer (A) The number of silicon groups is preferably 1.1 to 1.7 on average per molecule, and more preferably 1.2 to 1.6. Moreover, when the number of terminal hydroxyl groups of the precursor polymer of the polymer (A) is 3, the average number of reactive silicon groups is preferably 1.1 to 2.5 per molecule, and 1.2 to 2 .4 is more preferable.

  The reactive silicon group may be present at either the molecular chain terminal, the side chain terminal, or both of the polymer (A). In particular, when the reactive silicon group is at the end of the molecular chain, the molecular weight between the crosslinking points is increased, and a rubber-like cured product having high strength and high elongation is easily obtained.

The average number of reactive silicon groups in the polyoxyalkylene polymer (A) is 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. It is defined as In the calculation of the average number of reactive silicon groups in the polymer (A) in the present invention, when the reactive silicon group was introduced into the precursor polymer, the precursor polymer in which no reactive silicon group was introduced and A polymer obtained by a side reaction and having no reactive silicon group introduced is regarded as a part of the component of the polymer (A) having the same main chain structure, and is contained in one molecule of the reactive silicon group. The calculation is performed by including the average number in the population parameter (number of molecules).

  The curable composition of the present invention may be used in combination with two or more polyoxyalkylene polymers (A) having different structures such as linear and branched, molecular weight, and the number and position of reactive silicon groups. Good. Each polymer may be produced separately, or may be produced simultaneously so that an arbitrary polymer can be obtained.

  A terpene resin (B) is added to the curable composition of the present invention in order to ensure adhesion.

The terpene resin is obtained by polymerizing monoterpenes represented by the chemical formula (C ₅ H ₈ ) _n such as α-pinene, β-pinene, limonene, terpinolene, myrcene, etc., respectively, or copolymerizing them. It is a general term for things that have a basic skeleton. Also included are those modified with aromatic monomers, those modified with alkyl monomers, and those modified with phenol.

Specific examples of the terpene resin include a terpene resin (for example, Yasuhara Chemical Co., Ltd., trade name: YS Resin PX1000), and an aromatic modified terpene resin (for example, Yashara Chemical Co., Ltd., trade name: YS Resin TO115). Terpene phenol resin (for example, product name: YS Resin CP, manufactured by Yasuhara Chemical Co., Ltd.) and the like, but is not limited thereto. Moreover, what hydrogenated these is also contained. Among these terpene resins, terpene phenol resins are preferable because they have high compatibility with the polyoxyalkylene polymer (A) and high adhesiveness with asphalt sheets. The hydroxyl value of the terpene phenol resin is preferably 1.0 to 10.0 mmol / g, more preferably 1.4 to 8.0 mmol / g, and 1.7 to 5.0 mmol. Some are more preferred. If the hydroxyl value is 1.0 mmol / g or less, it is not preferable because the adhesion to the asphalt sheet cannot be secured, and if it exceeds 10.0 mmol / g, the curability of the polyoxyalkylene polymer (A) is lowered. It is not preferable.
The amount of the terpene resin used is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, and most preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). If the amount of the terpene resin used is less than 1 part by weight, the adhesion with the modified asphalt may be insufficient. On the other hand, when the usage-amount of terpene-type resin exceeds 200 weight part, the viscosity of a curable composition will become high too much and there exists a tendency for workability | operativity to be inferior.

  The curable composition of the present invention has a (meth) acrylic acid ester-based polymer (C) having reactive silicon represented by the general formula (1) for the purpose of improving the adhesion to a substrate. It may contain.

  As the silicon group of the reactive silicon group-containing (meth) acrylic acid ester polymer (C), the silicon groups listed above may be single or plural types may be mixed.

There is no restriction | limiting in particular as a monomer unit which comprises the reactive silicon group containing (meth) acrylic acid ester type polymer (C) of this invention, Various (meth) acrylic acid ester type monomers can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , S-butyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, (meth) acrylic acid Hexadecyl, stearyl (meth) acrylate, behenyl (meth) acrylate, (meth) acryl Cyclohexyl, (meth) acrylic acid (3-trimethoxysilylpropyl), (meth) acrylic acid (3- (dimethoxymethylsilyl) propyl), (meth) acrylic acid (2-trimethoxysilylethyl), (meth) acrylic Acid (2- (dimethoxymethylsilyl) ethyl), (meth) acrylic acid trimethoxysilylmethyl, (meth) acrylic acid triethoxysilylmethyl, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid 2 -Methoxyethyl, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethylene oxide adduct of (meth) acrylic acid, (meth) acrylic acid 2,2,2-trifluoroethyl, (meth) acrylic acid 3,3 -Trifluoropropyl, 3,3,4,4,4-pentafluorobutyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, trifluoromethyl (meth) acrylate , Perfluoroethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoro (meth) acrylate Hexylethyl, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, tetrahydro (meth) acrylate Furfuryl, glycidyl (meth) acrylate, etc. . Moreover, methacrylic acid and acrylic acid which are not esterified can also be utilized as a monomer which comprises a polymer (C).
In addition to the (meth) acrylic acid ester monomer, the following vinyl monomers can be copolymerized. 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 monomers may be used alone or a plurality of monomers may be copolymerized.

