JP2023010631A - Multiple liquid type curable composition - Google Patents

Abstract

To provide a multiple liquid type curable composition which contains an agent A containing a reactive silicon group-containing polymer and an agent B containing an epoxy resin, exhibits good miscibility of the agent A and the agent B, and can maintain the shape when mixed and coated.SOLUTION: An agent A contains a polyoxyalkylene-based polymer (A) having a reactive silicon group and/or a (meth)acrylate-based polymer (B), and a silanol condensation catalyst (E). An agent B contains an epoxy resin (C) and water (F). The agent A has a second viscosity ratio [viscosity at shear rate of 5×10-3(1/sec)/viscosity at shear rate of 0.1(1/sec) measured using rheometer] of 300 or more. The agent B has a second viscosity ratio [viscosity at shear rate of 5×10-3(1/sec)/viscosity at shear rate of 0.1(1/sec) measured using rheometer] of 300 or more.SELECTED DRAWING: None

Description

The present invention relates to a multi-component curable composition and a cured product obtained by curing the composition.

In order to reduce the weight of automobiles, aircraft, and railways, the use of lightweight materials other than steel, such as aluminum, magnesium, and carbon fiber composite materials, is progressing as structural members. It is increasing. Since it is sometimes difficult to join dissimilar materials by spot welding or laser welding, adhesive joining using an adhesive is attracting attention. Since steel plates, aluminum alloys, and fiber-reinforced composite materials have different linear expansion coefficients, the adhesive is required to have flexibility to follow thermal strain. For this reason, epoxy resins, which are highly rigid, may be disadvantageous, so materials with high elastic modulus and flexibility are needed as new structural adhesives.

As a curable composition that can be used as a structural adhesive and gives a cured product having high strength, high rigidity and flexibility, for example, Patent Document 1 discloses Agent A containing a polyoxyalkylene polymer having a reactive silicon group. and a multicomponent curable composition comprising a B agent containing an epoxy resin and a silanol condensation catalyst.
The same document discloses that by further blending water into the B agent containing an epoxy resin and a silanol condensation catalyst, the curing of the A agent and the B agent when mixed is promoted (paragraph [0090] and Table 2).

Further, Patent Document 2 describes a two-liquid type resin composition composed of a main agent containing an epoxy resin and water, and a curing agent containing a modified silicone resin and a modified silicone resin catalyst (silanol condensation catalyst). It is

WO2019/069866 JP-A-63-273625

In the structure disclosed in Patent Document 1, since the silanol condensation catalyst and water are blended in the same agent, the silanol condensation catalyst is hydrolyzed by water during storage, which may affect the development of initial strength. be.

In contrast, in the configuration disclosed in Patent Document 2, the silanol condensation catalyst and water are blended in different agents, so hydrolysis of the silanol condensation catalyst by water can be avoided.
However, in this configuration, when the agent containing the reactive silicon group-containing polymer and the agent containing the epoxy resin are mixed, it is difficult to mix uniformly, and the shape cannot be maintained when mixed and applied. This problem is particularly conspicuous in a method of use in which the A and B agents are mixed in a mixing device to form a mixture, and the mixture is immediately discharged from the device and directly applied to an object.

In view of the above-mentioned current situation, the present invention includes an A agent containing a reactive silicon group-containing polymer and a B agent containing an epoxy resin, and the A agent and the B agent exhibit good miscibility and are mixed and applied. An object of the present invention is to provide a multicomponent curable composition that can maintain its shape at times.

As a result of intensive studies by the present inventors in order to solve the above problems, a polyoxyalkylene polymer (A) having a reactive silicon group / or a (meth) acrylic acid ester polymer having a reactive silicon group A silanol condensation catalyst (E) is blended with A agent containing (B), water (F) is blended with B agent containing epoxy resin (C), and each of A agent and B agent has a specific viscosity. The inventors have found that the above problems can be solved by adjusting the characteristics so as to satisfy them, and completed the present invention.

That is, the present invention provides a multi-component curable composition containing agent A and agent B, wherein agent A contains a polyoxyalkylene polymer (A) having a reactive silicon group and/or a reactive silicon group. (Meth)acrylic acid ester polymer (B) having, and silanol condensation catalyst (E), B agent contains epoxy resin (C) and water (F), A agent contains The second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] is 300 or more, and agent B The second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] is 300 or more. It relates to a multi-component curable composition.

According to the present invention, a component A containing a reactive silicon group-containing polymer and a component B containing an epoxy resin are included, and the component A and the component B exhibit good mixability and form when mixed and applied. A sustainable multi-part curable composition can be provided. In the multi-component curable composition, hydrolysis of the silanol condensation catalyst by the water contained therein can be avoided, and good initial strength can be developed after mixing the A component and the B component.
According to a preferred embodiment of the present invention, after the mixture of agent A and agent B is applied to a substrate, the property of maintaining the shape at the time of application can be improved.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to these embodiments.

This embodiment is a multi-component curable composition containing at least agent A and agent B.
Agent A includes at least a polyoxyalkylene polymer (A) having a reactive silicon group and/or a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a silanol condensation catalyst (E ), and the second viscosity ratio [viscosity at a shear rate of 5×10 ⁻³ (1/sec)/viscosity at a shear rate of 0.1 (1/sec) measured using a rheometer] is 300 or more.
Agent B contains at least epoxy resin (C) and water (F), and has a second viscosity ratio of 300 or more.

<<Polyoxyalkylene polymer (A) having a reactive silicon group>>
Agent A preferably contains a polyoxyalkylene polymer (A) having a reactive silicon group.
<Reactive silicon group>
The polyoxyalkylene polymer (A) has reactive silicon groups. The reactive silicon group means a silicon group having a hydroxyl group or a hydrolyzable group on the silicon atom and capable of forming a siloxane bond by hydrolysis/condensation reaction. Specifically, it is represented by the following general formula (1).
—SiR ⁵ _3-a X _a (1)
(Wherein, R ⁵ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a is 1, 2 or 3.)

The number of carbon atoms in the hydrocarbon group of R ⁵ is preferably 1-10, more preferably 1-5, even more preferably 1-3. Specific examples of R ⁵ include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group. Preferred are methyl group, ethyl group, chloromethyl group and methoxymethyl group, and more preferred are methyl group and methoxymethyl group. When multiple R ⁵ are present, they may be the same or different.

X includes, for example, hydroxyl group, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group. Among these, alkoxy groups such as methoxy and ethoxy groups are more preferred, and methoxy and ethoxy groups are particularly preferred, since they are moderately hydrolyzable and easy to handle. When there are multiple X's, they may be the same or different.

Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and dimethoxymethyl silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N ,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto. Among these are methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- A diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties. A methyldimethoxysilyl group is preferred because it is excellent in shape retention after application. A trimethoxysilyl group is preferred because it exhibits good initial strength and provides a highly rigid cured product.

The polyoxyalkylene polymer (A) may have an average of 1 or less reactive silicon groups at one terminal site, or an average of more than 1 reactive silicon group at one terminal site may have a silicon group.
Having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) has two or more reactive silicon groups at one terminal site Polyoxyalkylene indicates that it contains That is, the polyoxyalkylene-based polymer (A) may contain only a polyoxyalkylene having two or more reactive silicon groups at one terminal site, or two or more at one terminal site. and polyoxyalkylenes having one reactive silicon group at one terminal site. In addition, the plurality of terminal sites possessed by one molecule of polyoxyalkylene may include both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group. Furthermore, the polyoxyalkylene polymer (A) as a whole has an average of more than one reactive silicon group at one terminal site, but a poly having a terminal site having no reactive silicon group It may contain oxyalkylene.

A terminal site having two or more reactive silicon groups can be represented, for example, by the following general formula (2).

(In the formula, R ¹ and R ³ each independently represent a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R ¹ and R ³ are carbon, oxygen, nitrogen Each of R ² and R ⁴ independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ , X, and a represent the above formula (1) is as described above.)

R ¹ and R ³ may be a divalent organic group having 1 to 6 carbon atoms, or may be a hydrocarbon group which may contain an oxygen atom. The number of carbon atoms in the hydrocarbon group is preferably 1-4, more preferably 1-3, even more preferably 1-2. Specific examples of R ¹ include -CH ₂ OCH ₂ -, -CH ₂ O- and -CH ₂ -, but -CH ₂ OCH ₂ - is preferred. Specific examples of R ³ include -CH ₂ - and -CH ₂ CH ₂ -, preferably -CH ₂ -.

The number of carbon atoms in the hydrocarbon groups of R ² and R ⁴ is preferably 1-5, more preferably 1-3, even more preferably 1-2. Specific examples of R ² and R ⁴ include a hydrogen atom, a methyl group and an ethyl group, preferably a hydrogen atom and a methyl group, more preferably a hydrogen atom.

According to a particularly preferred embodiment, the terminal portion represented by the general formula (2) is such that R ¹ is —CH ₂ OCH ₂ —, R ³ is —CH ₂ —, and R ² and R ⁴ are each hydrogen atoms. is. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2. However, n is not limited to one value, and may be a mixture of multiple values.

The polyoxyalkylene polymer (A) may have an average of 1.0 or less reactive silicon groups at one terminal site, but a reactive silicon group at one terminal site. It is preferable to have more than 1.0 on average. The average number is more preferably 1.1 or more, still more preferably 1.5 or more, and even more preferably 2.0 or more. Also, the number is preferably 5 or less, more preferably 3 or less.

The number of terminal sites having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A) is preferably 0.5 or more on average, and 1.0 It is more preferably 1 or more, still more preferably 1.1 or more, and even more preferably 1.5 or more. Also, the number is preferably 4 or less, more preferably 3 or less.

The polyoxyalkylene polymer (A) may have reactive silicon groups in addition to the terminal sites, but having them only in the terminal sites yields a rubber-like cured product with high elongation and low elastic modulus. It is preferable because it becomes easy to be

The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, from the viewpoint of the strength of the cured product. , is more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. From the viewpoint of elongation of the cured product, the number is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.

<Main chain structure>
The main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and examples include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, Examples include polyoxypropylene-polyoxybutylene copolymers. Among them, polyoxypropylene is preferred.

