WO2023090255A1

WO2023090255A1 - Multi-part type curable composition

Info

Publication number: WO2023090255A1
Application number: PCT/JP2022/041972
Authority: WO
Inventors: 聖宮藤
Original assignee: 株式会社カネカ
Priority date: 2021-11-18
Filing date: 2022-11-10
Publication date: 2023-05-25
Also published as: JPWO2023090255A1; CN118251461A

Abstract

Provided is a multi-part type curable composition that comprises a main agent containing an organic polymer having a reactive silicon group and an assistant containing water, and that can improve the adhesive property thereof with respect to plastic base materials. This multi-part type curable composition contains an agent A and an agent B. The agent A contains: a polyoxyalkylene-based polymer (A) having a reactive silicon group; a (meth)acrylic acid ester-based polymer (B) having a reactive silicon group; and at least one compound (C) selected from the group consisting of dialkoxy dialkyl silanes, dialkoxy diaryl silanes, and alkyl sulfonic acid esters. The agent B contains: at least one compound selected from the group consisting of the polyoxyalkylene-based polymer (A) having a reactive silicon group, the (meth)acrylic acid ester-based polymer (B) having a reactive silicon group, and a plasticizing agent (D); an inorganic filler (E); and water (F). One or both of the agent A and the agent B contain a silanol condensation catalyst (G).

Description

Multi-component curable composition

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

Organic polymers having hydroxyl groups or hydrolyzable groups on silicon atoms and having silicon groups capable of forming siloxane bonds by hydrolysis/condensation reactions (hereinafter also referred to as "reactive silicon groups") are It is known to cure with moisture contained in to give a rubber-like cured product. Such polymers are used as adhesives, sealants, fillers, etc. by utilizing their physical properties.

However, moisture-curable compositions containing such polymers are said to be insufficient in depth curability because the progress of the curing reaction depends on moisture in the air, and curing progresses from the surface of the applied composition. There's a problem.

Therefore, it has been reported that deep-part curability is improved by constructing a two-liquid type composition in which an organic polymer having a reactive silicon group is used as a main component and water is used as an auxiliary agent (for example, Patent Document 1).

U.S. Patent Application Publication No. 2007/0088110

However, it has been found that such a two-component composition containing water as a coagent tends to have lower adhesion to plastic substrates than a one-component composition that cures with moisture. bottom.

In view of the above-mentioned current situation, the present invention provides a multicomponent curable composition containing a main agent containing an organic polymer having a reactive silicon group and an auxiliary agent containing water, which has improved adhesion to plastic substrates. It is an object of the present invention to provide a possible multi-component curable composition.

The inventors of the present invention have made intensive studies to solve the above problems, and have found that a polyoxyalkylene-based polymer and a (meth)acrylic acid ester-based polymer are used in combination as the organic polymer having a reactive silicon group in the main agent. The above problems are solved by blending a specific compound and blending an inorganic filler together with a polyoxyalkylene polymer having a reactive silicon group and / or a plasticizer in an auxiliary agent containing water. I found that it can be done, and completed the present invention.

That is, the present invention is a multi-component curable composition containing agent A and agent B, wherein agent A is a polyoxyalkylene polymer (A) having a reactive silicon group and a reactive silicon group ( A meth)acrylic acid ester-based polymer (B) and at least one compound (C) selected from the group consisting of dialkoxydialkylsilanes, dialkoxydiarylsilanes, and alkylsulfonic acid esters, and agent B Is selected from the group consisting of a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a plasticizer (D) containing at least one compound, an inorganic filler (E), and water (F); either or both of agent A and agent B contain a silanol condensation catalyst (G); The present invention relates to a multi-component curable composition in which the group is represented by the following general formula (1).
—SiR ¹ _3-a X _a (1)
(Wherein, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a is 2 or 3.)
Preferably, agent A contains a dialkoxydiarylsilane as compound (C).
Preferably, agent A contains a dialkoxydiarylsilane and an alkylsulfonate as compound (C).
Preferably, the (meth)acrylic acid ester polymer (B) contains 40% by weight or more of the total monomers of alkyl (meth)acrylates having 1 to 3 carbon atoms.
Preferably, the A agent further contains an amino group-containing silane coupling agent (H).
Preferably, the multi-component curable composition is a two-component curable composition comprising an A agent and a B agent.
The present invention also relates to a cured product obtained by curing the multicomponent curable composition.

