JP2021024958A - Curable composition - Google Patents

Abstract

To provide a curable composition in which reduction of stretching of a cured product that could be progressed by a curing and aging process is suppressed, and a cured product obtained by curing the composition.SOLUTION: A multi-liquid type curable composition contains: an agent A containing polyoxyalkylene-based polymer (A) having reactive silicon group shown in a general formula (1), (meth)acrylic acid ester-based polymer (B) having reactive silicon group shown in the general formula (1), and epoxy resin curing agent (D); and an agent B containing epoxy resin (C) and silanol condensation catalyst (F), in which either one or both agent A and agent B contain unsubstituted phenol and a phenolic compound (E) selected from the group consisting of substituted phenol having one or two substituent groups on a benzene ring. -SiR5cX3-c (1) (in the formula, R5 denotes a substituted or unsubstituted hydrocarbon group having a carbon number of 1 to 20. X denotes a hydroxyl group or a hydrolyzable group. c denotes 0 or 1).SELECTED DRAWING: None

Description

The present invention relates to a multi-component curable composition.

Vehicles, aircraft, and railroads are being replaced with lightweight materials such as aluminum, magnesium, and carbon fiber composite materials other than steel as structural members in order to reduce weight, and multi-materials that use multiple materials for one car body are becoming more common. It is increasing. Since spot welding and laser welding may be difficult for joining dissimilar materials, adhesive joining using an adhesive is drawing attention. Since steel sheets, aluminum alloys, and fiber-reinforced composite materials have different coefficients of linear expansion, the adhesive is required to have flexibility to follow thermal strain. For this reason, an epoxy resin having high rigidity may be disadvantageous, and therefore, a material having a high elastic modulus and flexibility is required as a new structural adhesive.

As an adhesive, a composition composed of a reactive silicon group-containing polyoxyalkylene polymer having high breaking strength and flexibility and an epoxy resin is known (see, for example, Patent Document 1), but is a structural member. As an adhesive, the strength may not be sufficient.

On the other hand, in Patent Document 2, an agent A containing a polyoxyalkylene polymer having more than one reactive silicon group at one terminal, a reactive silicon group-containing (meth) acrylic acid ester polymer, and an agent A. It is disclosed that a multi-component curable composition containing an agent B containing an epoxy resin can form a cured product exhibiting high strength, high rigidity and flexibility, and can be used as a structural adhesive.

Japanese Unexamined Patent Publication No. 02-214759 International Publication No. 2019/069866

In general, an adhesive composed of an organic polymer having a reactive silicon group and an epoxy resin exhibits predetermined physical properties by performing a long-term curing and curing step for several days after joining the adherends.

However, for structures containing three components, a polyoxyalkylene polymer containing a reactive silicon group, a (meth) acrylic acid ester polymer containing a reactive silicon group, and an epoxy resin, as described in Patent Document 2. With adhesives, while a high-strength cured product can be obtained by a long-term curing and curing step, there is a problem that the elongation of the cured product gradually decreases during that period.

In view of the above situation, the present invention contains a reactive silicon group-containing polyoxyalkylene polymer, a reactive silicon group-containing (meth) acrylic acid ester polymer, and an epoxy resin, and is subjected to a curing curing step. It is an object of the present invention to provide a curable composition in which a decrease in elongation of a cured product that can proceed is suppressed, and a cured product obtained by curing the composition.

As a result of diligent studies to solve the above problems, the present inventors have found reactive silicon group-containing polyoxyalkylene-based polymers, reactive silicon group-containing (meth) acrylic acid ester-based polymers, and epoxy resins. The present invention has been completed by finding that the above-mentioned problems can be solved by blending a specific phenolic compound with the contained multi-component curable composition.

That is, the present invention is a polyoxyalkylene polymer (A) having a reactive silicon group represented by the general formula (1), and a (meth) acrylic acid ester polymer having a reactive silicon group represented by the general formula (1). A multi-component curable composition containing an agent A containing (B) and an epoxy resin curing agent (D), and an agent B containing an epoxy resin (C) and a silanol condensation catalyst (F). A phenolic compound (E) selected from the group consisting of an unsubstituted phenol and a substituted phenol having one or two substituents on the benzene ring, wherein either or both of the agent A and the agent B are ) Containing a multi-component curable composition.
-SiR ⁵ _c X _3-c (1)
(Wherein, R ⁵ is a hydrocarbon group of a substituted or unsubstituted C 1 to 20 .X is .c showing a hydroxyl group or a hydrolyzable group is 0 or 1.)
Preferably, the content ratio of the epoxy resin curing agent (D) is 4% by weight or more in the entire curable composition. Preferably, [(Epoxy resin curing agent (D) hydroxyl equivalent Eqa (eq / g)) × (Epoxy resin curing agent (D) compounding weight) + (Phenolic compound (E) hydroxyl equivalent Eqa (eq / g)) g)) × (blended weight of phenolic compound (E))] / [(epoxy equivalent of epoxy resin (C) Eqb (eq / g)) × (blended weight of epoxy resin (C))] is 0.25 That is all. Preferably, the epoxy resin curing agent (D) is of the formula: -CH _2- NR ⁷ R ⁸ (in the formula, R ⁷ and R ⁸ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, respectively. ) Is an aromatic compound having two or more disubstituted aminomethyl groups in the molecule. Preferably, [((-CH _2- NR ⁷ R ⁸ ) equivalent of epoxy resin curing agent (D) Eqc (eq / g)) × (blending weight of epoxy resin curing agent (D))] / [(epoxy resin) The epoxy equivalent of (C) Eqb (eq / g)) × (blending weight of the epoxy resin (C))) is 0.35 or more. Preferably, the terminal site of the polyoxyalkylene polymer (A) is the general formula (2):

(In the formula, R ¹ and R ³ are independently divalent carbon atoms 1 to 6 bonding groups, and the atoms bonded to the respective carbon atoms adjacent to ^{R 1} and R ^{3 are carbon, oxygen, and nitrogen.} R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. N is an integer of 1 to 10. R ⁵ is a substituted or unsubstituted carbon. It is a hydrocarbon group of numbers 1 to 20. X is a hydroxyl group or a hydrolyzable group. C represents 0 or 1). Preferably, R ¹ is CH ₂ OCH ₂ and R ³ is CH ₂ . Preferably, R ² and R ⁴ are hydrogen atoms, respectively. Preferably, the (meth) acrylic acid ester-based polymer (B) has a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a (meth) acrylic acid ester having a polymerizable unsaturated group. It is a polymer having a macromonomer (b2), which is a system polymer, as a constituent monomer. Preferably, either or both of Agent A and Agent B further contain fumed silica as a filler.

The present invention is also a structural adhesive composed of the multi-component curable composition, and is also a cured product obtained by curing the multi-component curable composition.

According to the present invention, it contains a reactive silicon group-containing polyoxyalkylene polymer, a reactive silicon group-containing (meth) acrylic acid ester-based polymer, and an epoxy resin, and can proceed by a curing curing step. It is possible to provide a curable composition in which a decrease in elongation of the cured product is suppressed, and a cured product obtained by curing the composition.

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

The present invention relates to a polyoxyalkylene polymer (A) having a reactive silicon group represented by the following general formula (1), and a (meth) acrylic acid ester-based polymer having a reactive silicon group represented by the following general formula (1). A multi-component curable composition containing an agent A containing a coalescence (B) and an epoxy resin curing agent (D), and an agent B containing an epoxy resin (C) and a silanol condensation catalyst (F). A phenolic compound selected from the group consisting of an unsubstituted phenol and a substituted phenol having one or two substituents on the benzene ring, wherein either or both of the agent A and the agent B are used. It is a multi-component curable composition containing E).

<< Polyoxyalkylene polymer (A) having a reactive silicon group >>
<Reactive silicon group>
The polyoxyalkylene polymer (A) has a reactive silicon group represented by the general formula (1).
-SiR ⁵ _c X _3-c (1)
(Wherein, R ⁵ is a hydrocarbon group of a substituted or unsubstituted C 1 to 20 .X is .c showing a hydroxyl group or a hydrolyzable group is 0 or 1.)

The number of carbon atoms in the hydrocarbon group for R ⁵ preferably 1 to 10, more preferably 1 to 5, 1 to 3 is more preferable. Specific examples of R ⁵ include, for example, a methyl group, an ethyl group, a chloromethyl group, a methoxymethyl group, an N, N-diethylaminomethyl group, and preferably a methyl group, an ethyl group, and a chloromethyl group. It is a group or a methoxymethyl group, and more preferably a methyl group or a methoxymethyl group.