  The monomer unit constituting the main chain structure of the reactive silicon group-containing (meth) acrylic acid ester polymer (C) is compatible with the reactive silicon group-containing polyether polymer (A). The (meth) acrylic acid ester monomer is preferably contained in an amount of 50% by weight or more, more preferably 70% by weight or more. Furthermore, as a (meth) acrylic acid ester monomer, an alkyl (meth) acrylate (c1) having an alkyl group having 1 to 8 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 10 to 30 carbon atoms ( It is preferable to use c2) together. In this case, the ratio of the alkyl (meth) acrylate (c1) to the alkyl (meth) acrylate (c2) is preferably (c1) :( c2) = 95: 5 to 40:60 in terms of weight ratio, 90 : 10-60: 40 is more preferable. As a combination not using the component (c2), a combination of methyl (meth) acrylate, butyl (meth) acrylate and an alkyl (meth) acrylate having an alkyl group having 7 to 9 carbon atoms, or carbon number 1 The combined use of an alkyl (meth) acrylate having an alkyl group of ˜2 and an alkyl (meth) acrylate having an alkyl group of 7 to 9 carbon atoms is preferred.

  The (meth) acrylic acid ester polymer can be synthesized by various known polymerization methods. A radical polymerization method is preferred from the viewpoint of versatility of the monomer and ease of control.

  The radical polymerization method can be classified into “general radical polymerization method” and “controlled radical polymerization method”. The “general radical polymerization method” is simply a polymerization method using a polymerization initiator such as an azo compound or a peroxide, and is a simple polymerization method. On the other hand, the “controlled radical polymerization method” is a method capable of introducing a specific functional group at a controlled position such as a terminal. The “controlled radical polymerization method” can be further classified into a “chain transfer agent method” and a “living radical polymerization method”. The “chain transfer agent method” is characterized in that polymerization is carried out using a chain transfer agent having a specific functional group, and a vinyl polymer having a functional group at the terminal is obtained. On the other hand, the “living radical polymerization method” is characterized in that a polymer growth terminal grows without causing a side reaction such as a termination reaction, and a polymer having a molecular weight almost as designed can be obtained. In the present invention, any of these polymerization methods may be used.

  Specific examples of the “general radical polymerization method” include a solution polymerization method and a bulk polymerization method in which a polymerization initiator, a chain transfer agent, a solvent and the like are added and polymerization is performed at 50 to 150 ° C.

  Examples of the polymerization initiator include 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 1,1 Azo compounds such as' -azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3 , 5,5-trimethylhexanoyl) peroxide and other diacyl peroxides; Peroxydicarbonates such as propyl purge carbonate, di-sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge carbonate, dicyclohexyl purge carbonate; -Butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate Peroxyesters such as methyl ethyl ketone peroxide, ketone peroxides such as cyclohexanone peroxide, di-tert-butyl peroxide, dicumylpa -Dialkyl peroxides such as oxide, tert-butyl cumyl peroxide, 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane; cumene hydroxy peroxide, tert-butyl hydroperoxide, etc. Hydroperoxide; peroxides such as 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane and the like. These polymerization initiators may be used alone or in combination of two or more.

  Examples of the chain transfer agent include mercapto group-containing compounds such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan. Further, when a reactive silicon group is to be introduced into the molecular chain terminal of the (meth) acrylic acid ester polymer, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, (3-mercaptopropyl) ) (Chloromethyl) dimethoxysilane, (3-mercaptopropyl) (methoxymethyl) dimethoxysilane, mercaptomethyltrimethoxysilane, (mercaptomethyl) dimethoxymethylsilane and other mercaptosilane compounds having a mercapto group (c3) ) Is preferably used. These may be used alone or in combination of two or more.

  Examples of the solvent include aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane, and the like. Hydrocarbon compounds; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate Compounds: Alcohol compounds such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and amyl alcohol can be exemplified. Among these, at least one selected from dialkyl carbonate compounds and alcohol compounds is preferable from the viewpoints of not being a guideline formulating substance of the Ministry of Health, Labor and Welfare, odor, and environmental load. Furthermore, according to the measurement method described in the February 14, 2001 edition of the boiling point, GEV (Gemainshaft Emission Control Reelte Ferry Gewerkstoffe Ave) defined by GEV Specification and Classification Criteria From the point that the diffusibility of all volatile organic compounds from the composition can be suppressed, dimethyl carbonate, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl Alcohol is more preferable, and 2-propanol and isobutyl alcohol are particularly preferable.

  In addition to the solvent, it is also possible to polymerize with a reactive silicon group-containing polyether polymer, a precursor compound thereof, a plasticizer described later, and the like.

  The “chain transfer agent method” is a polymerization method in which a functional group can be introduced quantitatively to the polymer terminal in comparison with the “general radical polymerization method”. The radical polymerization using a chain transfer agent is not particularly limited. For example, a halogen-terminated polymer is obtained using a halogenated hydrocarbon as shown in JP-A-4-132706 as a chain transfer agent. A hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as shown in JP-A-61-271306, JP-A-2594402, JP-A-54-47782 as a chain transfer agent. The method of obtaining coalescence is mentioned.

  Unlike the above-described polymerization method, the “living radical polymerization method” can obtain a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity, and a monomer having a specific functional group. It is a polymerization method that can be introduced at almost any position. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state.

  The “living radical polymerization method” uses, for example, a cobalt porphyrin complex as shown in Journal of American Chemical Society (1994), Vol. 116, page 7943. J. Am. Chem. Soc. Initiators, those using nitrooxide radicals as shown in JP-A-2003-500378, organic halides and sulfonyl halides as shown in JP-A-11-130931, etc. And atom transfer radical polymerization (ATRP method) using a transition metal complex as a catalyst. Further, in the present application, so-called reverse atom transfer radical polymerization, that is, a normal atom transfer radical polymerization catalyst as shown in Macromolecules, 1999, 32, 2872, generates radicals. A general radical initiator such as a peroxide is allowed to act on a high oxidation state when it is used, for example, Cu (II ′) when Cu (I) is used as a catalyst, and as a result, an atom transfer radical Polymerization methods that produce an equilibrium state similar to polymerization are also included in the atom transfer radical polymerization method.