According to the present invention, there is provided a multicomponent curable composition comprising a main component containing an organic polymer having a reactive silicon group and an auxiliary agent containing water, wherein the multicomponent curable composition is capable of improving adhesion to plastic substrates. A liquid curable composition can be provided.
According to a preferred aspect of the present invention, it is possible to achieve both the dischargeability of a mixture obtained by mixing a main agent and an auxiliary agent and the shape retention property of a coating film obtained by coating the mixture on a substrate.

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

This embodiment is a multicomponent curable composition containing at least an A agent and a B agent.
Agent A includes at least a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic acid ester polymer (B) having a reactive silicon group, a dialkoxydialkylsilane, a dialkoxy It contains at least one compound (C) selected from the group consisting of diarylsilanes and alkylsulfonic acid esters.
Agent B comprises at least a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylate polymer (B) having a reactive silicon group, and/or a plasticizer (D). It contains at least one compound selected from the group, an inorganic filler (E), and water (F).
Either or both of the A agent and the B agent contain a silanol condensation catalyst (G).
In addition, the curable composition according to the present embodiment does not contain an epoxy resin.

<<Polyoxyalkylene Polymer (A) Having Reactive Silicon Group>>
<Reactive silicon group>
The polyoxyalkylene polymer (A) has a reactive silicon group represented by the following general formula (1).
—SiR ¹ _3-a X _a (1)
(Wherein, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a represents 2 or 3.)

The number of carbon atoms in the hydrocarbon group of R ¹ is preferably 1-10, more preferably 1-5, even more preferably 1-3. Specific examples of R ¹ include methyl group, ethyl group, chloromethyl group, methoxymethyl group and N,N-diethylaminomethyl group. Preferred are methyl group, ethyl group, chloromethyl group and methoxymethyl group, and more preferred are methyl group and methoxymethyl group.

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

Specific examples of the reactive silicon group possessed by the polyoxyalkylene polymer (A) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, a triacetoxysilyl group, and dimethoxymethyl silyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N ,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but are not limited thereto. Among these are methyldimethoxysilyl, trimethoxysilyl, triethoxysilyl, (chloromethyl)dimethoxysilyl, (methoxymethyl)dimethoxysilyl, (methoxymethyl)diethoxysilyl, (N,N- Diethylaminomethyl)dimethoxysilyl group is preferred because it exhibits high activity and gives a cured product with good mechanical properties, and a trimethoxysilyl group and a triethoxysilyl group are more preferred because a cured product with high rigidity can be obtained. A trimethoxysilyl group is more preferred.

The polyoxyalkylene polymer (A) may have an average of 1 or less reactive silicon groups at one terminal site, or an average of more than 1 reactive silicon group at one terminal site may have a silicon group. Here, having more than one reactive silicon group on average at one terminal site means that the polyoxyalkylene polymer (A) has two or more reactive silicon groups at one terminal site. It shows that polyoxyalkylene is included.

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

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

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

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

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

The polyoxyalkylene polymer (A) may have an average of 1.0 or less reactive silicon groups at one terminal site. In this case, the average number is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more.

In addition, the polyoxyalkylene polymer (A) may have an average of more than 1.0 reactive silicon groups at one terminal site. In this case, the average number is more preferably 1.1 or more, still more preferably 1.5 or more, and even more preferably 2.0 or more. Moreover, the average number is preferably 5 or less, more preferably 3 or less.