Examples of X include a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like. Among these, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.

Specific examples of the reactive silicon group contained in the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and a dimethoxymethyl. Cyril 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, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it shows high activity and a cured product having good mechanical properties can be obtained, and trimethoxysilyl group and triethoxysilyl group are more preferable because a cured product with high rigidity can be obtained. A trimethoxysilyl group is more preferred.

The polyoxyalkylene polymer (A) may have more than one reactive silicon group on average at one terminal site. Having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) has 2 at one terminal site as represented by the following general formula (2). It is shown that a polyoxyalkylene having two or more reactive silicon groups is contained. That is, the polyoxyalkylene polymer (A) may contain only polyoxyalkylene having two or more reactive silicon groups at one terminal site, or two or more at one terminal site. It may contain both a polyoxyalkylene having a reactive silicon group and a polyoxyalkylene having one reactive silicon group at one terminal site. Further, as a plurality of terminal sites contained in one molecule of polyoxyalkylene, there may be both a terminal site having two or more reactive silicon groups and a terminal site having one reactive silicon group. Further, the polyoxyalkylene polymer (A) as a whole is a poly having an average of more than one reactive silicon group at one terminal site, but having a terminal site having no reactive silicon group. It may contain oxyalkylene.

(In the formula, R ¹ and R ³ are independently divalent carbon atoms 1 to 6 bonding groups, and the atoms bonded to the respective carbon atoms adjacent to ^{R 1} and R ^{3 are carbon, oxygen, and nitrogen.} R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. N is an integer of 1 to 10. R ⁵ , X and c are the formulas (1). ) Is as described above.)

R ¹ and R ³ may be divalent organic groups having 1 to 6 carbon atoms, or hydrocarbon groups that may contain oxygen atoms. The hydrocarbon group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms. Specific examples of R ¹ _{include CH 2} OCH ₂ , CH ₂ O, and CH ₂ , but CH ₂ OCH ₂ is preferable. Specific examples of R ³ _{include CH 2} and CH ₂ CH ₂ , but CH ₂ is preferable.

The hydrocarbon groups of R ² and R ⁴ preferably have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 to 2 carbon atoms. Specific examples of R ² and R ⁴ include, for example, a hydrogen atom, a methyl group, and an ethyl group, but a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.

According to a particularly preferable embodiment, the terminal site represented by the general formula (2) has R ¹ being CH ₂ OCH ₂ , R ³ being CH ₂ , and R ² and R ⁴ being hydrogen atoms, respectively. 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 a plurality of values may be mixed.

The number of reactive silicon groups contained in the polyoxyalkylene polymer (A) is preferably more than 1.0 on average at one terminal site, and more preferably 1.1 or more. , 1.5 or more, and even more preferably 2.0 or more. Further, the number is preferably 5 or less, and 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 is 1.0. The number is more preferably 1, 1.1 or more, and even more preferably 1.5 or more. Further, the number is preferably 4 or less, and more preferably 3 or less.

The polyoxyalkylene polymer (A) may have a reactive silicon group in addition to the terminal portion, but if it is contained only in the terminal portion, a rubber-like cured product having high elongation and low elastic modulus can be obtained. It is preferable because it is easy to get rid of.

The average number of reactive silicon groups contained in the polyoxyalkylene polymer (A) per molecule is preferably more than 1.0, more preferably 1.2 or more, and further 1.3 or more. Preferably, 1.5 or more are even more preferable, and 1.7 or more are particularly preferable. Further, 6.0 or less is preferable, 5.5 or less is more preferable, and 5.0 or less is most preferable. If the average number of reactive silicon groups per molecule is 1.0 or less, a high-strength cured product may not be obtained. If the average number of reactive silicon groups per molecule exceeds 6.0, a cured product having high elongation may not be obtained.

<Main chain structure>
The main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, etc. Examples thereof include a polyoxypropylene-polyoxybutylene copolymer. Among them, polyoxypropylene is preferable.

The number average molecular weight of the polyoxyalkylene polymer (A) is 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 30, in terms of polystyrene-equivalent molecular weight in GPC. It is 000. If the number average molecular weight is less than 3,000, the amount of reactive silicon groups introduced increases, which may be inconvenient in terms of manufacturing cost. If it exceeds 100,000, the viscosity becomes high and workability is improved. Tends to be inconvenient.

As for the molecular weight of the polyoxyalkylene polymer (A), the organic polymer precursor before the introduction of the reactive silicon group is prepared according to the method for measuring the hydroxyl value of JIS K 1557 and the raw material as specified in JIS K 0070. Directly measure the terminal group concentration by titration analysis based on the principle of the measuring method, and indicate the terminal group equivalent molecular weight obtained in consideration of the structure of the organic polymer (branching degree determined by the polymerization initiator used). You can also do it. For the terminal group-equivalent molecular weight of the polyoxyalkylene-based polymer (A), a calibration line of the number average molecular weight obtained by general GPC measurement of the organic polymer precursor and the terminal group-equivalent molecular weight is prepared, and the polyoxyalkylene-based polymer is based. It is also possible to convert the number average molecular weight of the polymer (A) obtained by GPC into the terminal group equivalent molecular weight.

The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, but is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less. , 1.4 or less is particularly preferable. The molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight obtained by GPC measurement.

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

<Method for synthesizing polyoxyalkylene polymer (A)>
Next, a method for synthesizing the polyoxyalkylene polymer (A) will be described.
The polyoxyalkylene-based polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site has two at one end of the hydroxyl group-terminal polymer obtained by the polymerization. After introducing the above carbon-carbon unsaturated bond, it is preferable to obtain it by reacting a reactive silicon group-containing compound that reacts with the carbon-carbon unsaturated bond. The above-mentioned preferable synthesis method will be described below.

(polymerization)
As the polyoxyalkylene polymer (A), a method of polymerizing an epoxy compound with an initiator having a hydroxyl group using a composite metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable.

The initiator having a hydroxyl group includes one hydroxyl group such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polyoxypropylene glycol, polyoxypropylene triol, allyl alcohol, polypropylene monoallyl ether, and polypropylene monoalkyl ether. Those having the above can be mentioned.

Examples of the epoxy compound include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Of these, propylene oxide is preferable.

(Introduction of carbon-carbon unsaturated bond)
As a method of introducing two or more carbon-carbon unsaturated bonds into one terminal, an alkali metal salt is allowed to act on the hydroxyl group terminal polymer, and then an epoxy compound having a carbon-carbon unsaturated bond is first reacted. Then, it is preferable to use a method of reacting a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond. By using this method, it is possible to efficiently and stably introduce a reactive group while controlling the molecular weight and molecular weight distribution of the polymer main chain according to the polymerization conditions.

As the alkali metal salt used in the present invention, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide and potassium ethoxide are preferable, and sodium methoxide and potassium methoxide are more preferable. Sodium methoxide is particularly preferred in terms of availability.

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

As an epoxy compound having a carbon-carbon unsaturated bond used in the present invention, the general formula (3):

^{The compound represented by (R 1} and R ² in the formula are the same as those described above) can be preferably used. Specifically, allyl glycidyl ether, metallyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monooxide, and 1,4-cyclopentadiene monoepoxide are preferable from the viewpoint of reaction activity, and allyl glycidyl ether is particularly preferable.

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

In the present invention, the reaction temperature at the time of cycloaddition 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. More preferably, it is 110 ° C. or higher and 140 ° C. or lower.

Examples of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond used in the present invention include vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, and iodide. Examples thereof include allyl chloride, and it is more preferable to use allyl chloride and metallyl chloride from the viewpoint of ease of handling.

The amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond added is not particularly limited, but the molar ratio of the hydroxyl-terminated polymer to the hydroxyl group is preferably 0.7 or more, preferably 1.0 or more. More preferred. Further, 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, and 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, and more preferably 30 minutes or more and 3 hours or less.