The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, in terms of polystyrene equivalent molecular weight in GPC, and particularly preferably It is 3,000 or more and 30,000 or less. If the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may be disadvantageous in terms of production costs. tends to be inconvenient.

As the molecular weight of the polyoxyalkylene polymer (A), the organic polymer precursor before the introduction of the reactive silicon group was subjected to the hydroxyl value measurement method of JIS K 1557 and the iodine value specified in JIS K 0070. Directly measure the terminal group concentration by titration analysis based on the principle of the measurement method, and indicate the terminal group equivalent molecular weight obtained by considering the structure of the organic polymer (degree of branching determined by the polymerization initiator used). can also The terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A) is obtained by preparing a calibration curve of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the above-mentioned terminal-group-equivalent molecular weight. It is also possible to convert the number-average molecular weight of the polymer (A) obtained by GPC into a terminal group-equivalent molecular weight.

Although the molecular weight distribution (Mw/Mn) of the polyoxyalkylene polymer (A) is not particularly limited, it is preferably narrow, specifically less than 2.0, more preferably 1.6 or less. 5 or less is more preferable, and 1.4 or less is particularly preferable. Moreover, from the viewpoint of improving various mechanical properties such as improving the durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and weight average molecular weight obtained by GPC measurement.

Moreover, the main chain structure of the polyoxyalkylene polymer (A) may be linear or branched.

<Method for synthesizing polyoxyalkylene polymer (A)>
Next, a method for synthesizing the polyoxyalkylene polymer (A) will be described.
As an example of the synthesis method, the polyoxyalkylene polymer (A) is prepared by introducing a carbon-carbon unsaturated bond to the hydroxyl group terminal of the hydroxyl-terminated polymer obtained by polymerization, and then reacting with the carbon-carbon unsaturated bond. It can be obtained by reacting a reactive silicon group-containing compound.
The polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site, which is a preferred embodiment, is a hydroxyl group-terminated polymer obtained by polymerization. On the other hand, after introducing two or more carbon-carbon unsaturated bonds to one hydroxyl group end, it is preferable to react with a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bonds. These synthesizing methods are described below.

(polymerization)
The polyoxyalkylene polymer (A) is preferably produced by polymerizing an epoxy compound with an initiator having a hydroxyl group using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex.

Examples of initiators having a hydroxyl group include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polyoxypropylene monoallyl ether, polyoxypropylene monoalkyl ether, and the like. Examples include those having one or more hydroxyl groups.

Examples of epoxy compounds include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.

(Introduction of carbon-carbon unsaturated bond)
As a method for introducing a carbon-carbon unsaturated bond, a method of reacting a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond after reacting a hydroxyl group-terminated polymer with an alkali metal salt is preferred.
In addition, as a method for introducing two or more carbon-carbon unsaturated bonds to one terminal, an epoxy compound having a carbon-carbon unsaturated bond is first reacted with a hydroxyl group-terminated polymer after reacting with an alkali metal salt. A method of reacting and then reacting a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferred.
By using these methods, it is possible to efficiently and stably introduce reactive groups while controlling the molecular weight and molecular weight distribution of the polymer main chain by the polymerization conditions.

As the alkali metal salt, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferred, and sodium methoxide and potassium methoxide are more preferred. Sodium methoxide is particularly preferred because of its availability.

The temperature at which the alkali metal salt is allowed to act is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. or lower. The time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

As an epoxy compound having a carbon-carbon unsaturated bond, especially general formula (3):

(R ¹ and R ² in the formula are the same as above) can be preferably used. Specifically, allyl glycidyl ether, methallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferred from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferred.

The amount of the epoxy compound having a carbon-carbon unsaturated bond to be added can be any amount in consideration of the amount of carbon-carbon unsaturated bond introduced into the polymer and the reactivity. In particular, the molar ratio of the hydroxyl group-terminated polymer to the hydroxyl group is preferably 0.2 or more, more preferably 0.5 or more. Also, it is preferably 5.0 or less, more preferably 2.0 or less.

The reaction temperature for the ring-opening addition reaction of an epoxy compound having a carbon-carbon unsaturated bond with a polymer containing a hydroxyl group is preferably 60° C. or higher and 150° C. or lower, preferably 110° C. or higher, It is more preferably 140° C. or less.

Examples of halogenated hydrocarbon compounds having a carbon-carbon unsaturated bond include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and methallyl iodide. Allyl chloride and methallyl chloride are more preferable because of ease of handling.

The addition amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is not particularly limited, but the molar ratio to the hydroxyl group of the hydroxyl-terminated polymer is preferably 0.7 or more, more preferably 1.0 or more. . Moreover, 5.0 or less is preferable and 2.0 or less is more preferable.

The temperature at which the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferably 50° C. or higher and 150° C. or lower, more preferably 110° C. or higher and 140° C. or lower. The reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

(Introduction of reactive silicon group)
A method for introducing a reactive silicon group is not particularly limited, and a known method can be used. The introduction method is exemplified below.
(i) A method of adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.
(ii) a polymer having a carbon-carbon unsaturated bond and a compound having both a group capable of reacting with the carbon-carbon unsaturated bond to form a bond and a reactive silicon group (also called a silane coupling agent); How to react. A group capable of forming a bond by reacting with a carbon-carbon unsaturated bond includes, but is not limited to, a mercapto group.
(iii) A method of reacting a reactive group-containing polymer with a silane coupling agent. Combinations of the reactive groups of the reactive group-containing polymer and the silane coupling agent include hydroxyl groups and isocyanate groups, hydroxyl groups and epoxy groups, amino groups and isocyanate groups, amino groups and thioisocyanate groups, amino groups and epoxy groups, amino group and α,β-unsaturated carbonyl group (reaction by Michael addition), carboxy group and epoxy group, unsaturated bond and mercapto group, etc., but not limited to these.

Method (i) is preferable because the reaction is simple, the amount of reactive silicon groups to be introduced can be adjusted, and the physical properties of the resulting reactive silicon group-containing polyoxyalkylene polymer (A) are stable. The methods (ii) and (iii) are preferable because they have many reaction options and can easily increase the rate of introduction of reactive silicon groups.

Hydrosilane compounds that can be used in method (i) are not particularly limited, but examples include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, Dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N- diethylaminomethyl)diethoxysilane and the like.

The amount of the hydrosilane compound used is such that the molar ratio to the carbon-carbon unsaturated bond in the precursor polymer (number of moles of hydrosilane/number of moles of carbon-carbon unsaturated bond) is 0.05 to 10. It is preferable from the viewpoint of performance, and 0.3 to 2 is more preferable from the viewpoint of economy.

Hydrosilylation reactions are accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium and ruthenium may be used. For example, platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; platinum-olefin complexes [for example, Pt(CH ₂ =CH ₂ ) ₂ (PPh ₃ ), Pt(CH ₂ =CH ₂ ) ₂ Cl ₂ ]; platinum-vinyl siloxane complex [Pt {(vinyl)Me ₂ SiOSiMe ₂ (vinyl)}, Pt {Me(vinyl) SiO} ₄ ]; platinum-phosphine complex [Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complex [Pt{P(OPh) ₃ } ₄ ], etc. can be used. From the viewpoint of reaction efficiency, it is preferable to use a platinum catalyst such as chloroplatinic acid or a platinum vinylsiloxane complex.

Silane coupling agents that can be used in the method (ii) or (iii) include, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltri Mercaptosilanes such as ethoxysilane, mercaptomethyltriethoxysilane, and mercaptomethyldimethoxymethylsilane; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, and isocyanate that react with hydroxyl groups Isocyanatosilanes such as methyltrimethoxysilane, isocyanatomethyltriethoxysilane, and isocyanatomethyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyldimethoxy which react with hydroxyl groups, amino groups, or carboxy groups; Epoxysilanes such as methylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane; reaction with isocyanate groups or thioisocyanate groups 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2-aminoethyl)propyldimethoxymethyl Silane, 3-(2-aminoethyl)propyltriethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, Aminosilanes such as (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-(trimethoxysilyl)propyl)amine; 3-hydroxy hydroxyalkylsilanes such as propyltrimethoxysilane and hydroxymethyltriethoxysilane; .

The main chain of the polyoxyalkylene polymer (A) has an ester bond or general formula (4), as long as it does not impair the effects of the invention:
-NR ⁶ -C(=O)- (4)
(wherein R ⁶ represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

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

Examples of the amide segment represented by the general formula (4) include the reaction between an isocyanate group and a hydroxyl group, the reaction between an amino group and a carbonate, the reaction between an isocyanate group and an amino group, and the reaction between an isocyanate group and a mercapto group. etc. can be mentioned. The amide segment represented by the general formula (4) also includes those formed by the reaction of the amide segment containing an active hydrogen atom with an isocyanate group.

As a method for producing the polyoxyalkylene-based 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 form an isocyanate group at the terminal. After synthesizing a polymer having the general formula (5):
ZR ⁷ -SiR ⁵ _3-a X _a (5)
(In the formula, R ⁵ , X and a are the same as defined above. R ⁷ is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group, a carboxy group, a mercapto group, a primary amino group, or a secondary amino group) is reacted with all or part of the isocyanate groups of the synthesized polymer. can.

The silicon compound represented by the general formula (5) is not particularly limited, but examples include γ-aminopropyldimethoxymethylsilane, γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-amino Amino group-containing silanes such as propyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyldimethoxymethylsilane, (N-phenyl)-γ-aminopropyltrimethoxysilane, and N-ethylaminoisobutyltrimethoxysilane hydroxyl group-containing silanes such as γ-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane and mercaptomethyltriethoxysilane; In addition, JP-A-6-211879 (US Patent No. 5364955), JP-A-10-53637 (US Patent No. 5756751), JP-A-10-204144 (EP0831108), JP-A-2000-169544, JP-A-2000-169545 No. 1, 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. can also be used as the silicon compound represented by the general formula (5).