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

The average number of reactive silicon groups per molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, from the viewpoint of the strength of the cured product. , is more preferably 1.3 or more, even more preferably 1.5 or more, and particularly preferably 1.7 or more. The average number may be 2.0 or less, or may be more than 2.0. From the viewpoint of elongation of the cured product, the number is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.

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

The number average molecular weight of the polyoxyalkylene polymer (A) is preferably 3,000 or more and 100,000 or less, more preferably 3,000 or more and 50,000 or less, in terms of polystyrene equivalent molecular weight in GPC, and particularly preferably It is 3,000 or more and 30,000 or less.

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

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

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

<Method for synthesizing polyoxyalkylene polymer (A)>
The method for synthesizing the polyoxyalkylene polymer (A) is not particularly limited. To explain an example, first, an initiator having a hydroxyl group is polymerized with an epoxy compound to obtain a hydroxyl group-terminated polymer. After reacting the hydroxyl groups of the polymer with an alkali metal salt (for example, sodium methoxide), a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond (for example, allyl chloride) is reacted to attach a carbon- Introduce carbon unsaturated bonds. Then, a reactive silicon group-containing polyoxyalkylene polymer (A) can be obtained by reacting a reactive silicon group-containing hydrosilane compound (eg, dimethoxymethylsilane, trimethoxysilane).

A polyoxyalkylene polymer (A) having an average of more than 1.0 reactive silicon groups at one terminal site, which is a preferred embodiment, can be obtained as follows. After reacting the hydroxyl group of the hydroxyl-terminated polymer with the alkali metal salt in the same manner as described above, an epoxy compound having a carbon-carbon unsaturated bond (eg, allyl glycidyl ether) is first reacted, and then the carbon-carbon unsaturated bond is reacted. Two or more carbon-carbon unsaturated bonds are introduced at one end by reacting a halogenated hydrocarbon compound having a saturated bond (eg, allyl chloride). After that, a reactive silicon group-containing hydrosilane compound may be reacted.

It is also possible to introduce a reactive silicon group into the polymer by using a reactive silicon group-containing mercaptosilane instead of the reactive silicon group-containing hydrosilane compound.

The main chain of the polyoxyalkylene polymer (A) is an ester bond or the general formula (3):
-NR ⁶ -C(=O)- (3)
(wherein R ⁶ represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

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

Examples of the amide segment represented by the general formula (3) include the reaction between an isocyanate group and a hydroxyl group, the reaction between an amino group and a carbonate, the reaction between an isocyanate group and an amino group, and the reaction between an isocyanate group and a mercapto group. etc. can be mentioned. The amide segment represented by the general formula (3) also includes those formed by the reaction of the amide segment containing an active hydrogen atom with an isocyanate group.

As an example of a method for producing the polyoxyalkylene polymer (A) containing an amide segment, a polyoxyalkylene having an active hydrogen-containing group at its terminal is reacted with a polyisocyanate compound to produce a polymer having an isocyanate group at its terminal. A compound having both a functional group (for example, a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group) capable of reacting with the isocyanate group and a reactive silicon group after or simultaneously with the synthesis of the coalescence. can be mentioned. Another example is a method of reacting a polyoxyalkylene having an active hydrogen-containing group at its end with a reactive silicon group-containing isocyanate compound.

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

<<(Meth)acrylic acid ester polymer (B) having a reactive silicon group>>
Agent A includes a polyoxyalkylene polymer (A) having a reactive silicon group and a (meth)acrylic acid ester polymer (B) having a reactive silicon group (hereinafter referred to as "(meth)acrylic acid ester (also referred to as "polymer (B)"). This can improve adhesion to plastic substrates.
In addition, the (meth)acrylate polymer (B) is preferably contained in either or both of the A agent and the B agent. Moreover, it is preferable that the (meth)acrylic acid ester-based polymer (B) is blended with the A agent.
The (meth)acrylate monomer constituting the main chain of the (meth)acrylate 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, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-(meth)acrylate -octyl, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, phenyl (meth)acrylate, toluyl (meth)acrylate, (meth)acrylate Benzyl acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate , glycidyl (meth)acrylate, (3-trimethoxysilyl)propyl (meth)acrylate, (3-dimethoxymethylsilyl)propyl (meth)acrylate, (2-trimethoxysilyl)ethyl (meth)acrylate, (2-dimethoxymethylsilyl)ethyl (meth)acrylate, trimethoxysilylmethyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, ethylene oxide adduct of (meth)acrylic acid, (meth)acrylate Trifluoromethylmethyl acrylate, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, ( Meth) perfluoroethyl acrylate, trifluoromethyl (meth) acrylate, bis (trifluoromethyl) methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, (meth) ) (meth)acrylate monomers such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate.

