JP2017155225A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition good in storage stability and initial curability and providing a cured article having high tensile strength and excellent tensile physical property.SOLUTION: There is provided a curable composition containing an oxyalkylene polymer (A) having average 1.2 or more reactive silicon group represented by the general formula (1):-SiRX(1), where Rrepresents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms and X represents each independently a hydroxyl group or a hydrolyzable group in a molecule and a (meth)acrylic acid ester polymer (B) having total average 1.3 or more reactive silicon group represented by the general formula (2): -SiX(2), where X is same as above, in a molecule and the polymer (B) has one or more kind of compound unit selected from a compound having a mercapto group and the reactive silicon group of the general formula (2) and a compound unit having a polymerizable unsaturated group and a specific general formula (2).SELECTED DRAWING: None

Description

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

  It is known that an organic polymer having a reactive silicon group reacts with moisture or the like even at room temperature and is crosslinked by a siloxane condensation reaction of the reactive silicon group to obtain a rubber-like cured product. Among these organic polymers, polyoxyalkylene having a reactive silicon group has a relatively low viscosity, and therefore has excellent workability when used. In addition, a cured product obtained from a polyoxyalkylene having a reactive silicon group has a good balance of performance such as mechanical properties, weather resistance, and dynamic durability, so that the polymer is a sealing material, an adhesive, a paint, etc. (Patent Document 1).

  The curable composition containing the reactive silicon group-containing polymer can adjust workability and various physical properties by blending various components such as a filler and a plasticizer. In order to impart weather resistance and adhesion, it is useful to use a combination of a reactive silicon group-containing polyoxyalkylene and a reactive silicon group-containing poly (meth) acrylic ester (Patent Document 2). These are used as high weather resistant sealants and industrial adhesives.

  Patent Documents 3 and 4 disclose that a high-strength cured product can be obtained by a combination of a reactive silicon group-containing polyoxyalkylene and a poly (meth) acrylic acid ester having a trifunctional reactive silicon group. Yes.

  Further, Patent Document 5 discloses a poly (meth) acrylic acid ester having a dialkoxysilyl group and a trialkoxysilyl group.

JP-A-52-73998 JP 59-122541 A International Publication No. 2009/133811 International Publication No. 2014/192914 JP 2004-83606 A

  In order to give a cured product having a low viscosity and excellent tear strength and tensile strength, it is preferable to use a curable composition as disclosed in Patent Document 4. However, there was room for improvement in storage stability and initial curability. In view of such circumstances, an object of the present invention is to provide a curable composition having good storage stability and initial curability, low viscosity, and excellent tear strength and tensile strength.

As a result of intensive investigations to achieve the above object, the present inventors have completed the following invention. That is,
(1).
Formula (1): —SiR ¹ X ₂ (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group.)
An oxyalkylene polymer (A) having an average of 1.2 or more reactive silicon groups represented by
And general formula (1) and general formula (2):
-SiX ₃ (2)
(In formula, X represents a hydroxyl group or a hydrolysable group each independently.)
A curable composition containing a (meth) acrylic acid ester polymer (B) having an average of 1.3 or more total reactive silicon groups represented by ) As an essential ingredient,
A compound unit having a reactive silicon group represented by a mercapto group and general formula (2), a compound unit having a polymerizable unsaturated group and a reactive silicon group represented by general formula (2), and A curable composition having one or more compound units selected from the group consisting of two types of compound units:
A compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1),
A compound unit having a mercapto group and a reactive silicon group represented by the general formula (1),
(2). The curable composition according to (1), wherein the polymer (B) has the following three types of compound units:
A compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1),
A compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (2);
A compound unit having a mercapto group and a reactive silicon group represented by the general formula (2),
(3). The curable composition according to (1), wherein the polymer (B) has the following four types of compound units:
A compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1),
A compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (2);
A compound unit having a mercapto group and a reactive silicon group represented by the general formula (1),
A compound unit having a mercapto group and a reactive silicon group represented by the general formula (2),
(4). An oxyalkylene polymer (C1) and / or a (meth) acrylate polymer (C2) having an average of less than 1.2 reactive silicon groups represented by the general formula (1) in one molecule ) The curable composition according to any one of (1) to (3),
(5). The curable composition according to any one of (1) to (4), wherein the polymer (A) has an average of more than one reactive silicon group at one terminal site,
(6). The monomer constituting the polymer (B) has a glass transition temperature of 20 ° C. or higher of the homopolymer, and the monomer having no reactive silicon group is more than 50% by weight in all monomers. The curable composition according to any one of (1) to (5),
(7). The reactive silicon group equivalent represented by the general formula (2) of the polymer (B) is 0.15 mmol / g or more and 0.55 mmol / g or less, and the reaction represented by the mercapto group and the general formula (2) The curable composition according to any one of (1) to (6), wherein the amount of the compound having a functional silicon group is 0.15 mmol / g or more,
(8). The curable composition according to any one of (1) to (7), which contains titanium oxide as a filler,
(9). (1) to (8) a waterproofing coating film using the curable composition according to any one of
(10). (1) to a cured product obtained from the curable composition according to any one of (8),
About.

  The curable composition of the present invention provides a curable composition having good storage stability and initial curability, low viscosity, and excellent tear strength and tensile strength.

The present invention relates to a general formula (1): -SiR ¹ X ₂ (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group.)
An oxyalkylene polymer (A) having an average of 1.2 or more reactive silicon groups represented by
And general formula (1) and general formula (2):
-SiX ₃ (2)
(In formula, X represents a hydroxyl group or a hydrolysable group each independently.)
A curable composition containing a (meth) acrylic acid ester polymer (B) having an average of 1.3 or more total reactive silicon groups represented by ) As an essential ingredient,
A compound unit having a reactive silicon group represented by a mercapto group and general formula (2), a compound unit having a polymerizable unsaturated group and a reactive silicon group represented by general formula (2), and The present invention relates to a curable composition having one or more compound units selected from the group consisting of two types of compound units.
Compound unit having polymerizable unsaturated group and reactive silicon group represented by general formula (1) Compound unit having mercapto group and reactive silicon group represented by general formula (1) Curable composition of the present invention In the above, the polymer (A), the polymer (B) and other components described later may be used alone or in combination of two or more. Hereinafter, each component will be described in order.

  Here, the polymer having a compound unit means a polymer having a structural unit obtained by copolymerizing each compound.

<Polymer (A)>
The oxyalkylene polymer (A) has the following general formula (1):
-SiR ¹ X ₂ (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group (preferably a hydrolyzable group).)
It has the reactive silicon group represented by these.

R ¹ in the general formula (1) is, for example, an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; ') Triorganosiloxy group represented by ₃ (in the above formula, R' each independently represents an alkyl group (eg, a methyl group) or an aryl group (eg, a phenyl group)); a fluoromethyl group, Fluoroalkyl groups such as difluoromethyl groups; chloroalkyl groups such as chloromethyl groups and 1-chloroethyl groups; alkoxyalkyl groups such as methoxymethyl groups, ethoxymethyl groups, phenoxymethyl groups and 1-methoxyethyl groups; aminomethyl groups; Aminoalkyl groups such as N-methylaminomethyl group and N, N-dimethylaminomethyl group; acetoxymethyl group, methylcarbamate DOO group, 2-cyanoethyl group and the like. From the viewpoint of availability of raw materials, R ¹ is preferably a methyl group.

  Examples of the hydrolyzable group represented by X in the general formula (1) include known hydrolyzable groups. Here, the hydrolyzable group means a group that reacts and decomposes in the presence of water. Examples of the hydrolyzable group include hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, amino group, amide group, aminooxy group, mercapto group and the like. Among these, halogen, alkoxy group (eg, methoxy group, ethoxy group), alkenyloxy group (eg, isopropenyloxy group (also known as isopropenoxy group)) and acyloxy group are preferable because of high activity, and hydrolyzable. Is more preferable because it is gentle and easy to handle, and a methoxy group and an ethoxy group are particularly preferable. When the hydrolyzable group is an ethoxy group or an isopropenyloxy group, the compounds eliminated by the hydrolysis reaction are ethanol and acetone, respectively. Therefore, from the viewpoint of safety, an ethoxy group and an isopropenyloxy group are preferable as the hydrolyzable group.

  The reactive silicon group represented by the general formula (1) may be one type or two or more types. The reactive silicon group represented by the general formula (1) is preferably one kind, more preferably a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a (chloromethyl) dimethoxysilyl group, A (methoxymethyl) dimethoxysilyl group, a (methoxymethyl) diethoxysilyl group, or an (ethoxymethyl) dimethoxysilyl group, and a dimethoxymethylsilyl group is preferred because a cured product having high strength can be obtained.