  Further, as a polymerization method other than these, (meth) acrylic acid using a metallocene catalyst as disclosed in JP-A-2001-040037 and a thiol compound having at least one reactive silicon group in the molecule is used. A method for obtaining an ester polymer, or a reaction of a vinyl monomer as shown in JP-A-57-502171, JP-A-59-006207, JP-A-60-511992 with stirring tank type reaction It is also possible to use a high-temperature continuous polymerization method in which continuous polymerization is performed using a vessel.

  The number average molecular weight of the (meth) acrylic acid ester polymer (C) is not particularly limited, but is preferably a polystyrene-equivalent molecular weight by GPC measurement, preferably 500 to 100,000, more preferably 500 to 50,000, and 1,000. ˜30,000 is particularly preferred.

  The method for introducing the reactive silicon group represented by the general formula (1) into the (meth) acrylic acid ester polymer is not particularly limited. For example, the methods as shown in the following (iii) to (vi) Can be used.

  (Iii) A method in which a compound (c4) having a polymerizable unsaturated group and a reactive silicon-containing group represented by the general formula (1) is copolymerized together with the above-described monomer. When this method is used, reactive silicon groups tend to be randomly introduced into the main chain of the polymer.

  (Iv) A method of polymerizing a (meth) acrylate polymer using a mercaptosilane compound having a reactive silicon-containing group represented by the general formula (1) as a chain transfer agent. When this method is used, a reactive silicon group can be introduced into the polymer terminal.

  (V) A method in which a compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then a reactive silicon group and a compound having a functional group that reacts with the V group are reacted. Specifically, after copolymerizing 2-hydroxyethyl acrylate, a method of reacting this hydroxyl group with an isocyanate silane having a reactive silicon-containing group represented by the general formula (1), or copolymerizing glycidyl acrylate Then, a method of reacting this epoxy group with an aminosilane compound having a reactive silicon-containing group represented by the general formula (1) can be exemplified.

  (Vi) A method of introducing a reactive silicon group by modifying a terminal functional group of a (meth) acrylic acid ester polymer synthesized by a living radical polymerization method. The (meth) acrylic acid ester-based polymer obtained by the living radical polymerization method can easily introduce a functional group at the polymer end, and a reactive silicon group can be introduced at the polymer end by modifying this.

  Examples of the silicon compound that can be used for introducing the reactive silicon group of the (meth) acrylic acid ester-based polymer (C) of the present invention using the above method include the following compounds. The compound (c4) having a polymerizable unsaturated group and a reactive silicon group used in the method (iii) includes (meth) acrylic acid (3-trimethoxysilylpropyl), (meth) acrylic acid (3- (dimethoxy Methylsilyl) propyl), (meth) acrylic acid (2-trimethoxysilylethyl), (meth) acrylic acid (2- (dimethoxymethylsilyl) ethyl), (meth) acrylic acid (trimethoxysilyl) methyl, (meth ) (Dimethoxymethylsilyl) methyl acrylate, (meth) acrylic acid (triethoxymethylsilyl) methyl, (meth) acrylic acid (diethoxymethylsilyl) methyl, (meth) acrylic acid ((chloromethyl) dimethoxysilyl) methyl , (Meth) acrylic acid 3-((chloromethyl) dimethoxysilyl) propyl, (meth) acrylic 3-((chloromethyl) diethoxysilyl) propyl, (meth) acrylic acid ((methoxymethyl) dimethoxysilyl) methyl, (meth) acrylic acid 3-((methoxymethyl) dimethoxysilyl) propyl, (meth) acrylic acid 3-((methoxymethyl) diethoxysilyl) propyl and the like can be mentioned. From the viewpoint of availability, (meth) acrylic acid (3-trimethoxysilylpropyl), (meth) acrylic acid (3- (dimethoxymethylsilyl) propyl), and (meth) acryloxymethyltrimethoxysilane are particularly preferable.

  Examples of the mercaptosilane compound having a reactive silicon-containing group represented by the general formula (1) used in the method (iv) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, mercaptomethyltrimethoxysilane. , (Mercaptomethyl) dimethoxymethylsilane, mercaptomethyltriethoxysilane, 3-mercaptopropyl (chloromethyl) dimethoxysilane, 3-mercaptopropyl (methoxymethyl) dimethoxysilane, and the like.

  Examples of the compound having a reactive silicon group and a functional group that reacts with the V group used in the method (v) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, and isocyanate. Isocyanate silane compounds such as methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, isocyanatemethyldiethoxymethylsilane, 3-isocyanatepropyl (chloromethyl) dimethoxysilane, 3-isocyanatepropyl (methoxymethyl) dimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrie Xysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyldiethoxymethylsilane, 3-glycidoxypropyl (chloromethyl) dimethoxysilane, 3- Epoxysilane compounds such as glycidoxypropyl (methoxymethyl) dimethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 -Aminopropyltrimethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexyl Aminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, 3-aminopropyl (chloromethyl) dimethoxysilane, 3-aminopropyl (methoxymethyl) dimethoxysilane, etc. And the aminosilane compound.