(Introduction of reactive silicon group)
The method for introducing the reactive silicon group is not particularly limited, and a known method can be used. The introduction method is illustrated below.
(I) 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 a carbon-carbon unsaturated bond to form a bond and a reactive silicon group (also referred to as a silane coupling agent). How to react. Examples of the group capable of forming a bond by reacting with a carbon-carbon unsaturated bond include, but are not limited to, a mercapto group.
(Iii) A method for reacting a reactive group-containing polymer with a silane coupling agent. The combination of the reactive group of the reactive group-containing polymer and the silane coupling agent includes a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, and an amino. Examples include, but are not limited to, a group and an α, β-unsaturated carbonyl group (reaction by Michael addition), a carboxy group and an epoxy group, an unsaturated bond and a mercapto group.

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

The hydrosilane compound that can be used in the method (i) is not particularly limited, but for example, trimethoxysilane, triethoxysilane, tris (2-propenyloxy) silane, triacetoxysilane, dimethoxymethylsilane, diethoxymethylsilane, etc. 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 (number of moles of hydrosilane / number of moles of carbon-carbon unsaturated bond) to carbon-carbon unsaturated bond in the precursor polymer is 0.05 to 10. It is preferable from the viewpoint of property, and 0.3 to 2 is more preferable from the viewpoint of economy.

The hydrosilylation reaction is accelerated by various catalysts. As the hydrosilylation catalyst, known catalysts such as various complexes such as cobalt, nickel, iridium, platinum, palladium, rhodium, and ruthenium may be used. For example, a carrier such as alumina, silica, or carbon black on which platinum is supported, platinum chloride acid; a platinum chloride acid complex composed of platinum chloride acid and alcohol, aldehyde, ketone, or the like; a platinum-olefin complex [for example, Pt (CH). ₂ = CH ₂ ) ₂ (PPh ₃ ), Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ]; Platinum-vinylsiloxane 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 ] and the like 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.

Examples of the silane coupling agent that can be used in the method (ii) or (iii) above include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, and 3-mercaptopropyltri that react with unsaturated bonds. Mercaptosilanes such as ethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxymethylsilane; 3-isocyanuppropyltrimethoxysilane, 3-isocyanuppropyldimethoxymethylsilane, 3-isocyanuppropyltriethoxysilane, isocyanate that react with hydroxyl groups Isoisocyanates such as methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyldimethoxymethylsilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxy, which react with hydroxyl groups, amino groups or carboxy groups. Epoxysilanes such as methylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, glycidoxymethyldimethoxymethylsilane; react 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 Examples thereof include hydroxyalkylsilanes such as propyltrimethoxysilane and hydroxymethyltriethoxysilane. ..

<< Reactive Silicon Group-Containing (Meta) Acrylic Ester Polymer (B) >>
As a (meth) acrylic acid ester-based monomer constituting the main chain of a reactive silicon group-containing (meth) acrylic acid ester-based polymer (B) (also referred to as "(meth) acrylic acid ester-based polymer (B)") Is not particularly limited, and various types can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , (Meta) tert-butyl acrylate, (meth) n-pentyl acrylate, (meth) n-hexyl 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) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate , (Meta) glycidyl acrylate, (meth) acrylate (3-trimethoxysilyl) propyl, (meth) acrylate (3-dimethoxymethylsilyl) propyl, (meth) acrylate (2-trimethoxysilyl) ethyl, (Meta) acrylic acid (2-dimethoxymethylsilyl) ethyl, (meth) acrylic acid trimethoxysilylmethyl, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid ethylene oxide adduct, (meth) Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, ( Perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) ) Examples of (meth) acrylic acid-based monomers such as 2-perfluorohexyl ethyl acrylate, 2-perfluorodecyl ethyl (meth) acrylate, and 2-perfluorohexadecyl ethyl (meth) acrylate.

Examples of the monomer unit other than the above include acrylic acids such as acrylic acid and methacrylic acid; monomers containing an amide group such as N-methylolacrylamide and N-methylolmethacrylate, glycidyl acrylate and glycidyl methacrylate. , Monomers containing epoxy groups, monomers containing nitrogen-containing groups such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate.

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

Among the (meth) acrylic acid ester-based polymers obtained from the monomers, a copolymer composed of a (meth) acrylic acid ester-based monomer and, in some cases, a styrene-based monomer is preferable because of its excellent physical properties. A (meth) acrylic acid ester-based polymer composed of an acid ester monomer and a methacrylic acid ester monomer is more preferable, and an acrylic acid ester-based polymer composed of an acrylic acid ester monomer is particularly preferable.

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

Examples of X include hydroxyl groups, hydrogens, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like. Among these, an alkoxy group such as a methoxy group or an ethoxy group is more preferable, and a methoxy group or an ethoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.

Specific examples of the reactive silicon group contained in the (meth) acrylic acid ester-based 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, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (N, N- Diethylaminomethyl) dimethoxysilyl group is preferable because it shows high activity and a cured product having good mechanical properties can be obtained, and trimethoxysilyl group and triethoxysilyl group are more preferable because a cured product having a high young rate can be obtained. , Trimethoxysilyl group is more preferable.

The reactive silicon group equivalent of the (meth) acrylic acid ester 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 even more preferable. 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. Further, in order to obtain a highly rigid cured product having a high Young's modulus, it is particularly preferable that the reactive silicon group equivalent is 0.6 mmol / g or more and 1.0 mmol / g or less.

The method for introducing the reactive silicon group into the (meth) acrylic acid ester-based 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-mentioned monomer. Using this method, reactive silicon groups tend to be randomly introduced into the main chain of the polymer.
(V) A method for polymerizing a (meth) acrylic acid ester-based polymer using a mercaptosilane compound having a reactive silicon-containing group as a chain transfer agent. Using this method, a reactive silicon group can be introduced into the polymer terminal.
(Vi) A method in which a compound having a polymerizable unsaturated group and a reactive functional group (V group) is copolymerized, and then the compound having a reactive silicon group and a functional group that reacts with the V group is reacted. Specifically, a method of copolymerizing 2-hydroxyethyl acrylate and then reacting with an isocyanate silane having a reactive silicon-containing group, or an aminosilane compound having a reactive silicon-containing group after copolymerizing glycidyl acrylate. Can be exemplified as a method of reacting.
(Vii) A method for introducing a reactive silicon group by modifying the terminal functional group of the (meth) acrylic acid ester-based polymer synthesized by the living radical polymerization method. The (meth) acrylic acid ester-based polymer obtained by the living radical polymerization method can easily introduce a functional group at the polymer terminal, and by modifying this, a reactive silicon group can be introduced at the polymer terminal.

Examples of the silicon compound that can be used for introducing the reactive silicon group of the (meth) acrylic acid ester-based polymer (B) by the above method include the following compounds. Examples of the compound having a polymerizable unsaturated group and a reactive silicon-containing group used in the method (iv) include 3- (dimethoxymethylsilyl) propyl (meth) acrylate and 3- (trimethoxysilyl) (meth) acrylate. Propyl, 3- (triethoxysilyl) propyl (meth) acrylic acid, (meth) acrylic acid (dimethoxymethylsilyl) methyl, (meth) acrylic acid (trimethoxysilyl) methyl, (meth) acrylic acid (triethoxysilyl) Examples thereof include methyl, 3-((methoxymethyl) dimethoxysilyl) propyl (meth) acrylate. From the viewpoint of availability, 3- (dimethoxymethylsilyl) propyl (meth) acrylate and 3- (trimethoxysilyl) propyl (meth) acrylate are particularly preferable.

Examples of the mercaptosilane compound having a reactive silicon-containing group used in the method (v) include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) trimethoxy. Examples include silane.

Examples of the compound having a reactive silicon group and a functional group that reacts with the V group used in the method (vi) include 3-isocyanapropyldimethoxymethylsilane, 3-isocyanuppropyltrimethoxysilane, and 3-isocyanuppropyltriethoxysilane. Isocyanate silane compounds such as isocyanate methyldimethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane; 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 Aminosilane compounds such as, and the like can be mentioned.

In the method (vii), any modification reaction can be used. For example, a method using a compound having a functional group capable of reacting with the terminal reactive group obtained by polymerization and a reactive silicon group, a method using a terminal reactive group, and the like. A method of introducing a double bond at the terminal of the polymer using a compound having a reactive functional group and a double bond and introducing a reactive silicon group into the double bond by hydrosilylation or the like can be used.

In addition, these methods may be used in arbitrary combination. For example, by combining the method (vi) and the method (v), a (meth) acrylic acid ester-based polymer (B) having a reactive silicon group at both the end of the molecular chain and / or the side chain can be obtained.