  The oxyalkylene polymer (A) has a relatively low glass transition temperature, and the cured product obtained therefrom has excellent cold resistance. In addition, the oxyalkylene polymer (A) has high moisture permeability, and when the curable composition of the present invention is made into a one-component composition, it is excellent in deep-part curable and further excellent in adhesiveness of the cured product. It has the following characteristics.

  Examples of the main chain of the oxyalkylene polymer (A) (that is, a polyoxyalkylene moiety having no reactive silicon group) include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene. Examples thereof include an oxyethylene-polyoxypropylene copolymer and a polyoxypropylene-polyoxybutylene copolymer. The main chain of the oxyalkylene polymer (A) may be composed of only one structural unit or may be composed of two or more structural units. In particular, when the curable composition of the present invention is used in a sealant, an adhesive or the like, an oxypropylene component unit is contained in an amount of 50% by weight or more, preferably 80% by weight or more in all the structural units. It is desirable to use a propylene polymer (A). Such an oxypropylene polymer (A) is amorphous and has a relatively low viscosity.

  The polymer (A) may be linear or branched. Since a cured product having a high elongation is obtained, the polymer (A) is preferably linear. When the polymer (A) is branched, the number of the branched chains is preferably 1 to 4, more preferably 1.

  A polyoxyalkylene containing no reactive silicon group can be produced 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, propylene oxide is preferable because an amorphous and relatively low viscosity polyoxyalkylene can be obtained.

  Examples of the initiator include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, sorbitol and the like. Examples of alcohols include hydroxyl group-containing polyoxyalkylene having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.

  The method for synthesizing polyoxyalkylene containing no reactive silicon group is not particularly limited. For example, a polymerization method using an alkali catalyst such as KOH, and reacting an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623. Polymerization with a transition metal compound-porphyrin complex catalyst such as a complex obtained by the above, JP-B-46-27250, JP-B-59-15336, U.S. Pat. No. 3,278,457, U.S. Pat. No. 3,278,458, U.S. Pat. No. 3427256, U.S. Pat. No. 3,427,334, U.S. Pat. No. 3,427,335, a polymerization method using a double metal cyanide complex catalyst, a polymerization method using a catalyst comprising a polyphosphazene salt exemplified in JP-A-10-273512, and JP-A-11 -Phospha exemplified in 060722 Polymerization method using a catalyst comprising a down compounds. A polymerization method using a double metal cyanide complex catalyst (for example, a zinc hexacyanocobaltate glyme complex catalyst) is preferable because of a production cost and a polymer having a narrow molecular weight distribution.

  The method for introducing a reactive silicon group into polyoxyalkylene is not particularly limited, and a known method can be used. Examples of the method for introducing a reactive silicon group include the following methods (i) and (ii).

(I) Hydrosilylation A method in which an unsaturated bond is introduced into polyoxyalkylene (hereinafter also referred to as “precursor polymer”) as a raw material, and a hydrosilane compound is added to the unsaturated bond by a hydrosilylation reaction. There is no particular limitation on the method for introducing an unsaturated bond. For example, a precursor polymer having a functional group such as a hydroxyl group is reacted with a group that forms a bond by reacting with this functional group and a compound having an unsaturated bond, The method of obtaining the polymer containing an unsaturated bond; The method of polymerizing the monomer which has an unsaturated bond;

  Examples of the hydrosilane compound that can be used in the above method (i) include halogenated silanes such as dichloromethylsilane, dichlorophenylsilane, and (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, and (chloromethyl) dimethoxy. Examples thereof include alkoxysilanes such as silane and (methoxymethyl) dimethoxysilane; isopropenyloxysilanes such as (chloromethyl) diisopropenyloxysilane and (methoxymethyl) diisopropenyloxysilane.

(Ii) Reaction of a reactive group-containing polymer (precursor polymer) with a silane coupling agent A precursor polymer having a functional group such as a hydroxyl group, an amino group, or an unsaturated bond, reacts with the functional group to form a bond. Examples thereof include a method of reacting a compound (silane coupling agent) having both a group to be formed (hereinafter also referred to as “reactive group”) and a reactive silicon group. The combination of the functional group of the precursor polymer and the reactive group of the silane coupling agent includes hydroxyl group and isocyanate group, hydroxyl group and epoxy group, amino group and isocyanate group, amino group and thioisocyanate group, amino group and epoxy group, amino group Groups and α, β-unsaturated carbonyl groups (reaction by Michael addition), carboxy groups and epoxy groups, unsaturated bonds and mercapto groups, and the like.

  Examples of the silane coupling agent that can be used in the above method (ii) include mercaptosilanes such as 3-mercaptopropyldimethoxymethylsilane and mercaptomethyldimethoxymethylsilane that react with an unsaturated bond; Isocyanate silanes such as isocyanate propyl dimethoxymethyl silane and isocyanate methyl dimethoxymethyl silane; epoxy silanes such as 3-glycidoxypropyl dimethoxymethyl silane and glycidoxymethyl dimethoxymethyl silane that react with hydroxyl, amino or carboxy groups Class: 3-aminopropyldimethoxymethylsilane, 3- (2-aminoethyl) propyldimethoxymethylsilane, N-cyclohexylamino which reacts with isocyanate group or thioisocyanate group Methyl diethoxy methylsilane; hydroxyalkyl silanes such as 3-hydroxypropyl dimethoxymethylsilane and the like.

  The method (i) is advantageous in that the reaction is simple, the amount of reactive silicon groups introduced can be adjusted, and the physical properties of the resulting reactive silicon group-containing polymer (A) are stable. Have. The method (ii) has many reaction options and has the advantage that it is easy to increase the rate of introduction of reactive silicon groups. In addition, you may introduce | transduce a reactive silicon group into polyoxyalkylene by well-known methods other than said (i) and (ii).

The main chain of the polymer (A) is an ester bond or a general formula (3) as long as the effects of the present invention are not impaired.
—NR ² —C (═O) — (3)
(Wherein R ² represents an organic group having 1 to 10 carbon atoms or a hydrogen atom) and may contain an amide segment.

  A cured product obtained from the curable composition containing the polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonding or the like. However, the polymer (A) containing an amide segment or the like may be cleaved by heat or the like. Moreover, the curable composition containing the polymer (A) containing an amide segment or the like tends to have a high viscosity. In consideration of the above merits and demerits, polyoxyalkylene containing an amide segment or the like may be used as the polymer (A), or polyoxyalkylene containing no amide segment or the like may be used. .

  Examples of the amide segment represented by the general formula (3) include a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate, a reaction between an isocyanate group and an amino group, and a reaction between an isocyanate group and a mercapto group. Can be mentioned. Moreover, what is formed by reaction of the said amide segment containing an active hydrogen atom and an isocyanate group is also contained in the amide segment represented by General formula (3).

As a method for producing a polymer (A) containing an amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to obtain a polymer having an isocyanate group at the terminal. After the synthesis or simultaneously with the synthesis, the general formula (4):
_{^{Z-R 3 -SiR 1 X 2}} (4)
(Wherein R ¹ and X are the same as above. R ³ is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group or a carboxy group. , A mercapto group, a primary amino group, or a secondary amino group.) The Z group of the silicon compound represented by the above can be reacted with all or part of the isocyanate groups of the synthesized polymer.

  Although there is no limitation in particular in the silicon compound represented by General formula (4), For example, amino group containing silanes, such as (gamma) -aminopropyl dimethoxymethylsilane and N-((beta) -aminoethyl) -gamma-aminopropyl dimethoxymethylsilane A hydroxyl group-containing silane such as γ-hydroxypropyldimethoxymethylsilane; a mercapto group-containing silane such as γ-mercaptopropyldimethoxymethylsilane; 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 represented by the general formula (4).

Moreover, as a manufacturing method of the polymer (A) containing an amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at the terminal is represented by the general formula (5):
O = C = N—R ³ —SiR ¹ X ₂ (5)
(Wherein, R ³ , R ¹ and X are the same as described above), and a method of reacting the reactive silicon group-containing isocyanate compound.

  Although there is no limitation in particular in the reactive silicon group containing isocyanate compound represented by General formula (5), For example, (gamma) -methyldimethoxysilylpropyl isocyanate, (gamma) -methyldiethoxysilylpropyl isocyanate, (gamma)-(methoxymethyl) dimethoxysilyl Examples include propyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl) dimethoxysilylmethyl isocyanate, and the like.

  When the polymer (A) includes an amide segment, the number (average value) of amide segments per molecule of the polymer (A) is preferably 1 to 10, more preferably 1.5 to 5, and 2 to 3 Particularly preferred. When this number is less than 1, the curability may not be sufficient. Conversely, when it is greater than 10, the polymer (A) has a high viscosity and may be difficult to handle. In order to reduce the viscosity of the curable composition and improve workability, the polymer (A) preferably does not contain an amide segment.