Further, as a method for producing the polyoxyalkylene-based polymer (A) containing an amide segment, for example, a polyoxyalkylene having an active hydrogen-containing group at the terminal is added with the general formula (6):
O═C═N—R ⁷ —SiR ⁵ _3-a X _a (6)
(Wherein, R ⁷ , R ⁵ , X and a are the same as defined above).

The reactive silicon group-containing isocyanate compound represented by the general formula (6) is not particularly limited, but examples include γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate. , γ-methyldiethoxysilylpropyl isocyanate, γ-(methoxymethyl)dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl ) and dimethoxysilylmethyl isocyanate.

When the polyoxyalkylene polymer (A) contains amide segments, the number (average value) of amide segments per molecule of the polyoxyalkylene polymer (A) is preferably 1 to 10, and 1.5 to 5. is more preferred, and 2 to 3 are particularly preferred. If this number is less than 1, the curability may not be sufficient, and conversely if it is greater than 10, the polyoxyalkylene polymer (A) may become highly viscous and difficult to handle. There is In order to lower the viscosity of the curable composition and improve workability, the polyoxyalkylene polymer (A) preferably does not contain an amide segment.

<<Reactive Silicon Group-Containing (Meth)Acrylic Acid Ester Polymer (B)>>
Agent A may contain a (meth)acrylate polymer (B) having a reactive silicon group (hereinafter also referred to as "(meth)acrylate polymer (B)"). Agent A preferably contains a (meth)acrylate polymer (B) together with the polyoxyalkylene polymer (A). However, the (meth)acrylate polymer (B) is an optional component and may not be contained.
The (meth)acrylic ester-based monomer constituting the main chain of the (meth)acrylic ester-based polymer (B) is not particularly limited, and various monomers can be used. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate , glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, (meth)acrylate Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, ( Meth) perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) ) (meth)acrylic acid-based monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

Examples of monomer units other than the above include acrylic acid such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylol acrylamide and N-methylol methacrylamide; , epoxy group-containing monomers, and nitrogen-containing group-containing monomers such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

The (meth)acrylate polymer (B) may be a polymer obtained by copolymerizing a (meth)acrylate monomer and a vinyl monomer copolymerizable therewith. The vinyl-based monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, and the like. Fluorine-containing vinyl monomers; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; Maleic anhydride, maleic acid, maleic acid monoalkyl esters and dialkyl esters; Fumaric acid, fumaric acid monoalkyl esters and dialkyl esters; maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Containing vinyl-based monomers; amide group-containing vinyl-based monomers such as acrylamide and methacrylamide; vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenyl-based monomers such as ethylene and propylene Monomers; conjugated diene-based monomers such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc., and a plurality of these may be used as copolymerization components.

Among the (meth)acrylic acid ester polymers obtained from the above monomers, copolymers composed of (meth)acrylic acid ester monomers and optionally styrene monomers are preferable because of their excellent physical properties. A (meth)acrylic acid ester polymer comprising an acid ester monomer and a methacrylic acid ester monomer is more preferred, and an acrylic acid ester polymer comprising an acrylic acid ester monomer is particularly preferred.

The (meth)acrylic ester-based polymer (B) has a reactive silicon group represented by the general formula (1) shown above. The reactive silicon group of the (meth)acrylate polymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene polymer (A).
Specific examples of R ⁵ include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group, preferably methyl group and ethyl group.

Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, an alkoxy group such as a methoxy group and an ethoxy group is more preferred, and a methoxy group and an ethoxy group are particularly preferred, since they are moderately hydrolyzable and easy to handle.

Specific examples of the reactive silicon group possessed by the (meth)acrylate polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group. , dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group , (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto. Among these are methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- A diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties. A methyldimethoxysilyl group is preferred because it is excellent in shape retention after application. A trimethoxysilyl group is preferred because it exhibits good initial strength and provides a highly rigid cured product.

The reactive silicon group equivalent of the (meth)acrylate polymer (B) is not particularly limited, but is preferably 0.1 mmol/g or more, more preferably 0.5 mmol/g or more, and 0.6 mmol/g or more. is more preferred. The reactive silicon group equivalent is preferably 2.0 mmol/g or less, and more preferably 1.0 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product. Moreover, in order to obtain a highly rigid cured product with a high Young's modulus, the reactive silicon group equivalent is particularly preferably 0.6 mmol/g or more and 1.0 mmol/g or less.

A method for introducing a reactive silicon group into a (meth)acrylic acid ester polymer is not particularly limited, and for example, the following method can be used.
(iv) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive silicon-containing group together with the above monomers. Using this method, reactive silicon groups tend to be randomly introduced into the backbone of the polymer.
(v) A method of polymerizing a (meth)acrylate polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. Using this method, reactive silicon groups can be introduced at the polymer termini.
(vi) A method of copolymerizing a compound having a polymerizable unsaturated group and a reactive functional group (V group) and then reacting the compound having a reactive silicon group and a functional group that reacts with the V group. Specifically, after copolymerizing 2-hydroxyethyl acrylate, an isocyanate silane having a reactive silicon-containing group is reacted, or after copolymerizing glycidyl acrylate, an aminosilane compound having a reactive silicon-containing group is used. and the like can be exemplified.
(vii) A method of modifying a terminal functional group of a (meth)acrylic acid ester-based polymer synthesized by a living radical polymerization method to introduce a reactive silicon group. A (meth)acrylic ester polymer obtained by a living radical polymerization method is easy to introduce a functional group into the terminal of the polymer, and by modifying this, a reactive silicon group can be introduced into the terminal of the polymer.

Examples of the silicon compound that can be used to introduce the reactive silicon group of the (meth)acrylic acid ester polymer (B) using the above method include the following compounds. Compounds having a polymerizable unsaturated group and a reactive silicon-containing group used in method (iv) include 3-(dimethoxymethylsilyl)propyl (meth)acrylate and 3-(trimethoxysilyl)(meth)acrylate. Propyl, 3-(triethoxysilyl)propyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (trimethoxysilyl)methyl (meth)acrylate, (triethoxysilyl) (meth)acrylate methyl, 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate, and the like. From the standpoint of availability, 3-(dimethoxymethylsilyl)propyl (meth)acrylate and 3-(trimethoxysilyl)propyl (meth)acrylate are particularly preferred.

Mercaptosilane compounds having reactive silicon-containing groups used in method (v) include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxy silane and the like.

Compounds having a reactive silicon group and a functional group reactive with the V group used in method (vi) include 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, Isocyanatosilane compounds such as isocyanatomethyldimethoxymethylsilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane; 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltri Epoxysilane compounds such as ethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyldimethoxymethylsilane, glycidoxymethyltriethoxysilane; 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane and aminosilane compounds such as

In method (vii), any modification reaction can be used. A method of introducing a double bond to the end of a polymer using a compound having a reactive functional group and a double bond and then introducing a reactive silicon group thereon by hydrosilylation or the like can be used.

Note that these methods may be used in any combination. For example, by combining method (vi) and method (v), it is possible to obtain a (meth)acrylic acid ester polymer (B) having reactive silicon groups at both molecular chain terminals and/or side chains.

The (meth)acrylic acid ester polymer (B) preferably contains a polymer containing 40% by weight or more of the total monomers of an alkyl (meth)acrylate having 1 to 3 carbon atoms in the alkyl. It is preferable because it becomes rigid. The (meth)acrylic acid ester polymer (B) consists only of a polymer containing 40% by weight or more of the total monomers of the alkyl (meth)acrylate having 1 to 3 carbon atoms. Although it may be present, a polymer containing 40% by weight or more of the total monomers of an alkyl (meth)acrylate having 4 to 30 carbon atoms in the alkyl is also contained together with the polymer, and both are blended. It is preferable that the material is such that the rigidity, elongation, and strength are improved.

Further, the (meth)acrylic acid ester polymer (B) contains 40% by weight or more of the total monomers containing an alkyl (meth)acrylate having 1 to 3 carbon atoms and an alkyl having 4 to 4 carbon atoms. It is also preferable to contain a polymer obtained by copolymerizing a monomer mixture containing 40% by weight or more of alkyl (meth)acrylate of 30 based on all monomers, since rigidity, elongation and strength are improved.

Next, the (meth)acrylic acid ester polymer (B) polymerized using a macromonomer, which is one of preferred embodiments of the (meth)acrylic acid ester polymer (B), will be described.

The (meth)acrylic ester-based polymer (B) polymerized using a macromonomer is a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group represented by the general formula (1) described above. , and a macromonomer (b2), which is a (meth)acrylate polymer having a polymerizable unsaturated group, as constituent monomers. The polymer may further contain a (meth)acrylic acid alkyl ester (b3) as a constituent monomer. In the present application, "(meth)acryl" means "acryl and/or methacryl".

(Monomer (b1) having a reactive silicon group and a polymerizable unsaturated group)
Examples of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-( Compounds having a (meth)acryloxy group and a reactive silicon group, such as meth)acryloxypropyldimethoxymethylsilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples include compounds having a vinyl group and a reactive silicon group such as triethoxysilane. These compounds may use only 1 type and may use 2 or more types together.

The total content of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group is It is preferably 0.1% by weight or more and 50% by weight or less, more preferably 0.5% by weight or more and 30% by weight or less, and even more preferably 1% by weight or more and 20% by weight or less, relative to the monomer.

(Macromonomer (b2))
The macromonomer (b2) is a (meth)acrylate polymer having a polymerizable unsaturated group. The macromonomer (b2) itself is a polymer, but can be copolymerized with the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group by the polymerizable unsaturated group, It is a monomer that constitutes the (meth)acrylate polymer (B).

The main chain skeleton of the macromonomer (b2) is a (meth)acrylate polymer. The monomer constituting the main chain skeleton of the macromonomer (b2) is not particularly limited, and various types can be used. Examples of (meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, ( meth) n-butyl acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( meth)n-heptyl acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, (meth)acrylate Stearyl acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl, 2-hydroxypropyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3 (meth)acrylic acid -trifluoropropyl, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, trifluoromethyl (meth)acrylate , (meth) perfluoroethyl acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoro (meth) acrylate Hexylethyl, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydro(meth)acrylate furfuryl, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate and the like.