The (meth)acrylate polymer (B) has a reactive silicon group represented by the general formula (1) shown above. The reactive silicon group of the (meth)acrylate polymer (B) may be the same as or different from the reactive silicon group of the polyoxyalkylene polymer (A).

Specific examples of the reactive silicon group possessed by the (meth)acrylate polymer (B) include a trimethoxysilyl group, a triethoxysilyl group, a tris(2-propenyloxy)silyl group, and a triacetoxysilyl group. etc., but not limited to these. Among these, a trimethoxysilyl group and a triethoxysilyl group are more preferable, and a trimethoxysilyl group is even more preferable, since a cured product having a high Young's modulus can be obtained.

The method of introducing a reactive silicon group into the (meth)acrylate polymer (B) is not particularly limited, but for example, a method of copolymerizing a (meth)acrylate monomer having a reactive silicon group, Examples of the chain transfer agent include a method of performing polymerization in the presence of a mercaptosilane compound having a reactive silicon group.
Examples of mercaptosilane compounds having a reactive silicon group include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, (mercaptomethyl)dimethoxymethylsilane, (mercaptomethyl)trimethoxysilane and the like.

The reactive silicon group equivalent of the (meth)acrylate polymer (B) is not particularly limited, but is preferably 0.1 mmol/g or more, more preferably 0.5 mmol/g or more, and 0.6 mmol/g or more. is more preferred. The reactive silicon group equivalent is preferably 2.0 mmol/g or less, and more preferably 1.0 mmol/g or less from the viewpoint of suppressing a decrease in elongation of the cured product.

The (meth)acrylic acid ester-based polymer (B) contains 40% by weight or more of alkyl (meth)acrylate having 1 to 3 carbon atoms in the total monomer, so that the strength becomes high. preferable.

Although the number average molecular weight of the (meth)acrylic acid ester polymer (B) is not particularly limited, it is preferably 500 or more and 50,000 or less, more preferably 500 or more and 30,000 or less, in terms of polystyrene equivalent molecular weight by GPC measurement. ,000 or more and 10,000 or less is particularly preferable.

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

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

<<Compound (C)>>
Compound (C) is at least one compound selected from the group consisting of dialkoxydialkylsilanes, dialkoxydiarylsilanes, and alkylsulfonic acid esters. Compound (C) is included in the A agent. This can improve the adhesiveness of the multi-component curable composition according to the present embodiment to the plastic substrate.

The dialkoxydialkylsilane is a hydrolyzable compound in which two alkoxy groups and two alkyl groups are bonded to a silicon atom.
Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably 1 to 5, more preferably 1 to 3, for example. A methoxy group and an ethoxy group are particularly preferred.
The number of carbon atoms in the alkyl group is also not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3, for example. The alkyl group may or may not have a substituent such as a halogen group or an alkoxy group. However, it preferably does not have reactive substituents such as amino groups, isocyanate groups, mercapto groups, epoxy groups, vinyl groups, (meth)acryloyl groups, and the like.
Specific examples of the alkyl group include methyl group, ethyl group, chloromethyl group, methoxymethyl group and the like. A methyl group is preferred.
Specific examples of the dialkoxydialkylsilane include dimethoxydimethylsilane, diethoxydimethylsilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, t-butylisopropyldimethoxysilane, n-octylmethyldimethoxysilane, and the like. Among these, dimethoxydimethylsilane is particularly preferred.