  The polymer (A) is represented by the general formula (1), preferably 1.2 or more, more preferably 1.3 or more, and still more preferably 1.5 or more, on an average per molecule. Has a reactive silicon group. The upper limit of the number of reactive silicon groups (average value) in one molecule of the polymer (A) is preferably 6.0, more preferably 5.5, and even more preferably 5.0. When the number of reactive silicon groups is 1 or less, a high-strength cured product may not be obtained, and when the number of reactive silicon groups exceeds 6.0, a cured product with high elongation may not be obtained. is there.

In the present invention, the number of reactive silicon groups (average value) in one molecule of the polymer (A) is an average value obtained by measuring and calculating protons on carbon directly bonded with reactive silicon groups by high resolution ¹ H-NMR method. It is defined as In the measurement and calculation of the number of reactive silicon groups, when the reactive silicon group was introduced into the precursor polymer, the precursor polymer in which the reactive silicon group was not introduced and the reactive silicon group obtained by the side reaction were introduced. A polymer which is not present is regarded as a part of the polymer (A), and is included in the parameter (number of molecules of the polymer (A)) when calculating the number of reactive silicon groups (average value).

The polymer (A) may have an average of more than one reactive silicon group at one terminal site. As a method for producing a polymer (A) having an average of more than one reactive silicon group at one terminal site, for example,
(A) reacting a polyoxyalkylene having a hydroxyl group at the terminal (precursor polymer) with an epoxy compound having an unsaturated bond, introducing an unsaturated bond and a hydroxyl group at the terminal of the precursor polymer,
(B) A group that reacts with a hydroxyl group to form a bond (for example, a halogen atom) and a compound having an unsaturated bond are reacted with the resulting polymer to introduce a plurality of unsaturated bonds at the end of the polymer. ,
(C) A method in which a hydrosilane compound is added to a plurality of unsaturated bonds by a hydrosilylation reaction.

  Examples of the epoxy compound used in the reaction (a) include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, butadiene monoxide, 1,4-cyclopentadiene monoepoxide, and the like from the viewpoint of reactivity. Allyl glycidyl ether is preferred. In the present invention, “(meth) allyl” represents “allyl and / or methallyl”, and “(meth) acrylate” represents “acrylate and / or methacrylate”.

  The usage-amount of the epoxy compound in the said reaction (a) can be suitably set considering the introduction amount and reactivity of the unsaturated bond to the polyoxyalkylene (precursor polymer) which has a hydroxyl group at the terminal. The amount used is preferably 0.2 mol or more, more preferably 0.5 mol or more, preferably 5.0 mol or less, more preferably 2.0 mol per mol of hydroxyl group in polyoxyalkylene. It is below the mole.

  The reaction temperature in the reaction (a) is preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 110 ° C. or higher and 140 ° C. or lower. If the reaction temperature is low, the reaction hardly proceeds. If the reaction temperature is too high, the polyoxyalkylene main chain may be decomposed.

  Examples of the compound having an unsaturated bond and a group that reacts with a hydroxyl group to be used in the reaction (b) include 3-chloro-1-propene and 3-chloro-2-methyl-1-propene. Etc. The amount of the compound used in the reaction (b) is preferably 1.1 mol or more, more preferably 1.2 mol or more, and preferably 1.4 mol, relative to 1 mol of the hydroxyl group in the polymer. In the following, it is more preferably a mole or less.

  The terminal of the polymer obtained by the reaction (b) is represented by the general formula (6):

(In the formula, R ⁵ and R ⁷ are each independently a divalent organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom. R ⁶ and R ⁸ are each independently Or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10.

  Examples of the hydrosilane compound used in the reaction (c) include those exemplified by the method (i). The amount of the hydrosilane compound used in the reaction (c) is preferably 0.65 mol or more, more preferably 0.75 mol or more, preferably 1 mol or more per 1 mol of the unsaturated bond in the polymer. 1 mol or less, more preferably 1.2 mol or less.

  The average number of reactive silicon groups in the polymer (A) is preferably 0.5 or more, more preferably 1.0 or more, and 1.1 or more on one terminal site. More preferably, the number is 1.5 or more.

  The number average molecular weight of the polymer (A) is preferably 8,000 or more, more preferably 9,000 or more, still more preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 20,000 or more. Preferably, it is 50,000 or less, More preferably, it is 35,000 or less, More preferably, it is 30,000 or less. When the number average molecular weight of the polymer (A) is small, the viscosity is low, so that the workability when using the curable composition is improved, but the obtained cured product tends to be hard and the elongation tends to decrease. On the other hand, if the number average molecular weight of the polymer (A) is too large, the reactive silicon group concentration becomes too low, the curing rate may be slow, and the viscosity becomes too high, making handling difficult. Tend.

  The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A) is not particularly limited, but is preferably narrow, more preferably less than 2.0, and more preferably 1.6 or less, 1.5 or less is more preferable, 1.4 or less is particularly preferable, 1.3 or less is further particularly preferable, and 1.2 or less is most preferable.

  The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer (A) are values measured by GPC (polystyrene conversion), and the detailed measurement method is described in Synthesis Example 1 described later. The measurement methods for the number average molecular weight (Mn) of other components (polymer (B), high molecular weight plasticizer (C), etc.) are the same. If the number average molecular weight of the polymer (A) cannot be measured by GPC, titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method defined in JIS K 0070. Thus, the terminal group concentration (the sum of the hydroxyl value and iodine value) is directly measured, and the number average molecular weight of the polymer (A) is determined in consideration of the number of terminal branches in the structure of the polymer (A).

  The polymer (A) preferably has an average of 1.2 to 6.0 dimethoxymethylsilyl groups as reactive silicon groups in one molecule, and has a number average molecular weight of 10,000 to 50,000. A polyoxypropylene.

  More preferably, the polymer (A) has an average of 1.3 to 5.5 dimethoxymethylsilyl groups as reactive silicon groups in one molecule, and a number average molecular weight of 15,000 to 35,000. Is polyoxypropylene.

  More preferably, the polymer (A) has an average of 1.5 to 5.0 dimethoxymethylsilyl groups as reactive silicon groups in one molecule, and a number average molecular weight of 20,000 to 30,000. Is polyoxypropylene.

<Polymer (B)>
The (meth) acrylic acid ester polymer (B) has a total of 1.3 or more reactive silicon groups represented by the general formula (1) and the general formula (2) in one molecule. In the present invention, “(meth) acryl” means “acryl and / or methacryl”.

The (meth) acrylic acid ester polymer (A) has the following general formula (1):
-SiR ¹ X ₂ (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group (preferably a hydrolyzable group).)
And general formula (2): -SiX ₃ (2)
(In formula, X represents a hydroxyl group or a hydrolysable group each independently.)
It has the reactive silicon group represented by these.

  The description of the hydrolyzable group represented by the general formula (1) is the same as that in the polymer (A).

  The reactive silicon group represented by the general formula (2) may be one type or two or more types. The reactive silicon group represented by the general formula (2) is preferably one kind, more preferably a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, or a triacetoxysilyl group. A trimethoxysilyl group is preferred because a cured product having high strength can be obtained.

  The monomer constituting the (meth) acrylic acid ester polymer (B) includes (meth) acrylic acid ester (hereinafter also referred to as “monomer (b)”). That is, the polymer (B) includes a structural unit derived from the monomer (b) (hereinafter also referred to as “structural unit (b)”). In order to synthesize the polymer (B), only one type of monomer (b) may be used, or two or more types of monomers (b) may be used in combination.

  As the monomer (b), for example, 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, 2-Methylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate , Hexadecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate (Meth) acrylic acid alkyl such as methacrylic acid cyclohexyl; (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 3-methoxybutyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, ethylene oxide adduct of (meth) acrylic acid, 2,2,2-trifluoroethyl (meth) acrylic acid, 3,3,3-trifluoropropyl (meth) acrylic acid, (meth) acrylic acid 3,3,4,4,4-pentafluorobutyl, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, trifluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl (meth) acrylate 2-perfluoroethyl ethyl, 2-perfluorohexyl ethyl (meth) acrylate, 2-perfluorodecyl ethyl (meth) acrylate, 2-perfluorohexadecyl ethyl (meth) acrylate, (meth) acryl Examples include heteroatom-containing (meth) acrylic acid esters such as dimethylaminoethyl acid, chloroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and glycidyl (meth) acrylate.