  In the method (vi), any modification reaction can be used. For example, a method using a compound having a functional group capable of reacting with a terminal reactive group obtained by polymerization and a silicon group, a terminal reactive group, A method in which a double bond is introduced into a polymer terminal using a compound having a functional group capable of reacting and a double bond and a reactive silicon group is introduced thereto by hydrosilylation or the like can be used. In the former method, the above-mentioned isocyanate silane or the like can be used. Hydrosilanes used for hydrosilylation include (chloromethyl) dimethoxysilane, (chloromethyl) diethoxysilane, (methoxymethyl) dimethoxysilane, (methoxymethyl) diethoxysilane, (ethoxymethyl) dimethoxysilane, (amino Methyl) dimethoxysilane, (dimethylaminomethyl) dimethoxysilane, (diethylaminomethyl) dimethoxysilane, (N- (2-aminoethyl) aminomethyl) dimethoxysilane, (acetoxymethyl) dimethoxysilane, (acetoxymethyl) diethoxysilane, Examples include hydrosilanes such as dimethoxymethylsilane, diethoxymethylsilane, methyldiisopropoxysilane, trimethoxysilane, triethoxysilane, and triisopropoxysilane. If the method (vi) is used, the molecular weight is arbitrarily controlled, and a reactive silicon group-containing (meth) acrylic acid ester polymer (C) having a narrow molecular weight distribution can be obtained.

  These methods may be used in any combination. For example, when the method (iii) and the method (iv) are combined, a reactive silicon group can be introduced into both the molecular chain terminal and / or the side chain.

The reactive silicon group of the reactive silicon group-containing (meth) acrylic acid ester polymer (C) of the present invention may be introduced at either the molecular chain terminal or the main chain. When the polymer (C) in which the reactive silicon group is introduced only at the molecular chain end is used, the elongation characteristics of the obtained cured product tend to be improved. Moreover, when the polymer (C) in which the reactive silicon group is introduced into the main chain is used, the adhesiveness of the curable composition may be improved.
The average number of reactive silicon groups per molecule is preferably 0.5 to 4.0, more preferably 0.7 to 3.5, and particularly preferably 1.0 to 3.0.

  A method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive silicon group and a (meth) acrylic acid ester polymer having a reactive silicon group is disclosed in JP-A-59-122541. Japanese Laid-Open Patent Application No. 63-112642, Japanese Patent Application Laid-Open No. 6-172631, and Japanese Patent Application Laid-Open No. 11-116663. In addition, a method of polymerizing a (meth) acrylic acid ester monomer in the presence of a polyoxypropylene polymer having a reactive silicon group can be used. This production method is specifically disclosed in JP-A-59-78223, JP-A-60-228516, JP-A-60-228517, and the like. The polymers (A) and (C) of the present invention can be blended by the same method, but are not limited thereto.

  The mixing ratio of the polyoxyalkylene polymer (A) and the (meth) acrylic ester polymer (C) is not particularly limited, but (A) :( C) = 95: 5 to 10:90 (parts by weight) Is preferable, 80:20 to 20:80 (parts by weight) is more preferable, and 70:30 to 30:70 (parts by weight) is particularly preferable.

The curable composition of the present invention may contain a polymer having a main chain skeleton other than the polyoxyalkylene polymer (A) and the (meth) acrylate polymer (C) as an optional component. The main chain structure includes ethylene-propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, polychloroprene, polyisoprene, isoprene or a copolymer of butadiene and acrylonitrile and / or styrene, and polybutadiene. , Copolymers of isoprene or butadiene and acrylonitrile and styrene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; dibasic acids such as adipic acid and the like Polyester polymer obtained by condensation with glycol or ring-opening polymerization of lactones; Polysulfide-based polymer; Nylon 6 by ring-opening polymerization of ε-caprolactam; Nylon 6 by condensation polymerization of hexamethylenediamine and adipic acid 6. Hexamethy Nylon 6 · 10 by condensation polymerization of diamine and sebacic acid, Nylon 11 by condensation polymerization of ε-aminoundecanoic acid, Nylon 12 by ring-opening polymerization of ε-aminolaurolactam, and two or more components of the above nylon Examples thereof include polyamide polymers such as copolymer nylon; polycarbonate polymers obtained by condensation polymerization of bisphenol A and carbonyl chloride, diallyl phthalate polymers, and the like.
Of these, saturated hydrocarbon polymers such as polyisobutylene, hydrogenated polyisoprene, and hydrogenated polybutadiene are more preferable because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance.

In the curable composition of the present invention, the reaction of hydrolyzing and condensing the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C) is promoted, and the polymer is A condensation catalyst is used for the purpose of chain extension or crosslinking. Specific examples of the condensation catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dimethyltin diacetate, dimethyltin bis (acetylacetonate), dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate) , Dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (octyl maleate), dibutyltin bis (tridecyl maleate), dibutyltin bis (benzyl maleate) Dibutyltin diacetate, dioctyltin bis (triethoxysilicate), dioctyltin bis (ethyl maleate), dioctyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyl Tin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, reaction product of dibutyltin oxide and phthalate ester, dioctyltin dilaurate, dioctyl Tetravalent organotin compounds such as tin diacetate and dioctyltin bis (acetylacetonate); aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxy Organoaluminum compounds such as luminium ethyl acetoacetate; Zirconium compounds such as zirconium tetrakis (acetylacetonate); Carboxylic acids such as 2-ethylhexanoic acid, octylic acid, neodecanoic acid, oleic acid, or naphthenic acid; Tin carboxylate , Lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, carboxyl Carboxylic acid metal salts such as nickel acid and cerium carboxylate; organic acid phosphate ester; organic sulfonic acid such as trifluoromethanesulfonic acid; inorganic acid such as hydrochloric acid, phosphoric acid and boronic acid; boron trifluoride Boron trifluoride complexes such as boron trifluoride diethyl ether complex, boron trifluoride ethylamine complex; ammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, cesium fluoride, ammonium hydrogen fluoride, 1,1 , 2,3,3,3-hexafluoro-1-diethylaminopropane (MEC81, commonly known as Ishikawa reagent), potassium hexafluorophosphate, Na ₂ SiF ₆ , K ₂ SiF ₆ , (NH ₄ ) ₂ SiF _6, etc. Anion-containing compound: 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 6- (dibutylamino) -1,8 -Diazabicyclo [5,4,0] undecene-7 (DBA-DBU), 6- (2-hydroxypropyl) -1,8-di Zabicyclo [5,4,0] undec-7-ene (OH-DBU), a compound in which the hydroxyl group of OH-DBU is modified by urethanization, etc., 1,5-diazabicyclo [4,3,0] nonene-5 (DBN) ), Amidines such as 1,4-diazabicyclo [2,2,2] octane (DABCO); phenol salt of DBU (specifically, trade name: U-CAT SA1 (manufactured by San Apro)), octylic acid of DBU Salt (specifically, trade name: U-CAT SA102 (San Apro)), DBU p-toluenesulfonate (specifically, trade name: U-CAT SA506 (San Apro)), DBN octyl Acid salt (specifically, trade name: U-CAT 1102 (manufactured by San Apro)), 1- (o-tolyl) biguanide, 1-phenylguanidine, 1,2-dimethyl-1,4, , 6-tetrahydropyrimidine may be mentioned amidine compounds such as, but not limited thereto.