Furthermore, other monomers that are copolymerizable with the above (meth)acrylic monomers may be used. Other monomers include, for example, styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Monomer; Maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, and maleic acid dialkyl ester; Fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl ester, and fumaric acid dialkyl ester; Maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl ester monomers such as vinyl benzoate and vinyl cinnamate; olefin monomers such as ethylene and propylene; conjugated diene monomers such as butadiene and isoprene; (meth)acrylamide; (meth)acrylonitrile; Vinyl monomers such as vinyl, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether and butyl vinyl ether are included. Other monomers may be used alone or in combination of two or more.

The macromonomer (b2) has a polymerizable unsaturated group, thereby exhibiting polymerizability. In the macromonomer (b2), the polymerizable unsaturated group may be introduced at either the molecular chain terminal or the side chain of the (meth)acrylic acid ester polymer. is preferably introduced into

The polymerizable unsaturated group possessed by the macromonomer (b2) is not particularly limited as long as it is an unsaturated group that exhibits polymerizability in a general radical polymerization method. Examples include acryloyl group, methacryloyl group, vinyl group and allyl group. , a methallyl group, and the like. An acryloyl group and a methacryloyl group are preferred because they exhibit good polymerizability.

The method for introducing a polymerizable unsaturated group into the macromonomer (b2) is not particularly limited, and for example, the following methods (viii) to (x) can be used.
(viii) A method of copolymerizing a monomer having two types of polymerizable unsaturated groups with different reactivities (for example, allyl acrylate) with a monomer having a (meth)acrylic structure.
(ix) a compound having a polymerizable unsaturated group and a reactive functional group (Z group) (e.g., acrylic acid, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth)acrylic structure, followed by polymerization; A method of reacting a compound having a polyunsaturated group and a functional group that reacts with the Z group (for example, diethyl isocyanate (meth)acrylate).
(x) A method of polymerizing a monomer having a (meth)acrylic structure by a living radical polymerization method and then introducing a polymerizable unsaturated group at the molecular chain end.

Note that these methods may be used in any combination.
Among these methods, it is preferable to use the method (x) because it is possible to introduce a polymerizable unsaturated group at the end of the molecular chain. The "living radical polymerization method" uses a cobalt porphyrin complex as shown, for example, in J. Am. Chem. Soc., 1994, 116, 7943. Those using nitroxide radicals as shown in JP-A-2003-500378, organic halides and sulfonyl halide compounds as shown in JP-A-11-130931 as initiators. , Atom Transfer Radical Polymerization (ATRP method) using a transition metal complex as a catalyst, and the like. The atom transfer radical polymerization method is most preferable because it is easy to introduce a polymerizable unsaturated group to the terminal.

Alternatively, a method of obtaining a (meth)acrylic polymer using a metallocene catalyst and a thiol compound having at least one reactive silicon group in the molecule as disclosed in JP-A-2001-040037 is used. is also possible.

The polymerizable unsaturated group possessed by the macromonomer (b2) preferably has a structure represented by general formula (7) below.
_CH2 =C(R8)-COO-Z ( ⁷ )
(In the formula, R ⁸ represents hydrogen or a methyl group. Z represents the main chain skeleton of the macromonomer (b2).)

The number average molecular weight of the macromonomer (b2) is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, and preferably 50,000 or less, more preferably 30,000. It is below. When the number average molecular weight of the macromonomer (b2) is small, the viscosity of the (meth)acrylic acid ester polymer (B) is low, but there is a tendency that good adhesiveness cannot be obtained. On the other hand, if the number average molecular weight of the macromonomer (b2) is too large, the viscosity tends to be too high, making handling difficult.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the macromonomer (b2) is not particularly limited, but is preferably narrow, more preferably less than 2.0, and further preferably 1.6 or less. 1.5 or less is particularly preferred, 1.4 or less is more preferred, 1.3 or less is even more preferred, and 1.2 or less is most preferred.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the macromonomer (b2) are values measured by GPC (converted to polystyrene), and detailed measurement methods are described in Examples.

The (meth)acrylate polymer (B) is composed of the macromonomer (b2) and other monomers, and the main chain of the (meth)acrylate polymer (B) is the backbone. A polymer chain branched from the trunk chain derived from the macromonomer (b2) is called a branched chain. The monomers constituting the trunk chain and branch chains are composed of the monomers described above, and are not particularly limited. It is preferred that the Tg of the branch chains be lower than the Tg of the trunk chain, as this results in good adhesion.

The Tg of the trunk chain is preferably -60°C to 150°C, more preferably 0°C to 130°C, even more preferably 30°C to 100°C.

The Tg of the branched chain is preferably -100°C to 150°C, more preferably -90°C to 100°C, even more preferably -80°C to 50°C. Tg is obtained from the following Fox formula.
Fox formula:
1/(Tg(K))=Σ(Mi/Tgi)
(In the formula, Mi represents the weight fraction of the monomer i component constituting the polymer, and Tgi represents the glass transition temperature (K) of the homopolymer of the monomer i.)

For the glass transition temperature of the homopolymer, refer to the glass transition temperature (Tg) described in POLYMER HANDBOOK-FOURTH EDITION- (J. Brandrup et al.). When Tg is calculated by Fox's formula, it is calculated without including a monomer having a reactive silicon group.

The total content of the macromonomer (b2) is preferably 1% by weight or more and 50% by weight or less, and 5% by weight or more and 40% by weight, based on the total monomers constituting the (meth)acrylic acid ester polymer (B). The following are more preferable, and 10% by weight or more and 30% by weight or less are even more preferable.

The macromonomer (b2) may be introduced into either the molecular chain end or the side chain of the (meth)acrylic acid ester polymer (B), but it should be introduced into the side chain from the viewpoint of adhesiveness. is preferred. The average number of macromonomers contained in one molecule of the (meth)acrylate polymer (B) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.05 or more. Also, it is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.3 or less.

((Meth)acrylic acid alkyl ester (b3))
As the (meth)acrylic acid alkyl ester (b3), those exemplified for the main chain skeleton of the macromonomer (b2) can be used. It is preferable to use a (meth)acrylic acid alkyl ester having an alkyl group of 1 to 3 carbon atoms, because it increases the rigidity. Specific examples of (meth)acrylic acid alkyl esters in which the alkyl group has 1 to 3 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylate. Isopropyl acrylate can be mentioned. These may use only 1 type and may use 2 or more types together.

From the viewpoint of achieving both flexibility and high rigidity, the total content of the (meth)acrylic acid alkyl ester (b3) is the (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2). It is preferably 40% by weight or more, more preferably 45% by weight or more, still more preferably 50% by weight or more, and even more preferably 55% by weight or more, relative to the total monomers constituting the composition. , more preferably 60% by weight or more. Further, from the viewpoint of durable adhesion, it is preferably 50% by weight or more, more preferably 55% by weight or more, based on the total monomers constituting the (meth)acrylic acid ester polymer (B). , more preferably 60% by weight or more. In order to ensure compatibility with the polyoxyalkylene polymer (A), the content is preferably 70% by weight or less, more preferably 65% by weight or less.

The (meth)acrylate polymer (B) polymerized using the macromonomer (b2) comprises at least a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer (b2 ) as constituent monomers, but may contain (meth)acrylic acid alkyl ester (b3) or other monomers as constituent monomers. Examples of such monomers include (meth)acrylic monomers that do not fall under (b1) to (b3), and monomers other than (meth)acrylic monomers. can use various monomers exemplified for the macromonomer (b2).

The (meth)acrylic acid ester polymer (B) polymerized using the macromonomer (b2) comprises a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and other monomers. Synthesized by copolymerization. This can introduce reactive silicon groups randomly into the backbone of the polymer. However, in order to further introduce a reactive silicon group into the (meth)acrylic acid ester polymer (B), the above-described methods can be used in combination.

The monomer composition of the (meth)acrylic acid ester polymer (B) can be selected depending on the application and purpose, and in applications requiring strength, those having a relatively high glass transition temperature (Tg) are preferred. , 0° C. or higher and 200° C. or lower are preferable, and those having a Tg of 20° C. or higher and 100° C. or lower are more preferable. Note that Tg is obtained from the above-described Fox equation.

Although the number average molecular weight of the (meth)acrylic acid ester polymer (B) is not particularly limited, it is preferably 500 or more and 50,000 or less, more preferably 500 or more and 30,000 or less, in terms of polystyrene equivalent molecular weight by GPC measurement. ,000 or more and 10,000 or less is particularly preferable. Among them, the number average molecular weight of the (meth)acrylic acid ester polymer (B) is preferably 3000 or less because good adhesiveness is exhibited even after the heat and humidity resistance test.

(Meth) A method of blending an acrylic acid ester polymer (B) and a polyoxyalkylene polymer (A) is disclosed in JP-A-59-122541, JP-A-63-112642, JP-A-6- No. 172631, Japanese Patent Application Laid-Open No. 11-116763, and the like. Alternatively, a method of polymerizing a (meth)acrylic acid ester-based monomer in the presence of a polyoxypropylene-based polymer having a reactive silicon group can be used.

When using the (meth)acrylic acid ester polymer (B), the weight ratio (A) of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B): (B) is It is preferably 95:5 to 50:50, that is, the ratio of (A) is 50% by weight or more and 95% by weight or less. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Furthermore, from the viewpoint of achieving both high rigidity and flexibility, (A):(B) is more preferably 80:20 to 50:50, more preferably 70:30 to 50:50.

<<epoxy resin (C)>>
Commonly used epoxy resins can be used as the epoxy resin (C). Although not particularly limited, for example, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin , bisphenol A propylene oxide adduct glycidyl ether type epoxy resin, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxies Resin, N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, hydantoin type epoxy resin, petroleum resin and epoxidized unsaturated polymers such as
Among them, an epoxy resin having at least two epoxy groups in one molecule is preferable because it has high reactivity during curing and the cured product can easily form a three-dimensional network. More preferred are bisphenol A type epoxy resins and novolac type epoxy resins.