  Further, in order to synthesize the polymer (B) within the range not impairing the effects of the present invention, other monomers that are copolymerizable with the monomer (b) may be used. Examples of other monomers include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, and styrene sulfonic acid; fluorine-containing vinyl such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Monomer; maleic acid, maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and other maleic acid and derivatives thereof; fumaric acid, fumaric acid monoalkyl ester, fumaric acid dialkyl ester and other fumaric acids and derivatives thereof; Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Body: Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Olefin monomers such as ethylene and propylene; Conjugated diene monomers such as butadiene and isoprene Body; (meth) acrylamide; (meth) acrylonitrile; vinyl monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, butyl vinyl ether. Other monomers may use only 1 type and may use 2 or more types together.

  In order to obtain a cured product having high tear strength, the monomer constituting the polymer (B) is a monomer having a homopolymer glass transition temperature of 20 ° C. or higher and having no reactive silicon group It is preferable to contain (b1) in an amount of 40% by weight or more, more preferably 50% by weight or more in all monomers. That is, the polymer (B1) has a homopolymer glass transition temperature of 20 ° C. or higher and a structural unit derived from the monomer (b1) having no reactive silicon group (hereinafter “structural unit (b1)”). It is preferable to contain 40 wt% or more of all structural units. The amount of monomer (b1) in all monomers (that is, the amount of structural unit (b1) in all structural units) is more preferably 50% by weight or more. The glass transition temperature of the homopolymer means the glass transition temperature of the homopolymer of the monomer (b1), and the numerical value is the homopolymer glass described in POLYMER HANDBOOK -FOURTH EDITION- (J. Brandrup et al.). Reference is made to the transition temperature. The monomer (b1) may be one type or two or more types.

  The upper limit of the amount of the monomer (b1) is not particularly limited, but the amount of the monomer (b1) in all monomers constituting the polymer (B) is preferably 90% by weight or less, more preferably Is 80% by weight or less.

Examples of the monomer (b1) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and the like.
The glass transition temperature of the homopolymer of the monomer (b1) is preferably 20 ° C to 250 ° C, more preferably 30 ° C to 200 ° C, and further preferably 50 ° C to 150 ° C.

  When it is desired to obtain a cured product having a low viscosity of the curable composition and a high tensile strength, the monomer constituting the polymer (B) has a homopolymer glass transition temperature of 80 ° C. or less and is reactive. It is preferable that the monomer (b2) having no silicon group is contained in an amount of 30% by weight or more based on the total monomers. That is, the polymer (B2) has a homopolymer glass transition temperature of 80 ° C. or lower and a structural unit derived from the monomer (b2) having no reactive silicon group (hereinafter “structural unit (b2)”). It is preferable to contain 30% by weight or more of all structural units. The amount of monomer (b2) in all monomers (that is, the amount of structural unit (b2) in all structural units) is more preferably 40% by weight or more, particularly preferably 50% by weight or more. is there.

  The upper limit of the amount of the monomer (b2) is not particularly limited, but the amount of the monomer (b2) in all the monomers constituting the polymer (B) is preferably 90% by weight or less, more preferably Is 80% by weight or less.

  As the monomer (b2), for example, methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Tridecyl, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate , Behenyl (meth) acrylate, (meth) (meth) acrylic acid alkyl cyclohexyl acrylate; 2-methoxyethyl (meth) acrylate, and (meth) acrylic acid 3-methoxybutyl.

  In order to reduce the viscosity of the curable composition, the glass transition temperature of the homopolymer of the monomer (b2) is preferably −100 ° C. to 80 ° C., more preferably −100 ° C. to 70 ° C., still more preferably. It is -70 degreeC-60 degreeC, Most preferably, it is -65 degreeC-50 degreeC. Further, it is more preferable to use alkyl (meth) acrylate having 2 to 6 carbon atoms as the monomer (b2). Here, the carbon number of alkyl in the alkyl (meth) acrylate means the carbon number of the alkyl group (R) of the alkoxycarbonyl group (RO-CO-).

  In addition, the monomer (henceforth "monomer (b1-b2)") whose glass transition temperature of a homopolymer is 20 to 80 degreeC is the above-mentioned monomer (b1) and monomer (b2). Included in both concepts. The amount of monomer (b1-b2) is included in both the amount of monomer (b1) and the amount of monomer (b2). In order to reduce the viscosity of the curable composition and improve the strength of the resulting cured product, the amount of the monomer (b1-b2) in all the monomers constituting the polymer (B) (ie, The amount of the structural unit derived from the monomer (b1-b2) in all the structural units of the polymer (B) is preferably 5 to 90% by weight, more preferably 10 to 80% by weight.

  From the viewpoint of compatibility with the polymer (A), the amount of the structural unit derived from the alkyl (meth) acrylate of the polymer (B) is preferably 50% by weight or more, more preferably 70% in all the structural units. % By weight or more, preferably 98% by weight or less, more preferably 95% by weight or less.

  In order to enhance the compatibility with the polymer (A), the monomer constituting the polymer (B) is an alkyl (meth) acrylate having 1 to 6 carbon atoms (hereinafter “monomer”). (B3) "), and alkyl (meth) acrylate (hereinafter referred to as" monomer (b4) ") having 7 to 30 carbon atoms. That is, the polymer (B) includes a structural unit derived from the monomer (b3) (hereinafter also referred to as “structural unit (b3)”) and a structural unit derived from the monomer (b4) (hereinafter “structural unit”). (B4) ”is also preferably contained. The total amount of the monomer (b3) and the monomer (b4) in all monomers constituting the polymer (B) (that is, the structural unit (b3) in all the structural units of the polymer (B) and The total amount of the structural unit (b4) is preferably 50 to 95% by weight, more preferably 60 to 90% by weight. Further, the weight ratio of the monomer (b3) to the monomer (b4) (monomer (b3) :( b4)), that is, the weight ratio of the structural unit (b3) to the structural unit (b4) (structural unit). (B3): The structural unit (b4)) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.

  The polymer (B) can be obtained by various polymerization methods, and the polymerization method is not particularly limited, but the radical polymerization method is preferable 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) peroxides; diacyl peroxides; Peroxydicarbonate, di-sec-butylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-1-methylheptylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, dicyclohexylperoxy Peroxydicarbonates such as dicarbonate; tert-butylperoxybenzoate, tert-butylperoxyacetate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxypi Peroxyesters such as valate, tert-butyldiperoxyadipate, cumylperoxyneodecanoate; keto such as methyl ethyl ketone peroxide, cyclohexanone peroxide Peroxides; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane; Examples thereof include hydroperoxides such as cumene hydroxy peroxide and tert-butyl hydroperoxide; peroxides such as 1,1-di (tert-hexylperoxy) -3,3,5-trimethylcyclohexane. 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. In addition, when a reactive silicon group is to be introduced into the molecular chain terminal of the (meth) acrylic polymer, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxy It is preferable to use a compound having a reactive silicon group and a mercapto group, such as silane, 3-mercaptopropylmethoxymethyldimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) trimethoxysilane. These may use only 1 type and may use 2 or more types together. When it is desired to obtain a cured product having excellent weather resistance, it is preferable not to use a mercapto group-containing compound during polymerization.

  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, etc. 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 Compound: Alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol, amyl alcohol and the like can be mentioned. Among these, one or more selected from dialkyl carbonate compounds and alcohol compounds are preferable from the viewpoints of odor and environmental burden. 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 Dimethyl carbonate, n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, tert-butanol from the point of being able to suppress the release of all volatile organic compounds from the composition Are more preferable, and 2-propanol and isobutanol are more preferable.

  In the synthesis of the polymer (B), it is possible to polymerize the monomer of the polymer (B) together with the polymer (A), its precursor compound, 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. Examples include a method for obtaining a coalescence.

  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. This is a polymerization method that can be introduced at almost any position of the polymer. 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-2003-500388, organic halides or 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 invention, so-called reverse atom transfer radical polymerization, that is, a normal atom transfer radical polymerization catalyst as shown in Macromolecules, 1999, Vol. 32, p. A general radical initiator such as a peroxide is allowed to act on Cu (II) when Cu (I) is used as a catalyst, resulting in an atom transfer radical as a result. Polymerization methods that produce an equilibrium state similar to polymerization are also included in the atom transfer radical polymerization method.

  As other polymerization methods, an acrylic polymer is prepared 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. Or a vinyl monomer as shown in JP-A-57-502171, JP-A-59-006207, JP-A-60-511992 using a stirred tank reactor It is also possible to use a high temperature continuous polymerization method in which continuous polymerization is performed.