The (meth) acrylic acid ester-based polymer (B) often contains a polymer containing 40% by weight or more of the alkyl (meth) acrylic acid having 1 to 3 carbon atoms in all the monomers. It is preferable because it becomes rigid. The (meth) acrylic acid ester-based polymer (B) is composed of only a polymer containing 40% by weight or more of the alkyl (meth) acrylic acid having 1 to 3 carbon atoms in the total monomer. Although it may be present, a polymer containing 40% by weight or more of alkyl (meth) acrylate having 4 to 30 carbon atoms of alkyl in the total monomer is also contained together with the polymer, and both are blended. This is preferable because it improves rigidity, elongation, and strength.

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

Next, the (meth) acrylic acid ester-based polymer (B) polymerized using a macromonomer, which is one of the preferred embodiments of the (meth) acrylic acid ester-based polymer (B) used in the present invention, will be described. To do.

The (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer is a monomer (b1) having a reactive silicon group represented by the above general formula (1) and a polymerizable unsaturated group. , And a polymer having a macromonomer (b2), which is a (meth) acrylic acid ester-based polymer having a polymerizable unsaturated group, as a constituent monomer. The polymer may further contain a (meth) acrylic acid alkyl ester (b3) having an alkyl having 1 to 3 carbon atoms as a constituent monomer. In the present application, "(meth) acrylic" means "acrylic and / or methacrylic".

(Monomer having a reactive silicon group and a polymerizable unsaturated group (b1))
Examples of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, and 3-(. Compounds having a (meth) acryloxy group and a reactive silicon group, such as (meth) acryloxypropyldimethoxymethylsilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyl Examples thereof include compounds having a vinyl group such as triethoxysilane and a reactive silicon group. Only one of these compounds may be used, or two or more of these compounds may be used in combination.

The total content of the monomer (b1) having a reactive silicon group and a polymerizable unsaturated group is all the monomers constituting the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer. 0.1 to 50% by weight is preferable, 0.5 to 30% by weight is more preferable, and 1 to 20% by weight is even more preferable.

(Macromonomer (b2))
The macromonomer (b2) is a (meth) acrylic acid ester-based polymer having a polymerizable unsaturated group. Although the macromonomer (b2) itself is a polymer, it can be copolymerized with a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group by the polymerizable unsaturated group. It is a monomer constituting the (meth) acrylic acid ester-based polymer (B).

The main chain skeleton of the macromonomer (b2) is a (meth) acrylic acid ester-based polymer. The monomer constituting the main chain skeleton of the macromonomer (b2) is not particularly limited, and various types can be used. Examples of the (meth) acrylic monomer include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, and isopropyl (meth) acrylic acid. N-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) N-Heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, (meth) acrylate 2-Hydroxyethyl, 2-hydroxypropyl (meth) acrylic acid, ethylene oxide adduct of (meth) acrylic acid, 2,2,2-trifluoroethyl (meth) acrylic acid, 3,3,3 (meth) acrylic acid -Trifluoropropyl, 3,3,4,5,4-pentafluorobutyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate-2-perfluorobutylethyl (meth) acrylate, trifluoromethyl (meth) acrylate , (Meta) perfluoroethyl acrylate, (meth) bis (trifluoromethyl) methyl 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 Examples include furfuryl, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate and the like.

Further, another monomer exhibiting copolymerizability with the above (meth) acrylic monomer may be used. Examples of other monomers include styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, and styrenesulfonic acid; and fluorine-containing vinyls such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride. Monomer; maleic acid such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and its derivatives; fumaric acid such as fumaric acid, fumaric acid monoalkyl ester, fumaric acid dialkyl ester and its derivatives; Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; vinyl acetate, vinyl propionate, vinyl pivalate, etc. Vinyl ester-based monomers such as vinyl benzoate and vinyl cinnate; olefin-based monomers such as ethylene and propylene; conjugated diene-based monomers such as butadiene and isoprene; (meth) acrylamide; (meth) acrylonitrile; chloride Examples thereof include vinyl-based monomers such as vinyl, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. Only one type of other monomer may be used, or two or more types may be used in combination.

The macromonomer (b2) has a polymerizable unsaturated group, which exhibits polymerizable properties. In the macromonomer (b2), the polymerizable unsaturated group may be introduced into either the molecular chain end or the side chain of the (meth) acrylic acid ester-based polymer, but from the viewpoint of adhesiveness, the molecular chain end It is preferable that it is introduced in.

The polymerizable unsaturated group of the macromonomer (b2) is not particularly limited as long as it is an unsaturated group exhibiting polymerizable properties in a general radical polymerization method. For example, an acryloyl group, a methacryloyl group, a vinyl group, or an allyl group. , Metalyl group and the like. Acryloyl group and methacryloyl group are preferable because they show good polymerizability.

The method for introducing a polymerizable unsaturated group into the macromonomer (b2) is not particularly limited, and for example, the methods shown in (viii) to (x) below can be used.
(Viii) A method of copolymerizing a monomer having two kinds of polymerizable unsaturated groups having different reactivity (for example, allyl acrylate) together with a monomer having a (meth) acrylic structure.
(Ix) A compound having a polymerizable unsaturated group and a reactive functional group (Z group) (for example, acrylic acid, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth) acrylic structure, and then polymerized. A method of reacting a compound having a sex unsaturated group and a functional group that reacts with a Z group (for example, diethyl isocyanate (meth) acrylate).
(X) A method in which a monomer having a (meth) acrylic structure is polymerized by a living radical polymerization method, and then a polymerizable unsaturated group is introduced at the end of the molecular chain.

In addition, these methods may be used in arbitrary combination.
Of these methods, the method (x) is preferably used because a polymerizable unsaturated group can be introduced at the end of the molecular chain. The "living radical polymerization method" uses, for example, a cobalt porphyrin complex as shown in the Journal of American Chemical Society (J. Am. Chem. Soc), 1994, Vol. 116, p. 7943. As an initiator, those using nitrooxide radicals as shown in JP-A-2003-570378, organic halides and halide sulfonyl compounds as shown in JP-A-11-130931 are used 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 at the terminal.

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

The polymerizable unsaturated group of the macromonomer (b2) preferably has a structure represented by the following general formula (4).
CH ₂ = C (R ⁶ ) -COO-Z (4)
(In the formula, R ⁶ represents a hydrogen or methyl group. Z represents the main clavicle 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, further preferably 5,000 or more, and preferably 50,000 or less, more preferably 30,000. It is as follows. When the number average molecular weight of the macromonomer (b2) is small, the viscosity of the (meth) acrylic acid ester-based polymer (B) is low, but good adhesiveness tends not to 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 and handling tends to be difficult.

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

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

The (meth) acrylic acid ester-based polymer (B) is composed of a macromonomer (b2) and other monomers, and the main chain of the (meth) acrylic acid ester-based polymer (B) is a trunk chain. The polymer chain branched from the trunk chain derived from the macromonomer (b2) is called a branch chain. The monomers constituting the trunk chain and the branch chain are composed of the above-mentioned monomers and are not particularly limited. It is preferable that the Tg of the branch chain is lower than the Tg of the trunk chain because good adhesiveness can be obtained.

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

The Tg of the branch chain is preferably −100 ° C. to 150 ° C., more preferably −90 ° C. to 100 ° C., and 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, the glass transition temperature (Tg) described in POLYMER HANDBOOK-FOURTH EDITION- (J. Brandrup et al.) Is referred to. When calculating Tg from the Fox formula, the calculation does not include the monomer having a reactive silicon group.

The total content of the macromonomer (b2) is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, based on all the monomers constituting the (meth) acrylic acid ester-based polymer (B). ~ 30% by weight is 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 must be introduced into the side chain from the viewpoint of adhesiveness. Is preferable. The number of macromonomers contained in one molecule of the (meth) acrylic acid ester-based polymer (B) is preferably 0.01 or more, more preferably 0.03 or more, still more preferably 0.05 or more, on average. Further, it is preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.3 or less.

((Meta) acrylic acid alkyl ester (b3))
The alkyl group constituting the (meth) acrylic acid alkyl ester (b3) has 1 to 3 carbon atoms. Specific examples of the (b3) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Only one type of these may be used, or two or more types may be used in combination.