The amount of the epoxy resin (C) used is the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B), and the weight ratio of the epoxy resin (C) [(A + B): ( C)] is preferably 90:10 to 50:50, that is, the ratio of (A+B) is preferably 50% by weight or more and 90% by weight or less. From the viewpoint of the flexibility of the cured product, it is preferably 50% by weight or more, and from the viewpoint of the strength of the cured product, it is preferably 90% by weight or less. Furthermore, 80:20 to 60:40 is more preferable in terms of balance between flexibility and strength.

<<epoxy resin curing agent (D)>>
Agent A preferably further contains an epoxy resin curing agent (D) for curing the epoxy resin (C). As the epoxy resin curing agent (D), it is preferable to use an epoxy resin curing agent having a tertiary amine. By using an epoxy resin curing agent having a tertiary amine, a cured product with high rigidity, high strength and high elongation can be obtained.

As the epoxy resin curing agent having a tertiary amine, any compound having a tertiary amine can be used. Specifically, for example, N,N,N′,N′-tetramethyl-1,3-diaminopropane, N,N,N′,N′-tetramethyl-1,6-diaminohexane, N,N -dimethylbenzylamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, (dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tripropylamine, DBU, DBN and these Salts of tertiary amines can be exemplified, but are not limited to these. Moreover, you may use together 2 or more types. Also, a known epoxy resin curing agent other than the epoxy resin curing agent having a tertiary amine may be further added.

The tertiary amine-containing epoxy resin curing agent is preferably an aromatic amine, and more preferably has three or more amino groups. Specifically, 2,4,6-tris(dimethylaminomethyl)phenol can be exemplified.

The amount of the epoxy resin curing agent (D) used is preferably 0.1 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the epoxy resin (C). It is more preferably 0.5 parts by weight or more and 30 parts by weight or less.

<<Silanol condensation catalyst (E)>>
The silanol condensation catalyst (E) can promote the condensation reaction of the reactive silicon groups of the polyoxyalkylene polymer (A) and/or (meth)acrylate polymer (B). The silanol condensation catalyst (E) is blended with the agent A containing the polyoxyalkylene polymer (A) and/or the (meth)acrylate polymer (B). By blending the silanol condensation catalyst (E) with the A agent instead of the B agent, the hydrolysis of the silanol condensation catalyst (E) can be suppressed, and the initial strength after mixing the A and B agents can be improved. You can take advantage of getting better.

Examples of the silanol condensation catalyst (E) include organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, and alkoxy metals.

Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin oxide, reaction products of dibutyltin oxide and silicate compounds, dioctyl A reaction product of tin oxide and a silicate compound, a reaction product of dibutyltin oxide and a phthalic acid ester, and the like can be mentioned.

Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As the carboxylic acid metal salt, the following carboxylic acid and various metals can be combined.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, and stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,5 - nitrogen-containing heterocyclic compounds such as diazabicyclo[4,3,0]nonene-5(DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; butylbiguanide, 1-o-tolylbiguanide and 1-phenylbiguanide biguanides such as; amino group-containing silane coupling agents; and ketimine compounds.

Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum ethylacetate Examples include aluminum compounds such as acetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other curing catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

The curing catalyst may be used in combination of two or more different catalysts. For example, the combination of the amine compound and carboxylic acid, or the combination of the amine compound and alkoxy metal provides the effect of improving the reactivity. There is a possibility that it will be

The amount of the silanol condensation catalyst (E) used is 0.001 parts by weight or more and 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). parts by weight or less, more preferably 0.01 parts by weight or more and 15 parts by weight or less, and even more preferably 0.01 parts by weight or more and 10 parts by weight or less.

<<Water (F)>>
Water (F) is blended with the B agent containing the epoxy resin (C). By blending water (F), the reactive silicon groups possessed by the polyoxyalkylene polymer (A) and/or the (meth)acrylic acid ester polymer (B) when the agent A and agent B are mixed The hydrolysis reaction is accelerated, and the initial strength is developed well. In addition, since water (F) is blended in the B agent, deterioration of the storage stability of the A agent containing the polyoxyalkylene polymer (A) and/or the (meth)acrylic acid ester polymer (B) can be avoided.

The amount of water (F) added is 0.1 parts by weight or more and 10 parts by weight or less with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). is preferably 0.1 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight.

<<Fatty acid amide (G)>>
Agent A preferably further contains a fatty acid amide (G) so as to satisfy the viscosity characteristics described below. As the fatty acid amide, a fatty acid amide wax can be used, which is commercially available as a thixotropic agent, thickener, anti-settling agent, anti-sagging agent, and the like.

Commercially available products of fatty acid amide wax include a powdery product containing only the fatty acid amide wax component and a pre-swelling type in which fatty acid amide wax is made into a paste in a solvent. In addition, it may be a product compounded with other ingredients having thixotropic properties. Examples of commercially available products include Disparlon (registered trademark) manufactured by Kusumoto Kasei Co., Ltd. and products manufactured by ARKEMA.

The amount of the fatty acid amide (G) to be added is 0.1 parts by weight or more and 15 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight.

Since agent A satisfies the viscosity characteristics described later and the cured product obtained by curing the curable composition can exhibit high shear adhesive strength, the ratio of fatty acid amide (G) in agent A is , is preferably 0.9% by weight or more, more preferably 1.1% by weight or more, and particularly preferably 1.3% by weight or more. Although the upper limit is not particularly limited, it may be, for example, 10% by weight or less, preferably 5% by weight or less.

<<Rheology control agent>>
A rheology control agent other than the fatty acid amide (G) may be added to the curable composition. Rheology control agents other than fatty acid amide (G) are not particularly limited, but examples include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate; silica and the like. These rheology control agents may be used alone or in combination of two or more.
When adding a rheology control agent other than the fatty acid amide (G), the amount used is based on a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). , preferably 0.1 to 20 parts by weight.

<<Other Additives>>
The curable composition contains a polyoxyalkylene polymer (A), a (meth)acrylate polymer (B), an epoxy resin (C), an epoxy resin curing agent (D), and a silanol condensation catalyst (E). , In addition to water (F) and fatty acid amide (G), additives such as fillers, adhesion imparting agents, antioxidants, light stabilizers, ultraviolet absorbers, tackifying resins, and other resins are added. Also good. Moreover, various additives may be added to the curable composition as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, plasticizers, solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, agents, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents, and the like.

<Filler>
Various fillers can be blended into the curable composition. Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, Alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.

The amount of filler used is preferably 1 to 300 parts by weight, preferably 10 to 250 parts by weight, with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). part is more preferred.

Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition.

Since agent A satisfies the viscosity characteristics described later and the cured product obtained by curing the curable composition can exhibit high shear adhesive strength, agent A preferably contains calcium carbonate, The proportion of calcium carbonate in agent A is preferably 45% by weight or less, more preferably 35% by weight or less, particularly preferably 25% by weight or less, and most preferably 20% by weight or less. The lower limit is not particularly limited, but may be, for example, 5% by weight or more, preferably 10% by weight or more.

Agent A preferably does not contain dry silica. Dry silica has a high affinity with the reactive silicon groups possessed by the polyoxyalkylene polymer (A) and/or the (meth)acrylic acid ester polymer (B), and inhibits the viscosity characteristics of agent A, which will be described later. This is because there are cases where Dry silica mainly refers to what is obtained by reacting silicon tetrachloride in a high-temperature flame, and is also called fumed silica.

On the other hand, the B agent preferably further contains wet silica and/or dry silica. Thereby, the viscosity characteristics of the B agent can be adjusted within a preferable range. Wet silica is silicon dioxide particles synthesized by a neutralization reaction between an aqueous sodium silicate solution and a mineral acid. Among them, silica obtained by a production method in which the neutralization reaction is carried out in an alkaline state is called precipitated silica, and silica obtained by a production method in which the neutralization reaction is carried out in an acidic manner is called gel silica, and either wet silica may be used.

When the B agent further contains wet silica and / or dry silica, the total amount of wet silica and dry silica used is the amount of polyoxyalkylene polymer (A) and (meth)acrylic acid ester polymer (B) It is preferably from 0.1 to 50 parts by weight, more preferably from 0.5 to 20 parts by weight, and even more preferably from 1 to 10 parts by weight, based on a total of 100 parts by weight.

<Adhesion imparting agent>
Adhesion imparting agents can be added to the curable composition.
A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.

Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; . Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used.

The adhesiveness-imparting agent may be used alone or in combination of two or more. Reaction products of various silane coupling agents can also be used.

The amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B). 0.5 to 10 parts by weight is more preferred.

(solvent, diluent)
A solvent or diluent can be added to the curable composition. Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When a solvent or diluent is used, the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. . The above solvents or diluents may be used alone or in combination of two or more.

<Antioxidant>
An antioxidant (antiaging agent) can be used in the curable composition. The use of an antioxidant can enhance the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

The amount of antioxidant used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferred.

<Light stabilizer>
A light stabilizer can be used in the curable composition. The use of a light stabilizer can prevent photo-oxidative deterioration of the cured product. Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.

The amount of light stabilizer used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferred.

<Ultraviolet absorber>
A UV absorber can be used in the curable composition. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred, and are commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (manufactured by BASF).

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). .2 to 5 parts by weight is more preferred.

(Physical property modifier)
A physical property modifier may be added to the curable composition to adjust the tensile properties of the resulting cured product. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes; By using the physical property modifier, it is possible to increase the hardness of the curable composition when it is cured, or conversely decrease the hardness and increase the elongation at break. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without worsening the stickiness of the surface of the cured product. Compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups. Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). .5 to 5 parts by weight is more preferred.

<Tackifying resin>
A tackifying resin can be added to the curable composition for the purpose of enhancing the adhesiveness or adhesion to the substrate, or for other purposes. As the tackifier resin, there is no particular limitation and any commonly used one can be used.

Specific examples include terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.

The amount of the tackifying resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight, based on a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). Parts by weight is more preferred, and 5 to 30 parts by weight is even more preferred.