In the method of introducing a reactive silicon group into a (meth) acrylic acid ester polymer, a compound having a mercapto group and a reactive silicon group represented by the general formula (2) is used as a chain transfer agent. For example, the following methods (I) to (IV) can be used.
(I) A method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group together with a (meth) acrylic acid ester. By this method, a reactive silicon group can be introduced into the side chain of the polymer.
(II) A method of copolymerizing a (meth) acrylic acid ester in the presence of the above-mentioned compound having a reactive silicon group and a mercapto group as a chain transfer agent. Groups represented by general formula (7) and general formula (8) can be introduced at the ends of the polymer.
_{^{-S-R 9 -SiR 1 1 X}} 2 (7)
-S-R ¹⁰ -SiX ₃ (8)
(In formula, X represents a hydroxyl group or a hydrolysable group each independently. R < ⁹ > and R < ¹⁰ >) represents a C1-C10 bivalent organic group. )
(III) Copolymerizing a compound having a polymerizable unsaturated bond and a reactive functional group (Z group) (for example, acrylic acid, 2-hydroxyethyl acrylate) together with a (meth) acrylic acid ester having no Z group And then reacting a compound having a functional group that reacts with the reactive silicon group and the Z group (for example, an isocyanate silane compound).
(IV) A method of introducing a reactive silicon group at the end of a molecular chain after polymerizing a (meth) acrylic acid ester by a living radical polymerization method.

  These methods may be used in any combination.

  It is preferable to use a combination of the above methods (I) and (II) because a reactive silicon group can be introduced into both the molecular chain terminal and the side chain. In addition, the method (IV) is preferable because a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained.

  In order to ensure the mechanical properties of the cured product and ensure the storage stability of the curable composition, it is preferable to introduce a reactive silicon group by combining the methods (I) and (II).

Examples of the compound having a reactive silicon group and a mercapto group represented by the general formula (1) include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyl (methoxymethyl) dimethoxysilane, and 3-mercaptopropyldiethoxymethyl. Examples include silane, mercaptomethyldimethoxymethylsilane, mercaptomethyl (methoxymethyl) dimethoxysilane, mercaptomethyldiethoxymethylsilane, and the like. The number of parts of the compound having the reactive silicon group and mercapto group represented by the general formula (1) is 100 weights of all monomer units of the polymer (B) (the chain transfer agent is not considered a monomer). 0.5 parts or more is preferable, 2.0 parts or more is more preferable, 20 parts or less is preferable, and 10 parts or less is more preferable.
Examples of the compound having a reactive silicon group and a mercapto group represented by the general formula (2) include 3-mercaptopropyltrimethoxysilane, mercaptomethyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and mercaptomethyltriethoxy. Examples include silane, 3-mercaptopropyltris (2-propenyloxy) silane, mercaptomethyltris (2-propenyloxy) silane, and the like. The number of parts of the compound having the reactive silicon group and mercapto group represented by the general formula (2) is 100 weights of all monomer units of the polymer (B) (the chain transfer agent is not considered a monomer). In the case of parts, 0.5 part or more is preferable, 3 parts or more is more preferable, 20 parts or less is preferable, and 10 parts or less is more preferable.

  Examples of the compound having a polymerizable unsaturated bond and a reactive silicon group represented by the general formula (1) include 3- (meth) acryloxypropyldimethoxymethylsilane and 3- (meth) acryloxypropyl (methoxymethyl). ) Dimethoxysilane, 3- (meth) acryloxypropyldiethoxymethylsilane, (meth) acryloxymethyldimethoxymethylsilane, (meth) acryloxymethyl (methoxymethyl) dimethoxysilane, (meth) acryloxymethyldiethoxymethylsilane And compounds having a (meth) acryloxy group and a reactive silicon group, such as a compound having a vinyl group and a reactive silicon group, such as vinyldimethoxymethylsilane and vinyldiethoxymethylsilane. These may be used alone or in combination of two or more. As the number of parts of the compound having a polymerizable unsaturated bond and the reactive silicon group represented by the general formula (1), all monomer units of the polymer (B) (the chain transfer agent is not considered a monomer) Is preferably 1 part or more, more preferably 3 parts or more, particularly preferably 5 parts or more, preferably 30 parts or less, more preferably 20 parts or less.

  Examples of the compound having a polymerizable unsaturated bond and a reactive silicon group represented by the general formula (2) include 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane. 3- (meth) acryloxypropyltris (2-propenyloxy) silane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, (meth) acryloxymethyltris (2-propenyloxy) ) A compound having a (meth) acryloxy group and a reactive silicon group such as silane; a compound having a vinyl group and a reactive silicon group such as vinyltrimethoxysilane and vinyltriethoxysilane. These may be used alone or in combination of two or more. As the number of parts of the compound having a polymerizable unsaturated bond and the reactive silicon group represented by the general formula (2), all monomer units of the polymer (B) (the chain transfer agent is not considered a monomer) Is preferably 1 part or more, more preferably 3 parts or more, particularly preferably 5 parts or more, preferably 30 parts or less, more preferably 20 parts or less.

  In order to obtain a cured product having high strength, the number of reactive silicon groups in one molecule of the polymer (B) is preferably 1.3 or more, more preferably 1.4 or more, even more preferably on average. Is 1.5 or more, preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.

  The number of reactive silicon groups represented by the general formula (1) and the general formula (2) in the side chain of the polymer (B) is preferably 0.3 or more, more preferably 0.00. It is 7 or more, more preferably 1.0 or more, preferably 8.0 or less, more preferably 6.0 or less, and still more preferably 5.0 or less.

  The number of reactive silicon groups represented by the general formula (1) and the general formula (2) at the terminal of the polymer (B) is preferably 0.3 or more, more preferably 0.5 on average. More preferably, it is 0.8 or more, preferably 3.0 or less, more preferably 2.0 or less, and still more preferably 1.0 or less.

  The average number of bifunctional reactive silicon groups is preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, preferably 6.0 or less, More preferably, it is 5.0 or less, and still more preferably 4.0 or less.

  The average number of trifunctional reactive silicon groups is preferably 0.4 or more, more preferably 0.6 or more, still more preferably 0.8 or more, and preferably 6.0 or less. More preferably, it is 5.0 or less, and further preferably 4.0 or less.

  The reactive silicon group equivalent of the polymer (B) is preferably 0.40 mmol / g or more, more preferably 0.45 mmol / g or more, further preferably 0.50 mmol / g or more, preferably 3.0 mmol / g. g or less, more preferably 2.5 mmol / g or less, still more preferably 2.0 mmol / g or less. Here, the reactive silicon group equivalent means the amount of reactive silicon group (mmol) contained per weight (g) of the polymer (B), and is based on the amount of the monomer having a reactive silicon group. Can be calculated.

  The bifunctional reactive silicon group equivalent is preferably 0.15 mmol / g or more, more preferably 0.30 mmol / g or more, still more preferably 0.40 mmol / g or more, preferably 2.0 mmol / g or less. More preferably, it is 1.5 mmol / g or less, More preferably, it is 1.0 mmol / g or less.

  The trifunctional reactive silicon group equivalent is preferably 0.15 mmol / g or more, more preferably 0.30 mmol / g or more, still more preferably 0.40 mmol / g or more, preferably 2.0 mmol / g or less. More preferably, it is 1.5 mmol / g or less, More preferably, it is 1.0 mmol / g or less, Most preferably, it is 0.55 mmol / g or less.

  In order to obtain a curable composition having excellent storage stability, the amount of the compound having a mercapto group and a reactive silicon group represented by the general formula (2) is preferably 0.15 mmol / g or more, more preferably Is 0.20 mmol / g or more.

  The molecular weight of the polymer (B) is not particularly limited. In order to obtain a cured product having higher strength, the polymer (B) preferably has a high molecular weight. When the polymer (B1) is used, its number average molecular weight is preferably 1,500 or more, more preferably 2,000 or more, further preferably 2,500 or more, preferably 50, in terms of polystyrene by GPC. 30,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less.

  When the polymer (B2) is used, its number average molecular weight is preferably 2,000 or more, more preferably 4,000 or more, further preferably 6,000 or more, preferably 100, in terms of polystyrene by GPC. 30,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

  The weight ratio of the polymer (A) and the polymer (B) is not particularly limited, but the polymer (A): polymer (B) is preferably 90: 10-30: 70, and 85:15 40:60 is more preferable, and 80:20 to 50:50 is even more preferable. Moreover, the total content of the polymer (A) and the polymer (B) in the curable composition is preferably 30 to 90% by weight, more preferably 50 to 80% by weight.

<High molecular weight plasticizer (C)>
The curable composition of the present invention may contain a high molecular weight plasticizer (C) having an average of 0 to 1.2 reactive silicon groups in one molecule. By adding the high molecular weight plasticizer (C), the viscosity of the curable composition and the elongation of the cured product can be adjusted.