  The amount of the condensation catalyst used is preferably 0.001 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). 0.01-10 weight part is more preferable, and 0.05-1 weight part is especially preferable. If the amount of the condensation catalyst used is less than 0.001 part by weight, the curing rate may be insufficient, and the curing reaction may not proceed sufficiently. On the other hand, when the amount of the condensation catalyst used exceeds 20 parts by weight, the curing rate is too fast, and therefore the time that the curable composition can be used tends to be short, resulting in poor workability and poor storage stability.

  A plasticizer can 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 polycarboxylic acid ester compounds such as butyl; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; alkylsulfonic acid phenyl ester (specifically, trade name: Mesamol (manufactured by LANXESS)); Phosphate ester compounds such as cresyl phosphate and tributyl phosphate; trimellitic acid ester compounds; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyls and partially hydrogenated terphenyls; process oils; epoxidized soybean oil and epoxybenzyl stearate And epoxy plasticizers.

  Moreover, a polymeric plasticizer can 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.

  Among these polymer plasticizers, those compatible with both the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C) are preferable. From this point, a polyether polymer and a vinyl polymer are preferable. Further, when a polyether polymer is used as a plasticizer, it is preferable because surface curability and deep part curability are improved and curing delay after storage does not occur, and polypropylene glycol is more preferable. Moreover, a vinyl polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance. Among vinyl polymers, acrylic polymers such as poly (meth) acrylic acid alkyl esters are particularly preferred. 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 a (meth) acrylic acid alkyl ester monomer described in JP-A No. 2001-207157 at high temperature and high pressure.

  The number average molecular weight of the polymer plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, still more preferably 1,000 to 8,000, and particularly preferably 1,000. 5,000. Most preferably, it is 1,000 to 3,000. If the molecular weight is too low, the plasticizer will flow out over time due to heat and rain, and the initial physical properties cannot be maintained over a long period of time. 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 of the polymer plasticizer 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 have a reactive silicon group. When it has a reactive silicon group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product. When it has a reactive silicon group, it is preferably 1 or less, more preferably 0.8 or less on average per molecule. When using a plasticizer having a reactive silicon group, particularly a polyether polymer having a reactive silicon group, the number average molecular weight thereof must be lower than that of the polyoxyalkylene polymer (A).

  When using it as an adhesive for asphalt sheets, care must be taken in selecting the plasticizer. Usually, a plasticizer that dissolves an asphalt sheet such as a phthalate compound is not suitable for the curable composition of the present invention. In the unlikely event that it is used, there is a possibility that the waterproof system will malfunction and leak. Accordingly, a plasticizer that does not dissolve the asphalt sheet is suitable as the plasticizer, and a polyether plasticizer is preferable. Particularly preferred are polyether plasticizers having a number average molecular weight of 3000 or more.

  The amount of the plasticizer used is 5 to 100 parts by weight with respect to a total of 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer (A) and the reactive silicon group-containing (meth) acrylic acid ester polymer (C). 150 parts by weight is preferable, 10 to 120 parts by weight is more preferable, and 20 to 100 parts by weight is particularly preferable. 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 the silane coupling agent include γ-isocyanatepropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and α-isocyanatemethyltrimethoxysilane. Isocyanate group-containing silanes such as α-isocyanatomethyldimethoxymethylsilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N -Β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropy Triethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxy Silane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, (aminomethyl) dimethoxymethylsilane, (aminomethyl) trimethoxysilane, (phenylaminomethyl) dimethoxymethylsilane, (phenylaminomethyl) trimethoxysilane, bis Amino group-containing silanes such as (3-trimethoxysilylpropyl) amine; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopro Mercapto group-containing silanes such as rumethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4- Epoxy group-containing silanes such as epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (β-methoxyethoxy) Carboxysilanes such as silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyl Vinyl-type unsaturated group-containing silanes such as oxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris (trimethoxysilyl) isocyanurate; methyl (N- Carbamate silanes such as dimethoxymethylsilylmethyl) carbamate, methyl (N-trimethoxysilylmethyl) carbamate, methyl (N-dimethoxymethylsilylpropyl) carbamate, methyl (N-trimethoxysilylpropyl) carbamate; (methoxymethyl) dimethoxy Alkoxy group-containing silanes such as methylsilane, (methoxymethyl) trimethoxysilane, (ethoxymethyl) trimethoxysilane, and (phenoxymethyl) trimethoxysilane; Pills succinic anhydride, 3-may be mentioned acid anhydride-containing silanes such as (triethoxysilyl) 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.