The dialkoxydiarylsilane is a hydrolyzable compound in which two alkoxy groups and two aryl groups are bonded to a silicon atom.
Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably 1 to 5, more preferably 1 to 3, for example. A methoxy group and an ethoxy group are particularly preferred.
Although the number of carbon atoms in the aryl group is not particularly limited, it is preferably 6 to 10, more preferably 6 to 8, and even more preferably 6, for example. The aryl group may or may not have a substituent such as an alkyl group, a halogen group, or an alkoxy group. However, it preferably does not have reactive substituents such as amino groups, isocyanate groups, mercapto groups, epoxy groups, vinyl groups, (meth)acryloyl groups, and the like.
Specific examples of the aryl group include phenyl group, naphthyl group, methylphenyl group, dodecylphenyl group, chlorophenyl group, methoxyphenyl group and the like. A phenyl group is preferred.
Specific examples of the dialkoxydiarylsilane include dimethoxydiphenylsilane and diethoxydiphenylsilane. Dimethoxydiphenylsilane is particularly preferred.

The alkyl sulfonate ester is a compound known as a plasticizer. Specific examples include alkylsulfonic acid phenyl esters. Commercially available products of the compound include Mesamoll® manufactured by LANXESS.

From the viewpoint of the effect of improving adhesion to plastic substrates, it is preferable to use at least dialkoxydiarylsilane as compound (C). At this time, at least one kind of dialkoxydiarylsilane may be used alone, or a combination of dialkoxydiarylsilane, dialkoxydialkylsilane and/or alkylsulfonic acid ester may be used.

In particular, it is preferable to use a dialkoxydiarylsilane and an alkylsulfonic acid ester together as the compound (C). According to the combined system, in addition to the good effect of improving the adhesion to plastic substrates, the mixture obtained by mixing the main agent and the auxiliary agent can be discharged and the coating film obtained by applying the mixture to the substrate can be obtained. There is an advantage that it is possible to achieve both shape retention.

When a dialkoxydiarylsilane and/or a dialkoxydialkylsilane is used as the compound (C), the amount used is the same as the polyoxyalkylene polymer (A) and (meth ) with respect to a total of 100 parts by weight of the acrylic ester polymer (B), it is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 0.3 parts by weight or more and 15 parts by weight or less, and 0 .5 parts by weight or more and 10 parts by weight or less is more preferable, and 1 part by weight or more and 5 parts by weight or less is particularly preferable.

When an alkylsulfonate ester is used as the compound (C), the amount used is the same as the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer, from the viewpoint of the effect of improving the adhesion to plastic substrates. With respect to the total 100 parts by weight of (B), it is preferably 1 part by weight or more and 120 parts by weight or less, more preferably 5 parts by weight or more and 100 parts by weight or less, and further preferably 10 parts by weight or more and 50 parts by weight or less. 1 part by weight or more and 30 parts by weight or less is particularly preferable.

<<Plasticizer (D)>>
The plasticizer (D) is preferably blended with the B agent. It may be blended only in the B agent, or may be blended in each of the A agent and the B agent. When the plasticizer (D) is blended, the viscosity of the curable composition can be lowered and handling becomes easier. In particular, by blending in the B agent, mixing of the A agent and the B agent can be easily achieved. However, the alkylsulfonic acid ester described above as the compound (C) is not included in this plasticizer (D).
However, instead of blending the plasticizer (D) into the B agent, the polyoxyalkylene polymer (A) and/or the (meth)acrylate polymer (B) may be blended into the B agent. . Mixing of A agent and B agent can be easily realized also by this aspect. Further, the plasticizer (D) and the polyoxyalkylene polymer (A) and/or the (meth)acrylic acid ester polymer (B) may be blended in the B agent.
It is preferable to blend the (meth)acrylate polymer (B), the polyoxyalkylene polymer (A) and/or the plasticizer (D) into the B agent.