  The curable composition of the present invention may contain a low molecular weight plasticizer in addition to the high molecular weight plasticizer (C). However, it is not preferable to use only a low molecular weight plasticizer as the plasticizer because the tensile physical properties of the cured product are significantly lowered. In the present invention, the high molecular weight plasticizer (C) means a plasticizer having a number average molecular weight of 500 or more, and the low molecular weight plasticizer means a plasticizer having a number average molecular weight of less than 500.

  The number average molecular weight of the high molecular weight plasticizer (C) is preferably not less than 500, more preferably not less than 1,000, still more preferably not less than 1,500, particularly preferably not less than 2,000, in terms of polystyrene by GPC. Preferably it is 15,000 or less, More preferably, it is 10,000 or less, More preferably, it is 8,000 or less. If the number average molecular weight is too low, the high molecular weight plasticizer (C) flows out of the cured product over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time. Moreover, when this number average molecular weight is too high, the viscosity of a curable composition will become high and workability | operativity will worsen.

  The molecular weight distribution (Mw / Mn) of the high molecular weight plasticizer (C) is not particularly limited, but is preferably narrow, more preferably less than 1.80, even more preferably 1.70 or less, and even more preferably 1.60 or less. 1.50 or less is even more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.

  Examples of the high molecular weight plasticizer (C) include polyoxyalkylenes; (meth) acrylic acid ester polymers; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; sebacic acid, Polyester obtained from dibasic acids such as adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; the hydroxyl group of polyether polyol is urethanized Polyether (for example, trade name: LBU-25 (manufactured by Sanyo Chemical Co., Ltd.)), polyether esterified with carboxylic acid, polyether ether-terminated; polystyrene, poly- - polystyrene, such as methyl styrene; polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, although polychloroprene, and the like, the present invention is not limited thereto.

  As the high molecular weight plasticizer (C), those compatible with the polymer (A) and the polymer (B) are preferable. From this point, the high molecular weight plasticizer (C) is preferably an oxyalkylene polymer or a (meth) acrylic acid ester polymer. The description of the oxyalkylene polymer and the (meth) acrylic acid ester polymer is the same as that described for the polymer (A) and the polymer (B).

  When the oxyalkylene polymer (C1) is used as the high molecular weight plasticizer (C), the surface curability and the deep curability are improved, and the curing delay after storage does not occur. Of the oxyalkylene polymers, polyoxypropylene is more preferable. It is preferable to use an oxyalkylene polymer that does not have a hydroxyl group at the terminal, because strength reduction due to the addition of a plasticizer can be suppressed.

  In view of compatibility, weather resistance, and heat resistance, it is preferable to use a (meth) acrylic acid ester polymer (C2) as the high molecular weight plasticizer (C). Among the (meth) acrylic acid ester polymers, poly (meth) acrylic acid alkyl is more preferable. The synthesis method of the (meth) acrylic acid ester polymer is preferably the living radical polymerization method and more preferably the atom transfer radical polymerization method because the molecular weight distribution is narrow and the viscosity can be lowered. Further, a method (so-called SGO process) in which alkyl (meth) acrylate described in JP-A-2001-207157 is continuously bulk polymerized at high temperature and high pressure is also preferable.

The high molecular weight plasticizer (C) may be a high molecular weight plasticizer (C1) having an average of more than 0 and no more than 1.2 reactive silicon groups per molecule, and has a reactive silicon group. High molecular weight plasticizer (C2), or a mixture thereof. As a reactive silicon group, the reactive silicon group represented by General formula (1) or General formula (2) can be mentioned, for example. The reactive silicon groups of the polymer (A) and the high molecular weight plasticizer (C) may be different, but are preferably the same because a cured product having good elongation can be obtained. That is, it preferably has a reactive group represented by the general formula (1).
When the high molecular weight plasticizer (C) has a reactive silicon group, the average number of reactive silicon groups in one molecule is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 0.8. 6 or more. If the number of reactive silicon groups is less than 0.3, there is a possibility that the effect of the reactive silicon groups, that is, increasing the strength of the cured product, cannot be obtained sufficiently. On the other hand, if the number of reactive silicon groups is larger than 1.2, a cured product having high elongation may not be obtained.

  The high molecular weight plasticizer (C) having a reactive silicon group is prepared by synthesizing a polymer exemplified by the polymer (A) and the polymer (B), a method for introducing a reactive silicon group, and other known methods. Can be manufactured by.

  The content of the high molecular weight plasticizer (C) is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). 20 to 100 parts by weight are particularly preferred. If this content is less than 5 parts by weight, the effect of the high molecular weight plasticizer (C) may not be sufficiently exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product may be insufficient.

  As the high molecular weight plasticizer (C), a high molecular weight plasticizer having a reactive silicon group and a high molecular weight plasticizer having no reactive silicon group may be used in combination. Since a cured product excellent in workability and mechanical properties can be obtained, it is preferable to use a high molecular weight plasticizer having a reactive silicon group and a high molecular weight plasticizer not having a reactive silicon group in combination.

<Titanium oxide (D)>
The curable composition of the present invention preferably contains titanium oxide as a reinforcing agent. Addition of titanium oxide can improve the tensile properties and tear strength of the cured product.

  As the titanium oxide used in the present invention, either a rutile type or an anatase type may be used, but it is preferable to use a rutile type since weather resistance is good. What was manufactured by well-known and usual manufacturing methods, such as a sulfuric acid method and a chlorination method, can be used.

  Titanium oxide is preferably surface-treated with an inorganic oxide such as silica, alumina or zirconia in order to suppress the photocatalytic activity and increase the dispersibility in the polymer (A) and the polymer (B). In particular, the surface treatment with alumina is preferable because the dispersibility in the polymer (A) and the polymer (B) increases. Surface treatment with silica is preferable because the weather resistance of the cured product is increased.

  The surface treatment rate of alumina is preferably 0.5% by weight or more, more preferably 2.0% by weight or more, and particularly preferably 3.0% by weight or more with respect to the titanium oxide particles.

  The surface treatment rate of silica is preferably 0.1% by weight or more, more preferably 2.0% by weight or more, and particularly preferably 3.0% by weight or more with respect to the titanium oxide particles.

  The surface treatment rate of zirconia is preferably 0.1% by weight or more, more preferably 2.0% by weight or more, and particularly preferably 3.0% by weight or more with respect to the titanium oxide particles.

  The surface treatment may be performed with a surface treatment agent other than the inorganic oxide. For example, various silicone oils such as methylhydrogenpolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, octadecyltri Various alkyl silanes such as methoxysilane, dimethyldimethoxysilane, octyltriethoxysilane, n-octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, trifluoromethylethyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane Various fluoroalkyl silanes such as vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc. Organic metal compounds of various metal coupling agents such as silane, titanium, aluminum, alumina-zirconia, and the like, fatty acids such as isostearic acid and stearic acid and their metal salts, and surface activity An organic compound such as an agent can also be used, and these can be used alone or in admixture of two or more.

  The average primary particle diameter of titanium oxide is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less. This average primary particle diameter is an average value of 100 particles, and is a value measured by an electron microscope. The average primary particle diameter is an arithmetic average value of the major axis and minor axis of the primary particle, and is also called a biaxial average diameter.

  The content of titanium oxide is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and particularly preferably 100 parts by weight or more with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). The amount is preferably 250 parts by weight or less, more preferably 200 parts by weight or less, and particularly preferably 150 parts by weight or less.

<Other ingredients>
Unless the effect of this invention is inhibited, the curable composition of this invention may contain components other than the above (other components). Hereinafter, other components will be described.

  The curable composition of the present invention may contain a low molecular weight plasticizer, a filler other than titanium oxide, an organic balloon, an inorganic balloon, a tackifier resin, an epoxy compound, an epoxy resin, a curing agent for epoxy resin, and the like. . These blending amounts are preferably from 5 to 150 parts by weight, more preferably from 10 to 120 parts by weight, particularly from 20 to 100 parts by weight, based on 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part is preferred.

  In addition, the curable composition of the present invention includes a solvent or diluent, a silane coupling agent, a reaction product of a silane coupling agent, a silicate, an anti-sagging agent, an antioxidant (anti-aging agent), a light stabilizer, and an ultraviolet absorber. Agent, flame retardant, curability modifier, radical inhibitor, metal deactivator, ozone degradation inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foaming agent, antifungal agent, dehydrating agent, physical property modifier , A photo-curing substance, an oxygen-curing substance, etc. can be blended. About 0.01-20 weight part is preferable with respect to 100 weight part of total content of a polymer (A) and a polymer (B), and, as for these compounding quantities, 0.5-10 weight part is more preferable.