  The amount of the silane coupling agent used is based on a total of 100 parts by weight of the reactive silicon group-containing polyoxyalkylene polymer (A) and the reactive silicon group-containing (meth) acrylic acid ester polymer (C). 0.1 to 20 parts by weight is preferable, and 0.5 to 10 parts by weight is particularly 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 total amounts of a polymer (A) and a polymer (C), Preferably it is 0.5-10 weight part.

  Various fillers can be mix | blended with the curable composition of this invention. Fillers include reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, Resin powder such as 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, PVC powder, PMMA powder And fillers such as asbestos, 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.

  Further, when obtaining a highly transparent composition, as described in JP-A-11-302527, polymer powder made from a polymer such as methyl methacrylate or amorphous silica is used. Etc. can be used as fillers. Further, as described in JP-A-2000-38560, a composition having high transparency can be obtained by using hydrophobic silica or the like, which is a fine powder of silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler. Can be obtained. The surface of silicon dioxide fine powder is generally a silanol group (-SiOH), and (-SiO-hydrophobic group) is generated by reacting organosilanide or alcohol with this silanol group. What is made is hydrophobic silica. Specifically, dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane and the like are reactively bonded to the silanol group present on the surface of the silicon dioxide fine powder. The silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.

  When you want to obtain a hardened material with high strength by using these fillers, mainly fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, silicic anhydride, hydrous silicic acid and carbon black, surface treatment A filler selected from fine calcium carbonate, calcined clay, clay and activated zinc white is preferred, and the amount used is the sum of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). The amount is preferably 1 to 200 parts by weight with respect to 100 parts by weight.

  In addition, when it is desired to obtain a cured product having low strength and high elongation at break, mainly calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon When a filler selected from the above is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the polymer (C), 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 10 to 200 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). Part by weight is preferred.

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

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

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

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

  The scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight with respect to 100 parts by weight of a composition such as a sealing material composition or an adhesive composition. The blending amount is appropriately selected depending on the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.

  As the scale-like or granular substance, natural substances such as silica sand and mica, synthetic rubber, synthetic resin, and inorganic substances such as alumina are used. In order to enhance the designability when filling the joint, it is colored in an appropriate color according to the material and pattern of the outer wall.

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

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

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

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

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

  Moreover, the thermally expansible fine particle hollow body as described in Unexamined-Japanese-Patent No. 2004-51701, 2004-66749, etc. can be used. The thermally expandable fine hollow body is a polymer outer shell material (vinylidene chloride copolymer, acrylonitrile copolymer, or vinylindene chloride-acrylonitrile copolymer weight) such as a hydrocarbon having 1 to 5 carbon atoms. It is a plastic sphere wrapped in a spherical shape. By heating the bonding part using this composition, the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically and the bonding interface is Plays the role of peeling. By adding the thermally expandable fine hollow body, it is possible to obtain an adhesive composition that can be easily peeled off without destroying the material simply by heating when not necessary, and can be peeled off without using any organic solvent.

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

  The amount of the spherical hollow body used is preferably 0.01 to 30 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). 0.1-20 weight part is preferable. If it is less than 0.01 part by weight, there is no workability improvement effect, and if it exceeds 30 parts by weight, the elongation and breaking strength of the cured product tend to be low.

  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 with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C).

  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.

  The amount of the antioxidant used is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). 0.2-5 weight part is 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.

  The light stabilizer is preferably used in an amount of 0.1 to 10 parts by weight, particularly 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). 0.2-5 weight part is 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, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, but benzotriazole is particularly preferable, and commercially available names are Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (manufactured by BASF) are listed. 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.

  The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). 0.2-5 weight part is preferable.

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

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

  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 silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane is 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). On the other hand, 0.1-20 weight part is preferable, and 0.5-10 weight part is especially preferable.

  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, an organic polymer having a crosslinkable hydrolyzable silicon-containing group and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis described in JP-A-6-279893 can also be used.

In the present invention, a tackifying resin other than a terpene-based resin may be added for the purpose of enhancing the adhesiveness and adhesion to the substrate, or if necessary.
Specific examples include phenol resin, modified phenol resin, xylene-phenol 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).

  The amount of the tackifying resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). More preferably, it is 5-30 parts. 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 with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C).

  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 material is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). It is preferably used in the range of parts by weight, and if it is 0.1 parts by weight or less, there is no effect of improving the weather resistance, and if it 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 amine compounds. The amount of the oxygen curable substance used is in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (C). The amount is preferably 0.5 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. 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. These epoxy resins, polyoxyalkylene polymer (A) and (meth) acrylic acid ester polymer (C) are used in a weight ratio of (A) + (C) / epoxy resin = 100/1. The range is 1/100. When the ratio of (A) + (C) / epoxy resin is less than 1/100, the effect of improving the impact strength and toughness of the cured epoxy resin is difficult to obtain, and (A) + (C) / epoxy resin If the ratio exceeds 100/1, 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 total amount of the component (A) and the component (C) is 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, 1-200 weight part of epoxy resins are used with respect to the total amount of 100 weight part of (A) component and (C) component, More preferably, 5-100 weight part is used. It is good.

  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 amine compound and a carbonyl compound.