The total content of the (meth) acrylic acid alkyl ester (b3) is the total content of the (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer from the viewpoint of achieving both flexibility and high rigidity. It is preferably 40% by weight or more, more preferably 45% by weight or more, and further preferably 50% by weight or more with respect to the monomer. In order to ensure compatibility with the polyoxyalkylene polymer (A), it is preferably 70% by weight or less, and more preferably 65% by weight or less.

The (meth) acrylic acid ester-based polymer (B) polymerized using the macromonomer constitutes at least a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer (b2). Although it is a polymer as a monomer, it may contain a (meth) acrylic acid alkyl ester (b3) having an alkyl carbon number of 1 to 3 or a monomer other than these as a constituent monomer. .. Specific examples of such monomers include (meth) acrylic monomers that do not fall under (b1) to (b3) and monomers other than (meth) acrylic monomers. It is possible to use various monomers exemplified for the macromonomer (b2).

The (meth) acrylic acid ester-based polymer (B) polymerized using a macromonomer copolymerizes a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group with another monomer. It is synthesized by. As a result, reactive silicon groups can be randomly introduced into the main chain of the polymer. However, in order to further introduce a reactive silicon group into the (meth) acrylic acid ester-based polymer (B), the above-mentioned method can also be used in combination.

The monomer composition of the (meth) acrylic acid ester-based 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 preferable. , 0 ° C. or higher and 200 ° C. or lower, and more preferably 20 ° C. or higher and 100 ° C. or lower with Tg. Tg can be obtained from the Fox formula described above.

The number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is not particularly limited, but the polystyrene-equivalent molecular weight measured by GPC is preferably 500 to 50,000, more preferably 500 to 30,000, and 1,000. ~ 10,000 is particularly preferable. Among them, the number average molecular weight of the (meth) acrylic acid ester-based polymer (B) is preferably 3000 or less because it exhibits good adhesiveness even after the moist heat resistance test.

The method for blending the (meth) acrylic acid ester polymer (B) and the polyoxyalkylene polymer (A) is described in JP-A-59-122541, JP-A-63-112642, and JP-A-6-. It has been proposed in Japanese Patent Application Laid-Open No. 172631 and Japanese Patent Application Laid-Open No. 11-116763. In addition, 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.

The weight ratio (A): (B) of the polyoxyalkylene polymer (A) to the (meth) acrylic acid ester polymer (B) is preferably 95: 5 to 50:50. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Further, in terms of achieving both high rigidity and flexibility, (A): (B) is preferably 80:20 to 50:50, and more preferably 70:30 to 50:50.

<< Epoxy resin (C) >>
Examples of the epoxy resin (C) include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame-retardant epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, and hydrogenated bisphenol A type epoxy resin. , Bisphenol A propylene oxide adduct glycidyl ether type epoxy resin, p-oxybenzoate glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy Resins, N, N-diglycidyl aniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydride-in epoxy resins, petroleum resins. Epoxy products of unsaturated polymers such as, etc. are exemplified, but the present invention is not limited to these, and commonly used epoxy resins can be used. An epoxy resin having at least two epoxy groups in one molecule is preferable because it has high reactivity at the time of curing and the cured product easily forms a three-dimensional network. More preferable ones include bisphenol A type epoxy resins and novolak 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 used so as to be 90: 10 to 50:50. When the ratio of (A + B) is larger than 90%, the strength is lowered, and when the ratio is less than 50%, the flexibility is lowered and the hardness becomes too hard. Further, 80:20 to 60:40 is more preferable in terms of the balance between flexibility and strength.

Young's modulus is an index showing rigidity, and control of Young's modulus shown by a cured product obtained by curing the curable composition of the present invention is the polyoxyalkylene polymer (A) and (meth) specified in the present invention. It can be arbitrarily adjusted by the weight ratio of the acrylic acid ester polymer (B) and the epoxy resin (C). For example, in order to prepare a cured product having a Young's modulus of less than 100 MPa measured at 23 ° C., (A): (B) is 95: 5 to 60:40, and (A + B): (C) is 90:10. It is preferably ~ 60: 40.

Further, in order to adjust a cured product having a Young's modulus of 100 MPa or more measured at 23 ° C., (A): (B) is set to 80:20 to 50:50, and (A + B): (C) is set to 80:20. It is preferably ~ 50:50.

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

As the epoxy resin curing agent (D) 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, dimethylaminomethylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, tripropylamine, DBU, DBN and their tertiary Examples of salts of amines can be exemplified, but are not limited thereto. Further, two or more kinds may be used in combination, or a known epoxy resin curing agent other than the component (D) may be further added.

The epoxy resin curing agent (D) having a tertiary amine is preferably an aromatic amine. Specifically, disubstituted represented by the formula: -CH _2- NR ⁷ R ⁸ (in the formula, R ⁷ and R ⁸ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, respectively). An aromatic compound having two or more aminomethyl groups in the molecule is more preferable, and an aromatic compound having three or more disubstituted aminomethyl groups in the molecule is further preferable. The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. Examples of the aromatic compound include 2,4,6-tris (dimethylaminomethyl) phenol.

The amount of the epoxy resin curing agent (D) used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin (C). It is more preferably 0.5 to 10 parts by weight.

Further, from the viewpoint of enhancing the effect of suppressing the decrease in elongation after curing and curing, the content ratio of the epoxy resin curing agent (D) in the curable composition of the present invention is 100% by weight of the entire curable composition. It is preferably 4% by weight or more, and more preferably 4.5% by weight or more. The upper limit of the content ratio is not particularly limited, but is preferably 25% by weight or less, more preferably 15% by weight or less, and further preferably 10% by weight or less.

<< Phenolic compound (E) >>
The phenolic compound (E) is an organic compound having a phenolic hydroxyl group and is selected from the group consisting of an unsubstituted phenol and a substituted phenol having one or two substituents on the benzene ring. Is. A curable composition containing this compound, a reactive silicon group-containing polyoxyalkylene polymer (A), a reactive silicon group-containing (meth) acrylic acid ester polymer (B), and an epoxy resin (C). By blending with the product, it is possible to provide a curable composition in which a decrease in elongation of the cured product, which can proceed by the curing curing step, is suppressed.

As the phenolic compound (E), a ferrule compound having no amino group is preferable, and a compound having no reactive group other than a phenolic hydroxyl group is more preferable. The phenolic compound (E) may be a compound having only one phenolic hydroxyl group in one molecule, or a compound having two or more phenolic hydroxyl groups. Further, it may be a compound having only one benzene ring, or a compound having two or more benzene rings.

The phenolic compound (E) is a compound selected from the group consisting of an unsubstituted phenol and a substituted phenol having one or two substituents on the benzene ring. The substituent is not particularly limited, and examples thereof include an organic group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 1 to 12 carbon atoms. It is a hydrogen group. The hydrocarbon group may be saturated or unsaturated. The bond position of the substituent of the substituted phenol on the benzene ring is not particularly limited.

Specific examples of the phenolic compound (E) include phenol, mono-substituted alkylphenol (specifically, cresol, ethylphenol, butylphenol, pentylphenol, hexylphenol, nonylphenol, dodecylphenol, etc.), 4-cumyl. Examples thereof include phenol, naphthol, bisphenol A, and catechol. Of these, mono-substituted alkylphenols are preferred.

The amount of the phenolic compound (E) used is preferably 1 to 40 parts by weight, more preferably 3 to 35 parts by weight, and 5 to 25 parts by weight with respect to 100 parts by weight of the epoxy resin (C). Is more preferable.

From the viewpoint of enhancing the effect of suppressing the decrease in elongation after curing and curing, the ratio of the total amount of hydroxyl groups of the epoxy resin curing agent (D) and the phenolic compound (E) to the amount of epoxy of the epoxy resin (C) is set to a certain value or more. It is preferable to mix each component so as to be. Specifically, [(Epoxy resin curing agent (D) hydroxyl equivalent Eqa (eq / g)) × (Epoxy resin curing agent (D) compounding weight) + (Phenolic compound (E) hydroxyl equivalent Eqa ( eq / g)) × (blended weight of phenolic compound (E))] / [(epoxy equivalent of epoxy resin (C) Eqb (eq / g)) × (blended weight of epoxy resin (C))] is 0 It is preferably .25 or more, more preferably 0.30 or more, further preferably 0.35 or more, and particularly preferably 0.40 or more. Each hydroxyl group equivalent and epoxy equivalent can be measured by a conventional method. In addition, the same unit value may be used as the compounding weight of each component.