In the curable composition of the present invention, a curing catalyst may be used for the purpose of curing the polymers (A) and (B). Specific examples of the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis ( Butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridecyl maleate), dibutyl tin bis (benzyl maleate), dibutyl tin diacetate, dibutyl tin dimethoxide, dibutyl tin bis Nonylphenoxide), dibutenyl tin oxide, dibutyltin oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (ethylacetoacetonate), reaction product of dibutyltin oxide and silicate compound, dibutyltin oxide and phthalate ester Dibutyltin compounds such as dioctyltin bis (triethoxysilicate), dioctyltin bis (ethyl maleate), dioctyltin bis (octylmaleate), dioctyltin dilaurate, dioctyltin diacetate, dioctyltin bis Dioctyltin compounds such as (acetylacetonate); Organic tin compounds such as dimethyltin diacetate and dimethyltin bis (acetylacetonate) (excluding dibutyltin compounds and dioctyltin compounds); Organic aluminum compounds such as mutris (acetylacetonate), aluminum tris (ethylacetoacetate), diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetrakis (acetylacetonate); 2-ethylhexanoic acid, octylic acid, neodecane Carboxylic acids such as acid, oleic acid and naphthenic acid; tin carboxylic acid such as tin bisneodecanoate, tin bis (2-ethylhexanoate), lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, carboxylic acid Carbohydrates such as barium, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, cerium carboxylate Metal acid salts; boron trifluoride complexes such as boron trifluoride, 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), and the like fluorine-anion-containing compounds such as ₂ SiF _6, but is not limited thereto. In these, since the hardened | cured material with high intensity | strength and elongation is obtained, a dibutyltin type compound, a dioctyl tin type compound, carboxylic acid tin, and carboxylic acid are preferable. Dioctyl tin compounds, tin carboxylates and carboxylic acids are more preferred because of their low toxicity.

  When a curing catalyst is used, its content is preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part by weight is more preferred. In recent years, there has been a movement to limit the amount of tin-based compounds used due to increasing environmental problems. Therefore, when using a tin-type compound, it is preferable that the content is less than 1 weight part.

    There is no limitation in particular in the manufacturing method of the curable composition of this invention. For example, the curable composition of the present invention is prepared by blending the above components and kneading them at room temperature or under heating using a mixer, roll, kneader, or the like, or by dissolving and mixing the above components in a small amount of solvent. Can be manufactured.

  The curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration damping material, a vibration damping material, a soundproof material, a foam material, a paint, and a spraying material. It can be used in coating waterproofing agents. The curable composition of the present invention has a low viscosity and is excellent in workability. Moreover, the hardened | cured material obtained from the curable composition of this invention has the characteristics that intensity | strength and elongation are high. Therefore, the curable composition of the present invention is preferably used in a sealing material, an adhesive or a waterproofing film, and more preferably used in a waterproofing film. Therefore, this invention also provides the coating-film waterproofing agent containing the above-mentioned curable composition.

  In addition, the curable composition of the present invention includes an electrical / electronic component material such as a solar cell back surface sealing material, an electrical insulating material such as an insulating coating material for electric wires and cables, an elastic adhesive, a contact adhesive, and a spray seal. Materials, crack repair materials, tile adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical equipment seal materials, food packaging materials, sealing materials for joints of exterior materials such as sizing boards , Coating materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and prevention of meshed glass and laminated glass end faces (cut parts) It can be used for various applications such as liquid sealants used in rust / waterproof sealing materials, automobile parts, electrical parts, various machine parts, and the like. Furthermore, since the curable composition of the present invention alone or the mixture of the curable composition of the present invention and a primer can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded product, The curable composition can also be used as various types of sealing 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. Adhesive, vehicle panel adhesive, electrical / electronic / precision equipment assembly adhesive, direct glazing sealant, multi-layer glass sealant, SSG method sealant, or building working joint sealant It can 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: Synthesis of polymer (A-1))
Polyoxypropylene diol having a number average molecular weight of about 2,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene diol having a number average molecular weight of about 28,500. It was. Subsequently, a methanol solution containing 1.0 equivalent of NaOMe is added to 1 equivalent of the hydroxyl group of the polyoxypropylene diol to distill off the methanol, followed by addition of 1.0 equivalent of allyl glycidyl ether. The reaction was carried out at 2 ° C. for 2 hours. Thereafter, a methanol solution containing 0.28 equivalents of sodium methoxide was added to remove the methanol, and then 1.79 equivalents of 3-chloro-1-propene was added to convert the terminal hydroxyl group into an allyl group. did. As described above, polyoxypropylene having an average of 2.1 carbon-carbon unsaturated bonds at one terminal site was obtained. Next, 36 parts by weight of platinum divinyldisiloxane complex (3% by weight of isopropanol solution in terms of platinum) is added to 100 parts by weight of the obtained polymer, and 1.9 parts by weight of dimethoxymethylsilane is slowly added while stirring. After dropping and reacting at 90 ° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure, whereby the end is a dimethoxymethylsilyl group and the number of reactive silicon groups per molecule is 3.2. A linear polyoxypropylene (polymer (A-1)) having a number average molecular weight of 28,500 was obtained.

  The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer (A-1) are Tosoh HLC-8120GPC as the liquid feeding system and Tosoh TSK-GEL as the column. This is a value measured using H type, THF as a solvent, and polystyrene as a standard. The same applies to Mn, Mw and Mw / Mn described later.

(Synthesis Example 2: Synthesis of Polymer (B-1))
48.6 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, 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 5.0 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 5.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3 -4.0 parts by weight of mercaptopropyldimethoxymethylsilane, 4.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) The mixed solution dissolved in 7 parts by weight was added dropwise over 5 hours. Polymerization was further carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.6 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,090 An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (B-1)) was obtained. Table 1 shows the monomer composition, molecular weight, number of reactive silicon groups, and the like.

(Synthesis Example 3: Synthesis of Polymer (B-2))
48.6 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, 59.8 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.2 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 5.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3 -4.0 parts by weight of mercaptopropyltrimethoxysilane, 4.5 parts by weight of n-dodecyl mercaptan, and 2.5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) 22.7 parts by weight of isobutanol The mixed solution dissolved in was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.6 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,150 An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (B-2)) was obtained.

(Synthesis Example 4: Synthesis of Polymer (B-3))
48.6 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, 59.4 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 4.7 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 10.9 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3 -4.0 parts by weight of mercaptopropyltrimethoxysilane, 4.5 parts by weight of n-dodecyl mercaptan, and 2.5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) 22.7 parts by weight of isobutanol The mixed solution dissolved in was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.6 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,100 An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (B-3)) was obtained.

(Synthesis Example 5: Synthesis of Polymer (B-4))
48.6 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, 63.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 5.0 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 7.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 3 -4.0 parts by weight of mercaptopropyldimethoxymethylsilane, 4.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) The mixed solution dissolved in 7 parts by weight was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.7 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,070 An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (B-4)) was obtained.

(Synthesis Example 6: Synthesis of Polymer (P-1))
48.6 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, 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 8.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2 , 2'-azobis (2-methylbutyronitrile) in a mixed solution of 2.5 parts by weight in 22.7 parts by weight of isobutanol was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) having an average of 1.8 trimethoxysilyl groups (reactive silicon groups) in one molecule and a number average molecular weight of 2,400. An isobutanol solution (solid content 60% by weight) of an acrylate ester (polymer (P-1)) was obtained.

(Synthesis Example 7: Synthesis of Polymer (P-2))
48.6 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, 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.3 parts by weight of 3-mercaptopropyldimethoxymethylsilane, and 2 , 2'-azobis (2-methylbutyronitrile) in a mixed solution of 2.5 parts by weight in 22.7 parts by weight of isobutanol was added dropwise over 5 hours. Polymerization was further carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.5 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,080 An acid ester (an isobutanol solution of polymer (P-2) (solid content: 60% by weight) was obtained.

(Synthesis Example 8: Synthesis of Polymer (P-3))
26.7 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer and heated to 105 ° C. in a nitrogen atmosphere. There, 30.0 parts by weight of methyl methacrylate, 41.0 parts by weight of n-butyl methacrylate, 15.0 parts by weight of stearyl methacrylate, 7.0 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxy A mixed solution in which 7.0 parts by weight of silane and 4.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) were dissolved in 43.1 parts by weight of isobutanol was dropped over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 2.8 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 4,960 An acid ester (an isobutanol solution of polymer (P-3) (solid content: 60% by weight) was obtained.

(Synthesis Example 9: Synthesis of Polymer (P-4))
48.6 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, 64.7 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.3 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 4.0 parts by weight of 3-mercaptopropyltrimethoxysilane, n- A mixed solution in which 4.0 parts by weight of dodecyl mercaptan and 2.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) were dissolved in 22.7 parts by weight of isobutanol was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.3 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 2,270. An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (P-4)) was obtained.