  For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, as amine 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 Polyvalent amines such as ethyl) amine and tetra (aminomethyl) methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine and tetraethylenepentamine; polyoxyalkylene-based polyamines; γ-aminopropyltri Tokishishiran, N-(beta-aminoethyl)-.gamma.-aminopropyltrimethoxysilane, etc. aminosilanes such as N-(beta-aminoethyl)-.gamma.-aminopropyl methyl dimethoxy silane can 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 Etc. can be used.

  When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. These ketimines may be used alone or in combination of two or more, and are used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount used is the kind of epoxy resin and ketimine It depends on.

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

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

  Various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, curability regulators, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, fungicides. Etc. 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 organic polymer composition are mixed before use. From the viewpoint of workability, a one-component type is preferable.

  When the curable composition is of a one-component type, all the ingredients are pre-blended, so the water-containing ingredients are dehydrated and dried before use, or dehydrated during decompression or the like during compounding and kneading. Is preferred. In the case where the curable composition is a two-component type, it is not necessary to add a curing catalyst to the main agent containing an organic polymer having a reactive silicon group, so that even if some moisture is contained in the compounding agent, the gel Although there is little concern about conversion, dehydration and drying are preferable when long-term storage stability is required. As the dehydration and drying method, a heat drying method is preferable for solid materials such as powder, and a dehydration method using a reduced pressure dehydration method or a synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide or the like is preferable for a liquid material. is there. Alternatively, a small amount of an isocyanate compound may be blended to react with an isocyanate group and water for dehydration. Further, an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be blended and reacted with water for dehydration. 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 silicon compound capable of reacting with water such as dehydrating agent, especially vinyltrimethoxysilane is based on 100 parts by weight of polyoxyalkylene polymer (A) and (meth) acrylic acid ester polymer (C). The range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight 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.

  In particular, the curable composition of the present invention can be suitably used as an adhesive for asphalt roofing materials. The asphalt sheet used for asphalt roofing is not particularly limited, and examples thereof include asphalt sheets using straight asphalt, blown asphalt, modified asphalt (one obtained by modifying straight asphalt with resin), and the like. Modified asphalts include rubber-based modifiers such as styrene-butadiene random copolymer (SBR), chloroprene rubber (CR), and natural rubber (NR); thermoplastic elastomers such as SBS, SIS, SEBS, SEPS, and SIBS System modifiers; thermoplastic resins such as ethylene / vinyl acetate copolymer (EVA), ethylene / ethyl acrylate copolymer (EEA), polyethylene (PE), etc., but are not limited thereto. . Among these, the curable composition is preferably used for modified asphalt from the viewpoint of adhesiveness. In particular, it is preferably used for modified asphalt modified with a rubber-based modifying material or a thermoplastic elastomer-based modifying material.

  It can also be used for adhesives, pressure-sensitive adhesives, sealing materials for buildings, ships, automobiles, roads, etc., mold preparations, vibration damping materials, vibration damping materials, soundproofing materials, foam materials, paints, and spray materials. Since the cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.

  Furthermore, electrical / electronic component 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, non-contact-type adhesives, spray-type sealing materials, cracks Repair materials, tile adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives, medical equipment sealing materials, food packaging materials, sealing materials for joints of exterior materials such as siding boards, coating materials , Primer, electromagnetic wave shielding conductive material, heat conductive material, hot melt material, electrical and electronic potting agent, film, gasket, various molding materials, and anticorrosion of meshed glass and laminated glass end face (cut part) It can be used for various applications such as liquid sealants used in waterproof sealing materials, 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 1)
Polyoxypropylene having a number average molecular weight of 20,000 (terminal molecular weight defined above) is obtained by polymerizing propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a polyoxypropylene diol having a molecular weight of about 3,000 as an initiator. Diol was obtained. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and then 1.5 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, with respect to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, 36 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) was added and stirred while slowly adding 0.96 parts by weight of dimethoxymethylsilane. And dripped. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby the reactive silicon group equivalent was 0.09 mmol / g and the number average molecular weight was 20,000. A linear reactive silicon group-containing polyoxypropylene polymer (A-1) having a dimethoxymethylsilyl group at the end was obtained.

(Synthesis Example 2)
44.7 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 ° C. in a nitrogen atmosphere. There, 9.0 parts by weight of methyl methacrylate, 62.7 parts by weight of butyl acrylate, 14.9 parts by weight of stearyl methacrylate, 2.4 parts by weight of 3-methacryloxypropylmethyldimethoxysilane, and 2,2′-azobis (2 -Methylbutyronitrile) A mixed solution prepared by dissolving 0.40 parts by weight in 24.3 parts by weight of isobutanol was added dropwise over 5 hours. Polymerization was further carried out at 105 ° C. for 2 hours, and the average number of silicon groups per molecule was 2.0 and the number average molecular weight was 17,000 (Tosoh's HLC-8120GPC was used as the liquid feeding system, and the column was Tosoh's TSK-GEL. An isobutanol solution (solid content 60%) of a reactive silicon group-containing (meth) acrylic acid ester polymer (C-1) having a H type and a solvent having a polystyrene equivalent molecular weight measured with THF is obtained. It was.

(Synthesis Example 3)
Polyoxypropylene diol having a molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 20,000 (calculated in the same manner as in Synthesis Example 1). Oxypropylene diol was obtained. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and then 1.5 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, while adding 36 ppm of platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) to 100 parts by weight of the allyl group-terminated polyoxypropylene obtained, 0.70 part by weight of dimethoxymethylsilane was slowly added while stirring. And dripped. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby the reactive silicon group equivalent was 0.07 mmol / g and the number average molecular weight was 20,000. A linear reactive silicon group-containing polyoxypropylene polymer (A-2) having a dimethoxymethylsilyl group at the end was obtained.