The plasticizer (D) is not particularly limited, and examples thereof include phthalates such as dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), and butylbenzyl phthalate. Compounds; terephthalic acid ester compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate; non-phthalic acid ester compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, sebacin Aliphatic polyvalent carboxylic acid ester compounds such as dibutyl acid, diisodecyl succinate, and acetyl tributyl citrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phosphoric acid ester compounds; trimellitic acid ester compounds chlorinated paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oil; epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1, Epoxy plasticizers such as 2-dicarboxylate (E-PS), epoxyoctyl stearate, epoxybutylstearate and benzyl epoxystearate, and the like can be mentioned.
A polymeric plasticizer can also be used as the plasticizer (D). Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyether plasticizers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
Among them, polymer plasticizers are preferred, polyether plasticizers are more preferred, and polypropylene glycol is particularly preferred.
As the plasticizer (D), only one type may be used, or two or more types may be used in combination.

The total blending amount of the plasticizer (D) is 5 to 150 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). is preferred, 10 to 120 parts by weight is more preferred, and 20 to 100 parts by weight is particularly preferred.

<<Inorganic filler (E)>>
The inorganic filler (E) is blended at least with the B agent. It may be blended only in the B agent, or may be blended in each of the A agent and the B agent. The addition of the inorganic filler (E) can improve the strength of the cured product, and the addition of the inorganic filler (E) to the B agent also contributes to the improvement of the stability of the B agent.

The inorganic filler (E) is not particularly limited, but heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, wet silica, crystalline silica, fused silica, anhydrous Silicic acid, hydrous silicic acid, alumina, carbon black, ferric oxide, fine aluminum powder, zinc oxide, activated zinc white, glass fibers and filaments. Among these, calcium carbonate, fumed silica, wet silica, and titanium oxide are preferred.
As the inorganic filler (E), only one type may be used, or two or more types may be used in combination.

The total blending amount of the inorganic filler (E) is 1 to 300 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). is preferred, and 10 to 250 parts by weight is more preferred.

From the viewpoint of improving the stability of agent B, the proportion of the inorganic filler (E) contained in agent B to the total amount of agent B is preferably 10% by weight or more. The proportion is more preferably 15% by weight or more, and even more preferably 20% by weight or more. The upper limit of the ratio is preferably 60% by weight or less, more preferably 50% by weight or less, and even more preferably 40% by weight or less.

<<Water (F)>>
Water (F) is blended with the B agent. By blending water (F), the hydrolysis reaction of the reactive silicon groups of the polyoxyalkylene-based polymer (A) and the (meth)acrylic acid ester-based polymer (B) when the agents A and B are mixed. is promoted, and the expression of initial strength is improved. In addition, since water (F) is blended in the B agent, deterioration of the storage stability of the A agent containing the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) is avoided. can do.

The amount of water (F) added is, from the viewpoint of the effect of improving adhesion to plastic substrates, to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). , preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 0.1 to 3 parts by weight, and 0.1 parts by weight Parts by weight or more and 2 parts by weight or less are particularly preferred.
Further, the proportion of water (F) in the total amount of agent B is preferably 0.5 to 30% by weight. Within this range, mixing of the A agent and the B agent can be easily realized. More preferably 1 to 20% by weight, still more preferably 3 to 15% by weight.

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

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

Specific examples of organic tin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), phosphate), dioctyltin dilaurate, dioctyltin distearate, dioctyltin diacetate, dioctyltin oxide, etc., reaction products of dibutyltin oxide and silicate compounds, reaction products of dioctyltin oxide and silicate compounds, dibutyltin Reaction products of oxides and phthalates are also included.

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

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

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

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetoacetate), aluminum tris (acetylacetonate), and diisopropoxyaluminum ethylacetoacetate. and zirconium compounds such as zirconium tetrakis (acetylacetonate).

The amount of the silanol condensation catalyst (G) used is 100 parts by weight in total of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B) from the viewpoint of promoting the condensation reaction of the reactive silicon group. , preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and even more preferably 0.01 to 10 parts by weight.