When the epoxy resin curing agent (D) is an aromatic compound having two or more disubstituted aminomethyl groups represented by the _{formula: -CH 2-} NR ⁷ R ^{8 in the molecule, the decrease in elongation after curing is reduced.} From the viewpoint of enhancing the suppressing effect, the epoxy resin (C) and the epoxy resin curing agent (D) are arranged so that the ratio of the amount of _{−CH 2} −NR ⁷ R ⁸ to the epoxy amount of the epoxy resin (C) is equal to or more than a certain value. Is preferably blended. Specifically, [((-CH _2- NR ⁷ R ⁸ ) equivalent of epoxy resin curing agent (D) Eqc (eq / g)) × (blending weight of epoxy resin curing agent (D))] / [( The epoxy equivalent of the epoxy resin (C) Eqb (eq / g)) × (blending weight of the epoxy resin (C)) is preferably 0.35 or more, more preferably 0.40 or more, and 0. It is more preferably .60 or more, and particularly preferably 0.80 or more. The (-CH _2- NR ⁷ R ⁸ ) equivalent and the epoxy equivalent can be measured by a conventional method. In addition, the same unit value may be used as the compounding weight of each component.

<< Silanol Condensation Catalyst (F) >>
The purpose of the present invention is to promote the reaction of condensing the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B), and to extend or crosslink the polymer. A silanol condensation catalyst (F) is used.

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

Specific examples of the organic tin compound include dibutyl tin dilaurate, dibutyl tin dioctanoate, dibutyl tin bis (butyl maleate), dibutyl tin diacetate, dibutyl tin oxide, dibutyl tin bis (acetylacetonate), and dioctyl tin bis (acetylacetate). Nart), dioctyl tin dilaurate, dioctyl tin distearate, dioctyl tin diacetate, dioctyl tin oxide, reaction product of dibutyl tin oxide and silicate compound, reaction product of dioctyl tin oxide and silicate compound, dibutyl tin oxide and phthalate ester Such as the reactants of.

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

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

Specific examples of the carboxylic acid 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) and diisopropoxytitanium bis (ethylacetatete), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetate. Examples thereof include aluminum compounds such as, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

The amount of the silanol condensation catalyst (F) used is 0.001 to 20 parts by weight based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). Is more preferable, and 0.01 to 15 parts by weight is more preferable, and 0.01 to 10 parts by weight is particularly preferable.

<< Water (G) >>
Water (G) may be added to the agent B of the composition of the present invention. By adding water, the curing of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B) is promoted when the agent A and the agent B are mixed.

The amount of water (G) added is preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). 0.1 to 5 parts by weight is more preferable, and 0.1 to 2 parts by weight is further preferable. Further, the composition of the present invention may contain an agent C containing water (G) in addition to the agent A and the agent B. In this case, the composition of the present invention is a three-component type.

<< Other additives >>
The composition of the present invention includes a polyoxyalkylene polymer (A), a (meth) acrylic acid ester polymer (B), an epoxy resin (C), an epoxy resin curing agent (D), and a phenol compound (E). ), Cyranol condensation catalyst (F), water (G), as additives, fillers, adhesiveness-imparting agents, sagging inhibitors, antioxidants, light stabilizers, ultraviolet absorbers, tackifier resins, etc. Resin, may be added. Further, various additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product. Examples of such additives include, for example, plasticizers, solvents, diluents, photocurable substances, oxygen curable substances, surface improvers, silicates, curability modifiers, radical inhibitors, metal inactivations. Examples thereof include agents, ozone deterioration inhibitors, phosphorus-based peroxide decomposing agents, lubricants, pigments, fungicides, flame retardants, and foaming agents.

<Filler>
Various fillers can be added to the composition of the present invention. Fillers include heavy calcium carbonate, collagen carbonate, magnesium carbonate, silicic acid, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, molten silica, silicic acid anhydride, and hydrous silicic acid. Examples thereof include alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament. It is more preferable to use fumed silica because thixotropic property can be efficiently imparted. Hydrophobic fumed silica is more preferred because it can further enhance thixotropic properties. Known surface treatment agents for hydrophobic fumed silica can be used, but those treated with dimethylsiloxane are more preferable. Further, since a cured product having an excellent balance between Young's modulus and elongation can be obtained, it is preferable to use hydrophilic silica and hydrophobic silica in combination.

In the conventional formulation, when fumed silica is blended as a filler, the problem of a decrease in elongation after curing and curing has remarkably occurred. However, when the phenolic compound (E) is blended according to the present invention, the decrease in elongation after curing and curing can be effectively suppressed. Therefore, it is particularly important to blend the phenolic compound (E) in the system containing fumed silica. It is useful.

The amount of the filler used is preferably 0.5 to 100 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). 60 parts by weight is more preferable. The amount of fumed silica used is preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). ~ 15 parts by weight is more preferable, and 3 to 10 parts by weight is particularly preferable.

An organic balloon or an inorganic balloon may be added for the purpose of reducing the weight (lower specific gravity) of the composition.

<Adhesive imparting agent>
An adhesiveness-imparting agent can be added to the composition of the present invention.
As the adhesiveness-imparting agent, a silane coupling agent and a reaction product of the silane coupling agent can be added.

Specific examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, and N-β-aminoethyl-γ-. Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane; γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltri Isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, Examples thereof include mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; and epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. ..

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

The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). In particular, 0.5 to 10 parts by weight is preferable.

<Sauce preventive agent>
If necessary, a sagging inhibitor may be added to the composition of the present invention in order to prevent sagging and improve workability. The sagging inhibitor is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These anti-sauce agents may be used alone or in combination of two or more.

The amount of the sagging inhibitor used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B).

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

The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is preferably 0.2 to 5 parts by weight.

<Light stabilizer>
A light stabilizer can be used in the composition of the present invention. The use of a light stabilizer can prevent photooxidation deterioration of the cured product. Examples of the light stabilizer include benzotriazole-based compounds, hindered amine-based compounds, and benzoate-based compounds, but hindered amine-based compounds are particularly preferable.

The amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). 0.2 to 5 parts by weight is preferable.

<UV absorber>
An ultraviolet absorber can be used in the composition of the present invention. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted trill-based and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable, and commercially available names such as tinubin P, tinubin 213, tinubin 234 and tinubin 326, Examples thereof include chinubin 327, chinubin 328, chinubin 329, and chinubin 571 (all manufactured by BASF).

The amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is preferably 0.2 to 5 parts by weight.

<Adhesive-imparting resin>
A tackifier resin can be added to the composition of the present invention for the purpose of enhancing the adhesiveness and adhesion to the base material, or if necessary. The tackifying resin is not particularly limited, and a commonly used resin can be used.

Specific examples include terpen-based resins, aromatic-modified terpene resins, hydrocarbon-modified terpene resins, terpen-phenol resins, phenol resins, modified phenol resins, xylene-phenol resins, cyclopentadiene-phenol resins, kumaron inden resins, and rosin-based resins. Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and their hydrogen additives, petroleum resins (eg, C5 hydrocarbon resins, C9). Hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin, etc. can be mentioned. These may be used alone or in combination of two or more.

The amount of the tackifier resin used is preferably 2 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth) acrylic acid ester polymer (B). It is more preferable that the amount is 5 to 30 parts by weight.

<< Preparation of curable composition >>
The curable composition of the present invention contains a polyoxyalkylene polymer (A), an acrylic acid ester polymer (B), an epoxy resin curing agent (D), and other additives as the agent A, and B As the agent, it is preferable to mix an epoxy resin (C), a silanol condensation catalyst (F), and other additives, and prepare a two-component type in which the agent A and the agent B are mixed before use. The phenolic compound (E) may be blended in either or both of Agent A and Agent B. Further, in order to accelerate the curing reaction between the polyoxyalkylene polymer (A) and the acrylic ester polymer (B), water (G) may be added to the agent B.

The curable composition of the present invention may be cured at room temperature or may be heat-cured. When joining dissimilar materials with an adhesive, thermal strain due to the difference in linear expansion coefficient of the dissimilar materials may become a problem, especially when heat-curing. Generally, reaction-curable adhesives such as epoxy-based compositions and urethane-based compositions having high rigidity obtain high adhesive strength when heat-cured, and greatly decrease in flexibility, resulting in thermal strain when cooled. May occur. On the other hand, the curable composition of the present invention is rubber-like 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. .. Furthermore, since high rigidity can be exhibited by subsequent room temperature curing, it is possible to produce a highly rigid adhesive that does not generate thermal strain.