(Synthesis Example 4)
Polyoxypropylene diol having a molecular weight of about 3,000 is used as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 12,000 (calculated in the same manner as in Synthesis Example 1). Oxypropylene diol was obtained. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene diol to distill off the methanol, and then 1.5 equivalents of 3-chloro-1-propene was added. The terminal hydroxyl group was converted to an allyl group. Next, while adding 36 ppm of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene, 1.20 parts by weight of dimethoxymethylsilane was slowly added while stirring. And dripped. After the mixed solution was reacted at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby the reactive silicon group equivalent was 0.12 mmol / g and the number average molecular weight was 12,000. A linear reactive silicon group-containing polyoxypropylene polymer (A-3) having a dimethoxymethylsilyl group at the end was obtained.

Example 1
60.0 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the reactive silicon group-containing (meth) acrylic acid ester polymer obtained in Synthesis Example 2 ( 66.7 parts by weight of an isobutyl alcohol solution of C-1) was mixed, and isobutylalconol was distilled off under reduced pressure to obtain a polymer weight ratio (A-1) / (C-1) = 70/30 A coalescence mixture was obtained. To 100 parts by weight of the obtained polymer, 30 parts by weight of a terpene resin (manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Resin CP), fatty acid-treated calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., trade name: Shirakaka CCR ) 30 parts by weight, heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SB red) 150 parts by weight, plasticizer (manufactured by Jplus Co., Ltd., trade name: DIDP) 50 parts by weight, UV absorption 1 part by weight of an agent (manufactured by BASF, trade name: TINUVIN 326) and 1 part by weight of a light stabilizer (manufactured by Sankyo Lifetech Co., Ltd., trade name: Sanol LS770) were mixed and sufficiently kneaded into three paint rolls. Dispersed once. Next, the mixture was kneaded for 2 hours while being dehydrated by a planetary mixer under reduced pressure at 120 ° C. and 0.2 mmHg. After cooling to room temperature, 2 parts by weight of a dehydrating agent (manufactured by Momentive Co., Ltd., trade name: A-171), 3 parts by weight of an adhesion promoter (manufactured by Momentive Co., Ltd., trade name: A-1120), a condensation catalyst (Nitto After mixing 0.5 parts by weight of Kasei Co., Ltd., trade name: Neostan U-220H, and kneading sufficiently, the curable composition was filled into a moisture-proof cartridge type container.

(Skinning time)
The composition was extruded from the cartridge under an atmosphere of 23 ° C. and a relative humidity of 50%, filled in a mold having a thickness of about 5 mm using a spatula, and the time when the surface was flattened was defined as the curing start time. The surface was touched with a spatula, and the curing time was measured with the time until the composition no longer adhered to the spatula as the skinning time. The results are shown in Table 1.

(T-shaped peeling)
Modified asphalt surface (surface is 150mm x 15mm in width) modified with SBS in an atmosphere of 23 ° C and 50% relative humidity in accordance with JIS K 6854-3 (surface is sand) The curable composition was uniformly applied so that the thickness was 2.0 mm, and the modified asphalt surface of the modified asphalt sheet having the same size was bonded. After curing at 23 ° C. for 2 weeks, a T-peel test was performed (test speed 200 mm / min), and the adhesive strength was measured. The adhesive having a suppressed yellowing degree after the T-peeling test was evaluated as ◯, and the adhesive having a large yellowing degree was evaluated as △.

(Examples 2-7, Comparative Examples 1-3)
A formulation was prepared and evaluated in the same manner as in Example 1 except that the formulation was mixed at the blending ratio shown in Table 1.

  From the results of Table 1, from the comparison between Examples 1 to 7 and Comparative Examples 1 to 3, the curable composition containing the reactive silicon group-containing polyoxyalkylene polymer (A) and the terpene resin (B) is It can be seen that the adhesiveness with the modified asphalt sheet is excellent. In particular, good adhesion can be obtained when a terpene phenol resin having a hydroxyl value of 1.4 mmol / g or more is used.

Claims (12)

A curable composition containing a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1) and a terpene resin (B).
-SiR ¹ _a X _3-a (1)
(In the formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom on the 1st to 3rd carbon atoms may be substituted with a heteroatom. X is a hydroxyl group or hydrolysis. And a represents a condition satisfying a condition of 0 or 1. When a plurality of Xs are present, they may be the same or different. The reactive silicon group equivalent of a polyoxyalkylene polymer (A) is 0.15 mmol / g or less, The curable composition of Claim 1 characterized by the above-mentioned. The terpene resin which is (B) component is a terpene phenol resin, The curable composition of Claim 1 or 2 characterized by the above-mentioned. 4. The curable composition according to claim 3, wherein the terpene phenol resin as the component (B) has a hydroxyl value of 1.4 mmol / g or more. The curable composition according to any one of claims 1 to 4, wherein the polyoxyalkylene polymer as the component (A) is a polyoxypropylene polymer. The curable composition according to claim 1, comprising a (meth) acrylic acid ester-based polymer (C) having reactive silicon represented by the general formula (1). object. The curable composition according to any one of claims 1 to 6, comprising a polyether plasticizer. The adhesive agent which contains the curable composition of any one of Claims 1-7 as a component. The non-contact-type adhesive agent which contains the curable composition of any one of Claims 1-7 as a component. The adhesive for asphalt roofing materials which contains the curable composition of any one of Claims 1-7 as a component. The adhesive for asphalt roofing materials using the modified asphalt which contains the curable composition of any one of Claims 1-7 as a component. The sealing agent which contains the curable composition of any one of Claims 1-7 as a component.