<<amino group-containing silane coupling agent (H)>>
Agent A preferably further contains an amino group-containing silane coupling agent (H). Addition of the amino group-containing silane coupling agent (H) can further improve adhesion to plastic substrates.

The amino group-containing silane coupling agent (H) refers to a compound having both an amino group and a hydrolyzable silyl group in one molecule.
The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group, but is preferably a primary amino group or a secondary amino group.

The hydrolyzable silyl group refers to a silyl group having 1 to 3 hydrolyzable groups on a silicon atom. From the viewpoint of improving adhesiveness, a silyl group having two or three hydrolyzable groups is preferred, and a silyl group having three hydrolyzable groups is more preferred. As the hydrolyzable group, the groups described above for X in component (A) can be used. Among them, an alkoxy group is preferable, and a methoxy group or an ethoxy group is particularly preferable.

Specific examples of the amino group-containing silane coupling agent (H) are not particularly limited, but γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyl Dimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, 3- (N-ethylamino)-2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyltrimethoxysilane Silane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ- aminopropyltriethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxy Silane etc. are mentioned.

The amount of the amino group-containing silane coupling agent (H) used is 0.1 weight part with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). parts by weight or more and 20 parts by weight or less, more preferably 0.3 parts by weight or more and 15 parts by weight or less, even more preferably 0.5 parts by weight or more and 10 parts by weight or less, and particularly 1 part by weight or more and 5 parts by weight or less. preferable.

<<Other Additives>>
The curable composition according to the present embodiment includes a polyoxyalkylene polymer (A), a (meth)acrylic acid ester polymer (B), a compound (C), a plasticizer (D), an inorganic filler ( In addition to E), water (F), a silanol condensation catalyst (G), and an optional amino group-containing silane coupling agent (H), additives such as organic fillers, adhesion imparting agents, dehydrating agents, rheology Control agents, antioxidants, light stabilizers, UV absorbers, tackifying resins and other resins may be added.
In addition, various additives may be added to the curable composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the curable composition or cured product. Examples of such additives include solvents, diluents, photo-curing substances, oxygen-curing substances, surface property modifiers, silicates, curability modifiers, radical inhibitors, metal deactivators, ozone Degradation inhibitors, phosphorus-based peroxide decomposers, lubricants, pigments, antifungal agents, flame retardants, foaming agents and the like.

<Adhesion imparting agent>
Adhesion imparting agents can be added to the curable composition.
As the adhesiveness-imparting agent, a silane coupling agent other than the amino group-containing silane coupling agent (H) and a reactant of the silane coupling agent can be added.

Specific examples of silane coupling agents include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane, and the like. isocyanate group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, β- Epoxy group-containing silanes such as (3,4-epoxycyclohexyl)ethyltrimethoxysilane can be mentioned.

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

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

<Dehydrating agent>
A dehydrating agent can be added to the curable composition. A dehydrating agent is preferably added to the A agent to improve the stability of the A agent.
Here, the dehydrating agent is preferably a compound capable of reacting with water, more preferably a silicon compound capable of reacting with water (excluding compounds corresponding to component (C) or component (H)); Alkoxysilane compounds are particularly preferred.

Specific examples of the dehydrating agent include, but are not particularly limited to, vinyl group-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinylmethyldimethoxysilane. Only one type of dehydrating agent may be used, or two or more types may be used.

The amount of the dehydrating agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylic acid ester polymer (B). 5 to 10 parts by weight is more preferable, and 1 to 5 parts by weight is even more preferable.

<Rheology control agent>
If necessary, a rheology control agent may be added to the curable composition to prevent sagging and improve workability. Examples of rheology control agents include, but are not limited to, fatty acid amide waxes, hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These rheology control agents may be used alone or in combination of two or more.

The amount of the rheology control agent used is preferably 0.1 to 20 parts by weight with respect to a total of 100 parts by weight of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B).