The cured product obtained by curing the curable composition of the present invention preferably has a Young's modulus of 90 MPa or more, more preferably 200 MPa or more, at 23 ° C. from the viewpoint of achieving both high rigidity and flexibility. .. Further, the elongation at break at 23 ° C. is preferably 70% or more, and more preferably 80% or more. The method for measuring Young's modulus and elongation at break is as described in the section of Examples.

<< Surface treatment of adherend >>
The curable composition of the present invention can exhibit good adhesiveness 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 having rigid molecular chains such as polyphenylene sulfide, in order to improve the adhesiveness to these adherends and obtain stable adhesive strength, The adherend can be surface-treated in advance by a known method. For example, surface treatment techniques such as sanding treatment, frame treatment, corona discharge, arc discharge, and plasma treatment can be used. Plasma treatment is preferable because it causes less damage to the adherend and stable adhesiveness can be obtained. These surface treatments are also effective for removing the mold release agent used during molding and remaining on the surface of the adherend.

The curable composition of the present invention exhibits desired physical properties by performing a long-term curing and curing step after bonding the adherends, but is cured after the adherends are bonded and before curing. It is preferable to carry out a long-term curing and curing step after obtaining a semi-cured product by subjecting the sex composition to a relatively short-time heating step. In this case, the structural adhesive of the present invention can be suitably used for joining adherends in a continuously implemented line production method.

The conditions in the short-time heating step described above are not particularly limited, and examples thereof include a temperature of 50 to 200 ° C. and a time of 1 minute to 1 hour.

Further, the conditions of the final curing curing step for the curable composition of the present invention to exhibit 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. And so on.

<< Applications >>
The composition of the present invention is suitable for use as an adhesive composition, and can be used as a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, an adhesive, a waterproof material, and the like. The cured product obtained by curing the curable composition of the present invention has flexibility in spite of its high rigidity, and can be used as an adhesive, particularly a structural adhesive, among the above-mentioned applications. More preferred. In particular, when joining dissimilar materials such as aluminum-steel and aluminum-composite, the linear expansion coefficients of the two are different, so that thermal strain occurs due to temperature changes. In such a case, since an adhesive having high elongation is preferable in order to cope with thermal deformation, the curable composition of the present invention can be suitably used for joining the dissimilar materials. When joining dissimilar materials, it is preferable to cover the joint with a sealer to prevent corrosion. As the sealer, it is possible to use a polymer having a reactive silicon group as shown in the present application. The curable composition of the present invention is used in automobile parts such as vehicle panels, large vehicle parts such as trucks and buses, train vehicle parts, aircraft parts, marine parts, electrical parts, various mechanical parts, and the like. It is preferably used as the adhesive used.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present Examples do not limit the present invention.

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

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

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

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

(Synthesis Example 1)
Using polyoxypropylene glycol having a number average molecular weight of about 2,000 as an initiator, propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst, and the number average molecular weight is 28,500 (terminal group conversion) having hydroxyl groups at both ends. Polyoxypropylene (P-1) having a molecular weight of 17,700) and a molecular weight distribution of Mw / Mn = 1.21 was obtained. 1.0 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl group of the obtained hydroxyl-terminated polyoxypropylene. After evaporating methanol by vacuum volatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of the hydroxyl group-terminated polyoxypropylene, and the reaction was carried out at 130 ° C. for 2 hours. Then, 0.28 molar equivalents of a methanol solution of sodium methoxydo was added to remove methanol, and 1.79 molar equivalents of allyl chloride were added to convert the terminal hydroxyl groups into allyl groups. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with respect to 100 parts by weight of the obtained unpurified allyl group-terminated polyoxypropylene, and then water was removed by centrifugation, and then the obtained hexane solution was obtained. Further, 300 parts by weight of water was mixed and stirred, and water was removed by centrifugation again, and then hexane was removed by vacuum devolatile. From the above, polyoxypropylene (Q-1) having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. It was found that the polymer (Q-1) had an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.

Platinum divinyldisiloxane complex (3 wt% isopropanol solution in terms of platinum) with respect to 100 parts by weight of polyoxypropylene (Q-1) having an average of 2.0 carbon-carbon unsaturated bonds at one terminal site obtained. 36 ppm was added, and 2.2 parts by weight of trimethoxysilane was slowly added dropwise with stirring. After reacting the mixed solution at 90 ° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure to contain an average of 1.6 trimethoxysilyl groups at one terminal site, per molecule. A linear reactive silicon group-containing polyoxypropylene polymer (A-1) having an average of 3.2 silicon groups and a number average molecular weight of 28,500 was obtained.

(Synthesis Example 2)
0.42 parts by weight of cuprous bromide and 20.0 parts by weight of butyl acrylate were added to the deoxidized reactor, and the mixture was heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent and 1.90 parts by weight of ethyl 2-bromoadipate as an initiator were added and mixed, and when the temperature of the mixed solution was adjusted to about 80 ° C., pentamethyldiethylenetriamine (hereinafter referred to as triamine). (Omitted) was added to initiate the polymerization reaction. Then, 80.0 parts by weight of butyl acrylate was sequentially added to proceed with the polymerization reaction. During the polymerization, triamine was appropriately added to adjust the polymerization rate. The total amount of triamine used during the polymerization was 0.15 parts by weight. When the monomer conversion rate (polymerization reaction rate) was about 95% or more, the volatile matter was removed by devolatile under reduced pressure to obtain a polymer concentrate.

The above concentrate is diluted with toluene, a filtration aid, an adsorbent (Kyoward 700SEN: manufactured by Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyowa Chemical Industry Co., Ltd.) are added, and the mixture is heated and stirred at about 80 to 100 ° C. After that, the solid component was removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude polymer product.

A crude polymer product, 1.98 parts by weight of potassium acrylate, 100 ppm by weight of 4-hydroxy-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent were added, and the mixture was reacted at 70 ° C. for 3 hours, and then the solvent was distilled off under reduced pressure to obtain the polymer. A concentrate was obtained. The concentrate was diluted with toluene and the solid components were filtered off. The filtrate was concentrated under reduced pressure to obtain a macromonomer (b2-1) having an acryloyl group at one end, having a number average molecular weight of 10,500 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.18.

(Synthesis Example 3)
48.6 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 ° C. under a nitrogen atmosphere. There, 65.0 parts by weight of methyl methacrylate, 25.0 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2 A mixed solution prepared by dissolving 2.5 parts by weight of 2'-azobis (2-methylbutyronitrile) in 22.7 parts by weight of isobutanol was added dropwise over 5 hours. Further, polymerization is carried out at 105 ° C. for 2 hours, and a reactive silicon group-containing (meth) acrylic acid ester-based polymer (B-1) having an average of 1.6 silicon groups per molecule and a number average molecular weight of 2,300. ) Was obtained (solid content 60%). The reactive silicon equivalent of the solid content is 0.72 mmol / g.

(Synthesis Example 4)
48.0 parts by weight of isobutanol was placed in a four-necked flask equipped with a stirrer, and the temperature was raised to 105 ° C. under a nitrogen atmosphere. There, 60.0 parts by weight of methyl methacrylate, 10.0 parts by weight of stearyl methacrylate, 20 parts by weight of the macromonomer (b2-1) prepared in Synthesis Example 2, 10.0 parts by weight of 3-methacryloxypropyltrimethoxysilane, A mixed solution prepared by dissolving 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane and 2.5 parts by weight of 2,2'-azobis (2-methylbutyronitrile) in 22.7 parts by weight of isobutanol over 5 hours. Dropped. Further, polymerization was carried out at 105 ° C. for 2 hours, and an isobutanol solution (solid content 60) of a reactive silicon group-containing (meth) acrylic acid ester-based polymer (B-2) having a number average molecular weight of 2,120 (GPC molecular weight) was obtained. %) Was obtained. The macromonomer equivalent of the solid content of the solution is 0.018 mmol / g, and the reactive silicon group equivalent is 0.72 mmol / g.