<<Curable composition>>
The curable composition according to the present embodiment comprises, as agent A, a polyoxyalkylene polymer (A) and/or an acrylic acid ester polymer (B), an optional epoxy resin curing agent (D), and a silanol condensation catalyst. (E), etc. are blended, and epoxy resin (C), water (F), etc. are blended as B agent, and it is preferable to prepare as a multi-liquid type in which agent A and agent B are mixed before use. .

(first viscosity ratio)
In general, it is difficult to mix viscoelastic curable compositions. As the polyoxyalkylene-based polymer (A) having a reactive silicon group, a polymer having a main chain structure as exemplified can be used. The lower the molecular weight of the polyoxyalkylene polymer (A), the easier it is to mix. is more preferred.

Since the liquidity of the epoxy resin (C) varies greatly depending on its structure, it is preferably liquid at room temperature and has a low viscosity. Among them, bisphenol A type and bisphenol F type are preferable, and the lower the molecular weight, the easier it is to mix.

A curable composition containing a polyoxyalkylene polymer (A) and/or a (meth)acrylic acid ester polymer (B) exhibiting practically sufficient strength and elongation has a large viscosity relaxation during steady flow. (it takes time to relax the viscosity). On the other hand, the curable composition containing the epoxy resin (C), which is liquid at room temperature and has a low viscosity, has little viscosity relaxation (viscosity is relaxed in a short time). As a result, if the two are mixed, it is considered that the mixing properties become uneven immediately after ejection and after a certain period of time has passed since ejection.

In the present embodiment, an agent A containing a polyoxyalkylene polymer (A) having a reactive silicon group and/or a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and an epoxy resin ( C) The first viscosity ratio indicated by each agent B [measured using a rheometer, viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/at a shear rate of 0.1 (1/sec) viscosity] is preferably 5.0 or more. As a result, the relaxation of the respective viscosities of the A and B agents is reduced, thereby improving the mixing properties of the A and B agents and allowing them to be mixed more uniformly. When the first viscosity ratio is 5.0 or more, the rate of decrease over time in viscosity measured in a steady flow becomes small, as shown in Examples below. A small rate of decrease in viscosity over time means that viscosity relaxation is small.

The first viscosity ratio of agent A is preferably 6.0 or higher, more preferably 7.0 or higher, still more preferably 8.0 or higher, and particularly preferably 9.0 or higher. Although the upper limit is not particularly limited, it may be, for example, 30 or less, or 20 or less.

Although the technique for adjusting the first viscosity ratio of agent A to 5.0 or higher is not particularly limited, it is preferable to blend an appropriate rheology control agent with agent A. The rheology control agent includes the fatty acid amide (G) described above.

Agent B can be adjusted to have a first viscosity ratio of 5.0 or more by using the various rheology control agents exemplified. The first viscosity ratio of agent B is preferably 6.0 or higher, more preferably 7.0 or higher, still more preferably 8.0 or higher, and particularly preferably 9.0 or higher. Although the upper limit is not particularly limited, it may be, for example, 30 or less, or 20 or less.

(second viscosity ratio)
The curable composition according to the present embodiment can be used as an adhesive by mixing agent A and agent B before use, applying the mixture to a substrate, and then bonding it to an adherend. . In that case, it is desirable that the shape at the time of application is maintained even after a certain amount of time elapses after application to the base material and before bonding to the adherend.

From the viewpoint of the shape retention of the mixture before curing after such coating, and from the viewpoint of good mixing of agent A and agent B, the polyoxyalkylene polymer (A) having a reactive silicon group and / or The second viscosity ratio [measured using a rheometer, shear Viscosity at a speed of 5×10 ⁻³ (1/sec)/Viscosity at a shear rate of 100 (1/sec)] is adjusted to 300 or more. As a result, agent A and agent B exhibit good mixability, and the shape can be maintained when agent A and agent B are mixed and applied.

The second viscosity ratio of agent A is preferably 400 or higher, more preferably 500 or higher, still more preferably 600 or higher, and particularly preferably 650 or higher. Although the upper limit is not particularly limited, it may be, for example, 2000 or less, or 1000 or less.

Although the technique for adjusting the second viscosity ratio of agent A to 300 or more is not particularly limited, it is preferable to blend an appropriate rheology control agent with agent A. The rheology control agent includes the fatty acid amide (G) described above. At this time, the amount of fatty acid amide (G) added is 1.5 parts by weight or more with respect to a total of 100 parts by weight of polyoxyalkylene polymer (A) and (meth)acrylic acid ester polymer (B). Preferably, it is 2 parts by weight or more, more preferably 2.5 parts by weight or more.

Agent B can be adjusted to have a second viscosity ratio of 300 or more by using various rheology control agents exemplified. The second viscosity ratio of agent B is preferably 400 or higher, more preferably 500 or higher, even more preferably 600 or higher, and particularly preferably 700 or higher. Although the upper limit is not particularly limited, it may be, for example, 2000 or less, or 1000 or less.

From the viewpoint of the shape retention of the mixture after application and before curing, the viscosities of agent A and agent B at 23°C and a shear rate of 5 × 10 ^-3 (1/sec) are each 15,000 Pa s or more. Preferably. Such a viscosity value makes it easier to satisfy the second viscosity ratio described above. The viscosity value is more preferably 20,000 Pa·s or more, still more preferably 25,000 Pa·s or more, and particularly preferably 30,000 Pa·s or more. Although the upper limit is not particularly limited, it may be, for example, 50,000 Pa·s or less, or 40,000 Pa·s or less.

From the viewpoint of mixability of agents A and B, it is preferable that each of the viscosities of agent A and agent B at 23° C. and a shear rate of 100 (1/sec) is 120 Pa·s or less. Such a viscosity value makes it easier to satisfy the second viscosity ratio described above. In other words, it is easy to mix the A agent and the B agent, and it is excellent in shape retention after application and before curing. The viscosity value is more preferably 100 Pa·s or less, more preferably 90 Pa·s or less, and particularly preferably 70 Pa·s or less. Although the lower limit is not particularly limited, it may be, for example, 10 Pa·s or more, or 20 Pa·s or more.

Further, it is preferable that the difference between the viscosity values of agent A and agent B at 23° C. and a shear rate of 100 (1/sec) is small. Specifically, at a shear rate of 100 (1 / sec), the high viscosity value and the low viscosity value of the viscosity value of the agent A and the viscosity value of the agent B are determined, [(high viscosity value - low viscosity value) /(high viscosity value)]×100 is preferably 70% or less. It is more preferably 50% or less, still more preferably 40% or less, and particularly preferably 30% or less.

The curable composition according to the present embodiment may be cured at room temperature after mixing the agent A and the agent B, or may be cured by heating. When dissimilar materials are joined with an adhesive, thermal strain due to the difference in coefficient of linear expansion of the dissimilar materials may become a problem, especially in the case of heat curing. In general, reaction-curing adhesives such as epoxy-based compositions and highly rigid urethane-based compositions can obtain high adhesive strength and rigidity when cured by heating, and thermal distortion occurs when cooled. There is On the other hand, the curable composition according to the present embodiment is rubbery with a Young's modulus of several MPa to several tens of MPa even when heat-cured to such an extent that high adhesive strength can be obtained, and the occurrence of thermal strain can be suppressed. can be done. Furthermore, since high rigidity can be exhibited by subsequent curing at room temperature, it is possible to produce a highly rigid adhesive that does not generate thermal distortion.

When preparing agent A, it is preferable to preliminarily dehydrate and dry ingredients containing water before blending, or to dehydrate the ingredients by reducing pressure during blending and kneading.

As a method of dehydration drying, the heat drying method is suitable for solid substances such as powder, and the dehydration method under reduced pressure or the dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. is suitable for liquid substances. is. Alternatively, a small amount of an isocyanate compound may be blended to react the isocyanate groups with water to dehydrate. An oxazolidine compound such as 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazolidine may be blended and reacted with water for dehydration.

In addition to these dehydration drying methods, the storage stability can be further improved by adding a lower alcohol such as methanol or ethanol, or an alkoxysilane compound. Examples of the alkoxysilane compound include methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane. ethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like.

The amount of the dehydrating agent, especially the alkoxysilane compound used is 0.1 to 20 parts by weight with respect to the total 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). is preferred, and 0.5 to 10 parts by weight is more preferred.

<<Surface treatment of adherend>>
The curable composition according to this embodiment can exhibit good adhesion to various adherends such as plastics, metals and composite materials. In addition, when used as an adhesive for non-polar materials such as polypropylene and engineering plastics with rigid molecular chains such as polyphenylene sulfide, in order to increase adhesion to these adherends and obtain stable adhesive strength, The adherend can be previously surface-treated by known methods. For example, surface treatment techniques such as sanding, flame treatment, corona discharge, arc discharge, plasma treatment, etc. can be used. Plasma treatment is preferred because it causes less damage to the adherend and provides stable adhesion. These surface treatments are also effective for removing release agents used during molding and remaining on the adherend surface.

The curable composition according to the present embodiment exhibits the desired physical properties by performing a long-time curing (curing) step after joining the adherends, and has a characteristic that the strength rises quickly. Therefore, the curable composition according to the present embodiment can be suitably used as a structural adhesive for bonding adherends in a continuous line production system.

The conditions of the final curing (curing) step for the curable composition to express the final desired physical properties are not particularly limited, but for example, the temperature is 5 to 50 ° C. and the time is 24 hours to 1 week. be done.

<<Usage>>
The curable composition is suitable for use as an adhesive composition, sealing materials for buildings, ships, automobiles, roads, etc., adhesives for joining panels of buses, trailers, trains, etc., adhesives, waterproofing. It can be used for materials. The curable compositions are also particularly suitable for joining dissimilar materials such as aluminum-steel, steel-composites and aluminum-composites. When dissimilar materials are joined, it is preferable to cover the joint with a sealer to prevent corrosion. As a sealer, it is possible to use a polymer having reactive silicon groups as indicated in this application. Applications in which the curable composition is used include automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, ship parts, electrical parts, and various machine parts. It is preferably used as an adhesive.