(Synthesis Example 10: Synthesis of Polymer (P-5))
48.6 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, 64.7 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.3 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 4.0 parts by weight of 3-mercaptopropyldimethoxymethylsilane, 3- A mixed solution prepared by dissolving 4.0 parts by weight of mercaptopropyltrimethoxysilane and 2.5 parts by weight of 2,2′-azobis (2-methylbutyronitrile) in 22.7 parts by weight of isobutanol was dropped over 5 hours. did. Further, polymerization is carried out at 105 ° C. for 2 hours, and poly (meth) acryl having an average of 1.4 dimethoxymethylsilyl groups / trimethoxysilyl groups in one molecule and a number average molecular weight of 1,780. An isobutanol solution (solid content: 60% by weight) of acid ester (polymer (P-5)) was obtained.

(Synthesis Example 11: Synthesis of Polymer (C-1))
Propylene oxide was polymerized using butanol as an initiator and a zinc hexacyanocobaltate glyme complex catalyst to obtain a polyoxypropylene oxide having a number average molecular weight of 7,000. Subsequently, a 1.2-fold equivalent NaOMe methanol solution was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene oxide to distill off the methanol, and further 3-chloro-1-propene was added to remove the terminal hydroxyl group. Converted to an allyl group. Next, 1.97 parts by weight of dimethoxymethylsilane was added to 36 parts by weight of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and stirred with respect to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene polymer. Was slowly added dropwise. By reacting the mixed solution at 90 ° C. for 2 hours, a linear reaction in which the terminal is a dimethoxymethylsilyl group, the average number of silicon groups per molecule is 0.8, and the number average molecular weight is 7,000. Silicon group-containing polyoxypropylene (polymer C-1) was obtained.

Example 1
60.0 parts by weight of the polymer (A-1) obtained in Synthesis Example 1 and 66.7 parts by weight of the isobutanol solution of the polymer (B-1) obtained in Synthesis Example 2 were mixed to obtain isobutanol. Was distilled off under reduced pressure to obtain a polymer mixture in which the weight ratio of polymer (A-1) / polymer (B-1) was 60/40. 50 parts by weight of the high molecular weight plasticizer (C-1) obtained in Synthesis Example 4 and titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Taipei R-820) 120 with respect to 100 parts by weight of the polymer mixture. Parts by weight, antioxidant (BASF, trade name: Irganox 245), 3 parts by weight, UV absorber (Sumitomo Chemical Co., trade name: Sumisorb 400), 1 part by weight, hindered amine light stabilizer (HALS) (( After 1 part by weight of ADEKA (trade name: ADK STAB LA-63P) was mixed and sufficiently kneaded, the mixture was passed through 3 paint rolls 3 times to disperse each component. Thereafter, dehydration under reduced pressure is performed at 120 ° C. for 2 hours, and the dehydrated mixture is cooled to 50 ° C. or less. 1 part by weight of FA-600), 7 parts by weight of vinyltrimethoxysilane (manufactured by Momentive Co., Ltd., trade name: A-171) as a dehydrating agent, and N- (2-aminoethyl) -3-amino as an adhesion-imparting agent 5 parts by weight of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603) and 1 part by weight of dioctyltin dilaurate (manufactured by Nitto Kasei Co., Ltd., trade name: Neostan U-810) are added as a catalyst. After kneading in a substantially moisture-free state, the resulting composition was filled in a moisture-proof cartridge-type container and sealed to obtain a one-component curable composition.

(viscosity)
The viscosity of the curable composition was measured at 23 ° C. and a relative humidity of 50% using a BH viscometer (manufactured by Toki Sangyo Co., Ltd.) when the rotor rotation speed was 2 rpm or 20 rpm. Further, the cartridge container was cured at 50 ° C. for 4 weeks as the viscosity after storage, and the viscosity was measured in the same manner. The results are shown in Table 2.

(Tensile properties)
The curable composition was filled in a polyethylene mold having a thickness of 2 mm so as not to contain air bubbles, and cured at 23 ° C. and a relative humidity of 50% for 1 day to obtain a cured product. Further, a cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the obtained cured product, a No. 3 dumbbell was punched in accordance with JIS K 6251, a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed, and a modulus at 50% elongation (M50), The strength at break (TB) and the elongation at break (EB) were measured. The results are shown in Table 2.

(Tear strength)
The curable composition was filled in a polyethylene mold having a thickness of 3 mm so as not to contain bubbles, and cured at 23 ° C. and a relative humidity of 50% for 3 days, and further at 50 ° C. for 4 days to obtain a cured product. In accordance with JIS K 6252, the obtained cured product was punched into a non-cut angle type test piece and a trouser type test piece, the non-cut angle type test piece was pulled at a pulling speed of 500 mm / min, and the trouser type test piece was pulled. The tear strength was measured at a speed of 100 mm / min. The results are shown in Table 2.

(Example 2-7, Comparative Example 1-3)
Polymer (A-1), polymer (B-1, B-2, B-3, B-4, B-5, B-6), polymer (P-1, P) in the amounts shown in Table 2. -2, P-3), high molecular weight plasticizer (C-1), titanium oxide, antioxidant, ultraviolet absorber, hindered amine light stabilizer (HALS), antifoaming agent, dehydrating agent, adhesion promoter, A curable composition was prepared by mixing the catalyst and evaluated in the same manner as in Example 1. The results are shown in the table below.

  As shown in Table 2, it can be seen that the curable composition using the polymer (A) and the polymer (B) has a low viscosity and a cured product having excellent tensile strength and tear strength can be obtained. Usually, when a (meth) acrylic acid ester-based polymer having a trifunctional reactive silicon group is used, curing is accelerated and excellent tensile physical properties are exhibited even at the initial stage of curing. However, it can be seen that the cured product after 1 day of the composition using the polymer (A-1) / (P-1) shown in Comparative Example 1 of the present application is fragile and the storage stability of the composition is poor. However, when the polymer (B) having a bifunctional reactive silicon group and a trifunctional reactive silicon group of the present invention is used, it is considered that the curability is usually slower, but the curability is higher than that of the comparative example. You can see that it is getting faster. Furthermore, it turns out that the storage stability is also good.

Claims (10)

Formula (1): —SiR ¹ X ₂ (1)
(In the formula, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X independently represents a hydroxyl group or a hydrolyzable group.)
An oxyalkylene polymer (A) having an average of 1.2 or more reactive silicon groups represented by
And general formula (1) and general formula (2):
-SiX ₃ (2)
(In formula, X represents a hydroxyl group or a hydrolysable group each independently.)
A curable composition containing a (meth) acrylic acid ester polymer (B) having an average of 1.3 or more total reactive silicon groups represented by ) As an essential ingredient,
A compound unit having a reactive silicon group represented by a mercapto group and general formula (2), a compound unit having a polymerizable unsaturated group and a reactive silicon group represented by general formula (2), and A curable composition having one or more compound units selected from the group consisting of two types of compound units.
Compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1) Mercapto group and a compound unit having a reactive silicon group represented by the general formula (1) The curable composition of Claim 1 in which a polymer (B) has the following three types of compound units.
Compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1) Polymerizable unsaturated group, a compound unit having a reactive silicon group represented by the general formula (2) and a mercapto group Compound unit having reactive silicon group represented by formula (2) The curable composition of Claim 1 in which a polymer (B) has the following four types of compound units.
Compound unit having a polymerizable unsaturated group and a reactive silicon group represented by the general formula (1) Polymerizable unsaturated group, a compound unit having a reactive silicon group represented by the general formula (2) and a mercapto group Compound unit having a reactive silicon group represented by the formula (1) and a compound unit having a reactive silicon group represented by the general formula (2) An oxyalkylene polymer (C1) and / or a (meth) acrylate polymer (C2) having an average of less than 1.2 reactive silicon groups represented by the general formula (1) in one molecule The curable composition of any one of Claims 1-3 containing. The curable composition according to any one of claims 1 to 4, wherein the polymer (A) has an average of more than one reactive silicon group at one terminal site. The monomer constituting the polymer (B) has a glass transition temperature of 20 ° C. or higher of the homopolymer, and the monomer having no reactive silicon group is more than 50% by weight in all monomers. The curable composition of any one of Claims 1-5 to contain. The reactive silicon group equivalent represented by the general formula (2) of the polymer (B) is 0.15 mmol / g or more and 0.55 mmol / g or less, and the reaction represented by the mercapto group and the general formula (2) The curable composition according to any one of claims 1 to 6, wherein the addition amount of the compound having a functional silicon group is 0.15 mmol / g or more. The curable composition according to any one of claims 1 to 7, which contains titanium oxide as a filler. A waterproofing coating film using the curable composition according to any one of claims 1 to 8. Hardened | cured material obtained from the curable composition of any one of Claims 1-8.