(Example 1)
42 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the (meth) acrylic acid ester-based polymer (B-2) obtained in Synthesis Example 4 are solidified. After mixing so that the portion was 28 parts by weight, isobutanol was heated and devolatile. 7 parts by weight of AncamineK54 (manufactured by 2,4,6-tris (dimethylaminomethyl) phenol ebonic) as an epoxy resin curing agent (D) and 4 parts by weight of 4-tert-butylphenol as a phenolic compound (E) in the obtained mixture. , KBM-603 (N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a silane coupling agent, 2 parts by weight, AEROSIL R-202 (hydrophobic fumed) as a filler. A mixture of 2 parts by weight of silica manufactured by Nippon Aerosil Co., Ltd. and 2 parts by weight of AEROSIL 200 (hydrophilic fumed silica manufactured by Nippon Aerosil Co., Ltd.) was designated as Agent A.

36 parts by weight of jER828 (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd.) as epoxy resin (C), 3 parts by weight of Silohobic 200 (hydrophobic colloidal silica Fuji Silicia Chemical Co., Ltd.) as filler, and AEROSIL R -202 (hydrophobic fumed silica manufactured by Nippon Aerosil Co., Ltd.) 1 part by weight, Neostan U-810 (dioctyl tin dilaurate manufactured by Nitto Kasei Co., Ltd.) as a silanol condensation catalyst (F) 0.3 parts by weight, water 0. A mixture of 5 parts by weight was designated as Agent B.

(Dumbbell tension physical characteristics)
Agents A and B were mixed to prepare a sheet having a thickness of about 2 mm, which was heated at 80 ° C. for 15 minutes and then subjected to primary curing curing at 23 ° C. and 50% RH for 7 days. The obtained sheet was punched into a No. 1 dumbbell type (JIS K 6251) and subjected to a tensile strength test at 23 ° C. and 50% RH. 30% stress at elongation (M30), strength at break (TB), elongation at break (EB) and Young's modulus were measured. The tensile physical properties were measured at a tensile speed of 10 mm / min using an autograph (AGS-J) manufactured by Shimadzu Corporation. Young's modulus was measured in the range of displacement of 0.05 to 0.3%. The results are shown in Table 1.

Further, the sheet after the completion of the primary curing curing is subjected to the secondary curing curing at 50 ° C. for 14 days, and the obtained sheet is punched into a No. 1 dumbbell mold in the same manner as described above to perform a tensile strength test. It was. The results are shown in Table 1.

Further, the retention rate of the elongation at break (EB) is calculated by the formula: 100 × the elongation at break after the secondary curing (EB) / the elongation at break after the primary curing (EB). The results are shown in Table 1.

(Example 2-9, Comparative Example 1-2, and Reference Example 1-2)
A composition was prepared in the same manner as in Example 1 except that the composition was changed to that shown in Table 1-3, and the dumbbell tensile physical properties were evaluated. The results are shown in Table 1-3.

The following compounds were used in each table.
(1): 2,4,6-tris (dimethylaminomethyl) phenol (Evonik)
(2): N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
(3): Hydrophobic fumed silica (Nihon Aerosil Co., Ltd.)
(4): Hydrophilic fumed silica (Nihon Aerosil Co., Ltd.)
(5): Bisphenol A type epoxy resin (Mitsubishi Chemical Corporation)
(6): Hydrophobic colloidal silica (Fuji Silysia Chemical Ltd.)
(7): Dioctyl tin dilaurate (Nitto Kasei Co., Ltd.)

As shown in Table 1-3, in Examples 1 to 9 in which the phenolic compound (E) was blended, the retention rate of the elongation at break (EB) after long-term curing and curing was the phenolic compound (E). It is higher than that of Comparative Example 1 or 2 in which is not blended. From this, it can be seen that by blending the phenolic compound (E), the decrease in elongation of the cured product that can proceed in the curing curing step is suppressed.

On the other hand, Reference Example 1 contains a reactive silicon group-containing polyoxyalkylene polymer (A) and an epoxy resin (C), but the reactive silicon group-containing (meth) acrylic acid ester polymer (B). It is a system that does not contain the phenolic compound (E). In this case, the retention rate of EB is extremely high as compared with Comparative Example 1 or 2 containing the reactive silicon group-containing (meth) acrylic acid ester-based polymer (B), which also does not contain the phenolic compound (E). It showed a high number. From this, the problem of reduction in elongation after curing and curing is peculiar to the system (Comparative Examples 1 and 2) in which the reactive silicon group-containing (meth) acrylic acid ester polymer (B) is used in combination. I understand.

Further, in Reference Example 2 in which the phenolic compound (E) was blended with the system of Reference Example 1, the retention rate of EB was lower than that in Reference Example 1. From this, the effect of suppressing the decrease in elongation due to the compounding of the phenolic compound (E) was achieved in the system (each reference example) not containing the reactive silicon group-containing (meth) acrylic acid ester polymer (B). However, it can be said that the effect is remarkable in the system (each example) in which the polymer (B) is blended.

Claims (12)

A polyoxyalkylene polymer (A) having a reactive silicon group represented by the general formula (1), a (meth) acrylic acid ester polymer (B) having a reactive silicon group represented by the general formula (1), and A agent containing, epoxy resin curing agent (D), and
Agent B containing an epoxy resin (C) and a silanol condensation catalyst (F),
A multi-component curable composition containing
Either or both of Agent A and Agent B contain a phenolic compound (E) selected from the group consisting of an unsubstituted phenol and a substituted phenol having one or two substituents on the benzene ring. , Multi-component curable composition.
-SiR ⁵ _c X _3-c (1)
(Wherein, R ⁵ is a hydrocarbon group of a substituted or unsubstituted C 1 to 20 .X is .c showing a hydroxyl group or a hydrolyzable group is 0 or 1.) The multi-component curable composition according to claim 1, wherein the content ratio of the epoxy resin curing agent (D) is 4% by weight or more in the entire curable composition. [(Epoxy resin curing agent (D) hydroxyl equivalent Eqa (eq / g)) × (Epoxy resin curing agent (D) compounding weight) + (Phenolic compound (E) hydroxyl equivalent Eqa (eq / g)) × (blended weight of phenolic compound (E))] / [(epoxy equivalent of epoxy resin (C) Eqb (eq / g)) × (blended weight of epoxy resin (C))] is 0.25 or more. , The multi-component curable composition according to claim 1 or 2. The epoxy resin curing agent (D) is represented by the formula: -CH _2- NR ⁷ R ⁸ (in the formula, R ⁷ and R ⁸ are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, respectively). The multi-component curable composition according to any one of claims 1 to 3, which is an aromatic compound having two or more disubstituted aminomethyl groups in the molecule. [((-CH _2- NR ⁷ R ⁸ ) equivalent of epoxy resin curing agent (D) Eqc (eq / g)) x (blending weight of epoxy resin curing agent (D))] / [(Epoxy resin (C) The multi-component curable composition according to claim 4, wherein the epoxy equivalent of Eqb (eq / g) x (blending weight of the epoxy resin (C))) is 0.35 or more. The terminal site of the polyoxyalkylene polymer (A) has a general formula (2):

(In the formula, R ¹ and R ³ are independently divalent carbon atoms 1 to 6 bonding groups, and the atoms bonded to the respective carbon atoms adjacent to ^{R 1} and R ^{3 are carbon, oxygen, and nitrogen.} R ² and R ⁴ are each independently hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. N is an integer of 1 to 10. R ⁵ is a substituted or unsubstituted carbon. The multiple according to any one of claims 1 to 5, represented by the number 1 to 20 of the hydrocarbon group, X being a hydroxyl group or a hydrolyzable group, and c indicating 0 or 1). Liquid curable composition. The multi-component curable composition according to claim 6, wherein R ¹ is CH ₂ OCH ₂ and R ³ is CH _2. The multi-component curable composition according to claim 6 or 7, wherein R ² and R ^{4 are hydrogen atoms, respectively.} The (meth) acrylic acid ester-based polymer (B) is a monomer (b1) having a reactive silicon group and a polymerizable unsaturated group, and a (meth) acrylic acid ester-based polymer having a polymerizable unsaturated group. The multi-component curable composition according to any one of claims 1 to 8, which is a polymer having the macromonomer (b2) as a constituent monomer. The curable composition according to any one of claims 1 to 9, wherein either or both of the agent A and the agent B further contain fumed silica as a filler. A structural adhesive comprising the multi-component curable composition according to any one of claims 1 to 10. A cured product obtained by curing the multi-component curable composition according to any one of claims 1 to 10.