The following items list preferred embodiments in the present disclosure, but the present invention is not limited to the following items.
[Item 1]
A multi-component curable composition comprising agent A and agent B,
Agent A contains a polyoxyalkylene polymer (A) having a reactive silicon group and/or a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a silanol condensation catalyst (E). contains,
B agent contains epoxy resin (C) and water (F),
Agent A has a second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] of 300 or more. can be,
In agent B, the second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] is 300 or more. A multi-component curable composition.
[Item 2]
Agent A has a first viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 0.1 (1/sec) measured using a rheometer] of 5 .0 or more,
In agent B, the first viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 0.1 (1/sec) measured using a rheometer] is 5 The multicomponent curable composition according to item 1, which is 0.0 or more.
[Item 3]
3. The multi-component curable composition according to item 1 or 2, wherein the polyoxyalkylene polymer (A) has an average of more than one reactive silicon group at one terminal site.
[Item 4]
4. The multi-component curable composition according to any one of items 1 to 3, wherein the terminal portion of the polyoxyalkylene polymer (A) has a structure represented by the general formula (2).
[Item 5]
Any of items 1 to 4, wherein the total weight ratio of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) to the epoxy resin (C) is 90:10 to 50:50. The multi-component curable composition according to 1.
[Item 6]
6. The multi-component curable composition according to any one of items 1 to 5, wherein agent A further contains a fatty acid amide (G).
[Item 7]
7. The multicomponent curable composition according to item 6, wherein the content of fatty acid amide (G) in agent A is 0.9% by weight or more.
[Item 8]
8. The multicomponent curable composition according to any one of items 1 to 7, wherein the content of calcium carbonate in agent A is 45% by weight or less.
[Item 9]
The multicomponent curable composition according to any one of items 1 to 8, wherein the B agent further contains wet silica and/or dry silica.
[Item 10]
10. According to any one of items 1 to 9, wherein each of the viscosities of agent A and agent B at a shear rate of 5×10 ⁻³ (1/sec) measured using a rheometer is 15,000 Pa·s or more. A multi-component curable composition.
[Item 11]
11. The multicomponent curable composition according to any one of items 1 to 10, wherein each of the viscosities of agent A and agent B at a shear rate of 100 (1/sec) measured with a rheometer is 120 Pa s or less. thing.
[Item 12]
Among the viscosity values of agent A and agent B at a shear rate of 100 (1/sec) measured using a rheometer, [(high viscosity value - low viscosity value) / (high viscosity value) × 100 ] is 70% or less, the multi-component curable composition according to any one of items 1 to 11.
[Item 13]
13. The multi-component curable composition according to any one of items 1 to 12, which is a two-component curable composition comprising agent A and agent B.
[Item 14]
A cured product obtained by mixing and curing agent A and agent B in the multicomponent curable composition according to any one of items 1 to 13.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the Examples are not intended to limit the present invention.

The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid delivery system: Tosoh HLC-8120GPC
Column: TSK-GEL H type manufactured by Tosoh Solvent: THF
Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

The terminal group equivalent molecular weights in the examples were obtained by determining the hydroxyl value by the measuring method of JIS K 1557, determining the iodine value by the measuring method of JIS K 0070, and determining the structure of the organic polymer (degree of branching determined by the polymerization initiator used). It is the molecular weight obtained by taking into consideration.

The average number of carbon-carbon unsaturated bonds introduced per terminal of polymer (Q) shown in Examples was calculated by the following formula.
(Average introduction number) = [Unsaturated group concentration (mol/g) of polymer (Q) determined from iodine value - Unsaturated group concentration (mol/g) of precursor polymer (P) determined from iodine value] /[Hydroxy group concentration (mol/g) of precursor polymer (P) obtained from hydroxyl value].

The average number of silyl groups introduced per terminal of polymer (A) shown in Examples was calculated by NMR measurement.

(Synthesis example 1)
Polyoxypropylene glycol with 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. A polyoxypropylene having a molecular weight of 17,700) and a molecular weight distribution of Mw/Mn=1.21 was obtained. A 28% methanol solution of sodium methoxide was added in an amount of 1.2 molar equivalents to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene. After methanol was distilled off by vacuum devolatilization, 1.5 molar equivalents of allyl chloride was added to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and the mixture was reacted at 130° C. for 2 hours. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with 100 parts by weight of the unpurified allyl group-terminated polyoxypropylene obtained, and the water was removed by centrifugation. 300 parts by weight of water was further mixed and stirred, the water was removed by centrifugation again, and hexane was removed by vacuum devolatilization.
To 100 parts by weight of the obtained polyoxypropylene, 36 ppm of a platinum divinyldisiloxane complex (isopropanol solution of 3% by weight in terms of platinum) was added, and 0.9 parts by weight of dimethoxymethylsilane was slowly added dropwise while stirring. After the mixed solution was reacted at 90° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure to give an average of 1.6 dimethoxymethylsilyl groups per molecule and a number average molecular weight of 28,500. A linear reactive silicon group-containing polyoxypropylene polymer (A-1) with a molecular weight of 500 was obtained.

(Synthesis example 2)
Polyoxypropylene glycol with 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. A polyoxypropylene having a molecular weight of 17,700) and a molecular weight distribution of Mw/Mn=1.21 was obtained. Sodium methoxide was added as a 28% methanol solution in an amount of 1.0 molar equivalent to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene. After methanol was distilled off by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of hydroxyl-terminated polyoxypropylene, and reaction was carried out at 130° C. for 2 hours. Thereafter, 0.28 molar equivalent of sodium methoxide in methanol was added to remove the methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group to an allyl group. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with 100 parts by weight of the unpurified allyl group-terminated polyoxypropylene obtained, and the water was removed by centrifugation. 300 parts by weight of water was further mixed and stirred, the water was removed by centrifugation again, and hexane was removed by vacuum devolatilization. As described above, polyoxypropylene having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. This polymer was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.
36 ppm of a platinum-divinyldisiloxane complex (3% by weight in terms of platinum in isopropanol solution) was added to 100 parts by weight of the obtained polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one end and stirred. 1.9 parts by weight of dimethoxymethylsilane was slowly added dropwise. After the mixed solution was reacted at 90° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure. A linear reactive silicon group-containing polyoxypropylene polymer (A-2) having an average of 3.2 dimethoxymethylsilyl groups and a number average molecular weight of 28,500 was thus obtained.

(Synthesis Example 3)
Polyoxypropylene glycol with a number average molecular weight of about 4,020 (molecular weight as converted to terminal group: 2,980) is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 14,600 ( A polyoxypropylene glycol having a terminal group-equivalent molecular weight of 9,130) was obtained. Sodium methoxide was added as a 28% methanol solution in an amount of 1.0 molar equivalent to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene. After methanol was distilled off by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of hydroxyl-terminated polyoxypropylene, and reaction was carried out at 130° C. for 2 hours. Thereafter, 0.28 molar equivalent of sodium methoxide in methanol was added to remove the methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group to an allyl group. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with 100 parts by weight of the unpurified allyl group-terminated polyoxypropylene obtained, and the water was removed by centrifugation. 300 parts by weight of water was further mixed and stirred, the water was removed by centrifugation again, and hexane was removed by vacuum devolatilization. As described above, polyoxypropylene having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. This polymer was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.
36 ppm of a platinum-divinyldisiloxane complex (3% by weight in terms of platinum in isopropanol solution) was added to 100 parts by weight of the obtained polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one end and stirred. 3.3 parts by weight of dimethoxymethylsilane was slowly added dropwise. After the mixed solution was reacted at 90° C. for 2 hours, unreacted dimethoxymethylsilane was distilled off under reduced pressure. A linear reactive silicon group-containing polyoxypropylene polymer (A-3) having an average number of silicon groups of 3.2 and a number average molecular weight of 14,600 was thus obtained.

(Synthesis Example 4)
39.5 parts by weight of isobutanol was put into a four-necked flask equipped with a stirrer, and the temperature was raised to 105° C. under a nitrogen atmosphere. 67.7 parts by weight of methyl methacrylate, 6.0 parts by weight of butyl acrylate, 13.5 parts by weight of stearyl methacrylate, 5.5 parts by weight of 3-methacryloxypropyldimethoxymethylsilane, 7.5 parts by weight of 3-mercaptopropyldimethoxymethylsilane. A mixed solution of 3 parts by weight and 1.6 parts by weight of 2,2′-azobis(2-methylbutyronitrile) dissolved in 14.3 parts by weight of isobutanol was added dropwise over 5 hours. Further, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 11.6 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. 000 (GPC molecular weight), an isobutanol solution (solid content: 60%) of the reactive silicon group-containing (meth)acrylic acid ester polymer (B-1) was obtained. The reactive silicon group equivalent of the solid content of the solution is 0.64 mmol/g.

(Example 1)
70 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1, and 1 part by weight of Nocrack CD (antioxidant, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) as a stabilizer. , Adekastab AO-60 (antioxidant, manufactured by ADEKA Co., Ltd.) 1 part by weight, DINP (diisononyl phthalate, manufactured by Jplus Co., Ltd.) 5 parts by weight as a plasticizer, CCR-S10 (colloidal calcium carbonate) as a filler , Shiraishi Kogyo Co., Ltd.) 20 parts by weight, Asahi Thermal (carbon black, Asahi Carbon Co., Ltd.) 0.05 parts by weight, Crayvallac SL (fatty acid amide wax, manufactured by ARKEMA) 3 parts by weight as a rheology control agent, The mixture was mixed using a planetary mixer and dehydrated by heating under reduced pressure at 120° C. for 1 hour. The resulting composition was cooled, and 7 parts by weight of Ancamine K54 (2,4,6-tris(dimethylaminomethyl)phenol, manufactured by EVONIK) as an epoxy resin curing agent (D) and A-171 (vinyltrimethoxy Silane, manufactured by Momentive) 2.5 parts by weight, KBM-603 (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion imparting agent 2 parts by weight, silanol As a condensation catalyst (E), 3 parts by weight of Neostan S-1 (dioctyltin bistriethoxysilicate, manufactured by Nitto Kasei Co., Ltd.) was mixed to obtain agent A.

(viscosity)
A parallel disk plate with a diameter of 20 mm was used as a jig, the gap was set to 0.3 mm, and the shear rate was increased from 1 × 10 ^-3 (1/sec) to 100 (1/sec) for 7 minutes at 23 ° C. and the flow lamp measurement was performed. A rheometer (DHR-2) manufactured by TA Instruments was used as an apparatus. The viscosity was read at a shear rate of 5×10 ⁻³ (1/sec), 0.1 (1/sec), or 100 (1/sec).
The first viscosity ratio is a value calculated from [viscosity at 5×10 ⁻³ (1/sec)/viscosity at 0.1 (1/sec)], and the second viscosity ratio is [5×10 ⁻³ (viscosity at 1/sec)/viscosity at 100 (1/sec)]. Table 1 shows the results.

(Viscosity relaxation)
A parallel disk plate with a diameter of 20 mm was used as a jig, and the gap was set to 0.3 mm. A rheometer (DHR-2) manufactured by TA Instruments was used as an apparatus.
As an index of viscosity relaxation, the viscosity reduction rate [(viscosity after 0.05 minutes - viscosity after 2 minutes)/viscosity after 0.05 minutes] is calculated from the viscosity after 0.05 minutes and the viscosity after 2 minutes. Calculated. Table 1 shows the results.

(Examples 2-6, Comparative Examples 1-2)
Agent A was prepared in the same manner as in Example 1 except that the composition was changed to that shown in Table 1, and the viscosity and viscosity relaxation were evaluated. Table 1 shows the results.
However, in Example 5, Nanox #30 (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) was used as a filler, and in Comparative Example 1, AEROSIL 300 (hydrophilic fumed silica, Nippon Aerosil) was used as a rheology control agent. Co., Ltd.) and 3 parts by weight of AEROSIL R202 (hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.) were used.

(Example 7)
JER828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as an epoxy resin (C) 30 parts by weight, Nanox #30 as a filler (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) 13 parts by weight, R- 820 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 2 parts by weight, water (F) 2 parts by weight, NIPGEL CX-200 (wet silica, manufactured by Tosoh Silica Co., Ltd.) 1.5 parts by weight as a rheology control agent, Mixed using a planetary mixer to obtain a B agent.
The resulting B agent was evaluated for viscosity and viscosity relaxation in the same manner as for A agent. Table 2 shows the results.

(Examples 8-10)
A component B was prepared in the same manner as in Example 7 except that DINP (diisononyl phthalate, manufactured by J-Plus Co., Ltd.) was used as a plasticizer and the formulation was changed to that shown in Table 2. made an evaluation. Table 2 shows the results.

(Example 11)
The A agent prepared in Example 1 and the B agent prepared in Example 7 were mixed so that A agent: B agent = 2.4: 1 (weight ratio) or 3.0: 1 (volume ratio). It was filled in a liquid mixing cartridge (manufactured by NORDSON Co., Ltd.). Using a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture.

(mixed)
In the formulations of Examples and Comparative Examples, agent A is black and agent B is white. A mixture obtained by mixing agent A and agent B was observed with the naked eye, and when color unevenness was not observed, it was rated as "A", and when color unevenness was observed, it was rated as "X". Table 3 shows the results.

(Shape retention)
A 60 mm × 150 mm slate plate is leaned against the floor at 90°, and the mixture is discharged from the discharge port of the static mixer onto the surface of the slate plate to form a bead having a width of 10 mm and a height of 5 mm. was applied to The thickness of the coating film immediately after application and the thickness of the coating film after 1 hour were compared and shown as a ratio. Table 3 shows the results.

(Examples 12-13, Comparative Examples 3-4)
Mixability and shape retention were evaluated by mixing agents A and B in the same manner as in Example 11 except that agent A prepared in Examples 2 and 3 and Comparative Examples 1 and 2 was used. . Table 3 shows the results.

From Table 3, the second viscosity ratio [5 × 10 ^-3 (1/sec)/100 (1/sec)] of agents A and B is 300 or more. It can be seen that the product is superior to Comparative Examples 3 and 4 in which the second viscosity ratio of agent A is less than 300 in shape retention after mixing.
In addition, Examples 11 to 13 and Comparative Example 4 in which the first viscosity ratio [5 × 10 ^-3 (1/sec)/0.1 (1/sec)] of agent A and agent B is 5.0 or more , is superior to Comparative Example 3 in which the first viscosity ratio of agent A is less than 5.0.
Furthermore, when the viscosity relaxation of agents A and B is compared in Tables 1 and 2, the viscosity reduction rate of agents A and B of Examples 1 to 10 and Comparative Example 2 when steady flow viscosity measurement is performed is It can be seen that the viscosity reduction rate of agent A of Comparative Example 1 is as large as 29%, whereas the viscosity reduction rate is relatively small.

(Example 14)
The A agent prepared in Example 1 and the B agent prepared in Example 7 were mixed so that A agent: B agent = 2.4: 1 (weight ratio) or 3.0: 1 (volume ratio). It was filled in a liquid mixing cartridge (manufactured by NORDSON Co., Ltd.). Using a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture.

(Shear test)
A steel plate (SS400) used as an adherend was polished with sandpaper #400 and degreased with heptane. After applying a mixture of the A and B agents to one adherend, the other adherend was pasted so as to have a bonding area of 25 mm×12.5 mm and a thickness of 0.5 mm. Using this lamination time as the start time, after 2 hours under 23°C 50% RH conditions, 7 days under 23°C 50% RH conditions, and then 4 days at 50°C, the test speed was set to 10 mm / min. As well as measuring the shear bond strength, the fracture state was observed. The state of failure was visually confirmed using CF as cohesive failure (destruction at the adhesive portion) and AF as interfacial failure (peeling at the interface between the adhesive and the adherend). When both are mixed, the ratio of each is shown. For example, when the cohesive failure rate is 50% and the interfacial failure rate is 50%, it is described as C50A50. Table 4 shows the results.

(Examples 15-16)
A shear test was performed by mixing agents A and B in the same manner as in Example 14, except that agent A prepared in Examples 2 and 3 was used. Table 4 shows the results.

(Examples 17-19)
A shear test was performed by mixing agents A and B in the same manner as in Example 14 except that agent A prepared in Examples 4 to 6 was used and agent B prepared in Examples 8 to 10 was used. . Table 4 shows the results.

(Comparative Example 5)
In the same manner as in Example 14, except that the silanol condensation catalyst (E) was added to the B agent instead of the A agent, and the blending amount of the filler in the B agent was adjusted, the A and B agents were prepared and mixed. A shear test was performed. Table 4 shows the results.

(Comparative Example 6)
Agents A and B were prepared and mixed in the same manner as in Example 14 except that water (F) was not added to agent B and the amount of the filler in agent B was adjusted, and a shear test was performed. Table 4 shows the results.

From Table 4, after 2 hours at 23° C. after mixing, Examples 14-19 had a certain degree of shear strength and had good initial strength development, whereas the silanol condensation catalyst (E ) was blended in the B agent instead of the A agent, and in Comparative Example 6 where the water (F) was not blended, curing had not progressed at the above point and the shear strength could not be measured. In addition, in Comparative Example 5, the final strength after sufficient curing was also insufficient.

Claims (14)

A multi-component curable composition comprising agent A and agent B,
Agent A contains a polyoxyalkylene polymer (A) having a reactive silicon group and/or a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a silanol condensation catalyst (E). contains,
B agent contains epoxy resin (C) and water (F),
Agent A has a second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] of 300 or more. can be,
In agent B, the second viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 100 (1/sec) measured using a rheometer] is 300 or more. A multi-component curable composition. Agent A has a first viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 0.1 (1/sec) measured using a rheometer] of 5 .0 or more,
In agent B, the first viscosity ratio [viscosity at a shear rate of 5 × 10 ^-3 (1/sec)/viscosity at a shear rate of 0.1 (1/sec) measured using a rheometer] is 5 0.0 or more, the multi-part curable composition according to claim 1. 3. The multicomponent curable composition according to claim 1 or 2, wherein the polyoxyalkylene polymer (A) has an average of more than one reactive silicon group at one terminal site. The terminal portion of the polyoxyalkylene polymer (A) has the general formula (2):

(In the formula, R ¹ and R ³ each independently represent a divalent C 1-6 bonding group, and the atoms bonded to the respective carbon atoms adjacent to R ¹ and R ³ are carbon, oxygen, nitrogen R ² and R ⁴ each independently represent hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10. R ⁵ each independently represents a hetero-containing represents a hydrocarbon group having 1 to 20 carbon atoms which may have a group, X represents a hydroxyl group or a hydrolyzable group, and a is 1, 2, or 3. 3. The multi-component curable composition according to claim 1 or 2. The weight ratio of the total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) to the epoxy resin (C) is 90:10 to 50:50. A multi-part curable composition as described. 3. The multi-component curable composition according to claim 1 or 2, wherein agent A further contains a fatty acid amide (G). 7. The multicomponent curable composition according to claim 6, wherein the content of fatty acid amide (G) in agent A is 0.9% by weight or more. 3. The multicomponent curable composition according to claim 1, wherein the content of calcium carbonate in agent A is 45% by weight or less. 3. The multicomponent curable composition according to claim 1 or 2, wherein the B agent further contains wet silica and/or dry silica. The multi-liquid according to claim 1 or 2, wherein each of the viscosities of agent A and agent B at a shear rate of 5 × 10 ^-3 (1/sec) measured using a rheometer is 15,000 Pa s or more. Mold curable composition. 3. The multicomponent curable composition according to claim 1, wherein each of the viscosities of agent A and agent B at a shear rate of 100 (1/sec) measured with a rheometer is 120 Pa·s or less. Among the viscosity values of agent A and agent B at a shear rate of 100 (1/sec) measured using a rheometer, [(high viscosity value - low viscosity value) / (high viscosity value) × 100 ] is 70% or less, the multicomponent curable composition according to claim 1 or 2. 3. The multi-component curable composition according to claim 1 or 2, which is a two-component curable composition comprising an A component and a B component. A cured product obtained by mixing and curing agent A and agent B in the multicomponent curable composition according to claim 1 or 2.