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

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

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

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

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

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

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

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

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

<<Curable composition>>
The curable composition according to the present embodiment comprises a polyoxyalkylene polymer (A), an acrylic acid ester polymer (B), an A agent containing a compound (C), and the like, and a polyoxyalkylene polymer ( A), at least one of a (meth)acrylic acid ester polymer (B) and a plasticizer (D), an inorganic filler (E), and a B agent containing water (F), etc. It is preferable to prepare as a multi-liquid type in which agent A and agent B are mixed before use.

The curable composition according to this embodiment may be cured at room temperature or may be cured by heating. The heating temperature is not particularly limited, but is preferably 40° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher. However, if the temperature rises to 100°C or higher, the water in agent B evaporates and may cause voids, so the heating temperature is preferably lower than 100°C.

The curable composition according to the present embodiment can exhibit good adhesion to various adherends such as plastics, metals, and composites, and in particular adhesion to adherends made of plastic. can be improved, it can be suitably used for bonding plastic substrates. Here, the adhesion of plastic substrates may be adhesion between plastic substrates or adhesion between a plastic substrate and another substrate.

The plastic is not particularly limited, and examples include acrylonitrile-butadiene-styrene copolymer (ABS) resin; polycarbonate (PC) resin; polycarbonate alloy resin such as PC/ABS; polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT). ) polyester resin such as resin; polymethyl methacrylate (PMMA) resin; polystyrene (PS) resin; polyimide (PI) resin; polyolefin (PO) resin such as polyethylene, polypropylene, polyisoprene, polybutadiene, polymethylpentene; ; polyisocyanate resin; epoxy resin and the like.

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

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

The conditions of the final curing (curing) step for the curable composition to express the final desired physical properties are not particularly limited, but for example, the temperature is 5 to 90 ° C. and the time is 24 hours to 1 week. be done.

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

[Disclosure items]
Each of the following items is a disclosure of a preferred embodiment.

[Item 1]
A multi-component curable composition comprising agent A and agent B,
Agent A is a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylate polymer (B) having a reactive silicon group, dialkoxydialkylsilane, and dialkoxydiarylsilane. , and containing at least one compound (C) selected from the group consisting of alkylsulfonic acid esters,
Agent B is selected from the group consisting of a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a plasticizer (D). containing at least one compound, an inorganic filler (E), and water (F),
Either or both of the A agent and the B agent contain a silanol condensation catalyst (G),
A multicomponent curable composition, wherein the reactive silicon group is represented by the following general formula (1).
—SiR ¹ _3-a X _a (1)
(Wherein, R ¹ represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a is 2 or 3.)

[Item 2]
2. The multicomponent curable composition according to item 1, wherein agent A contains a dialkoxydiarylsilane as compound (C).

[Item 3]
2. The multi-component curable composition according to item 1, wherein the agent A contains a dialkoxydiarylsilane and an alkylsulfonic acid ester as the compound (C).

[Item 4]
Any one of items 1 to 3, wherein the (meth)acrylic acid ester polymer (B) contains 40% by weight or more of the total monomers of an alkyl (meth)acrylate having 1 to 3 carbon atoms in the alkyl. 2. The multi-component curable composition according to item 1.

[Item 5]
5. The multi-component curable composition according to any one of items 1 to 4, wherein agent A further contains an amino group-containing silane coupling agent (H).

[Item 6]
The multi-component curable composition according to any one of items 1 to 5, which is a two-component curable composition comprising agent A and agent B.

[Item 7]
A cured product obtained by curing the multicomponent curable composition according to any one of items 1 to 6.

Although the present invention will be specifically described below with reference to examples, the present examples are not intended to limit the present invention.

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

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

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

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

(Synthesis example 1)
Polyoxypropylene glycol with a number average molecular weight of about 2,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst. A polyoxypropylene having a molecular weight of 17,700) and a molecular weight distribution of Mw/Mn=1.21 was obtained.
Sodium methoxide was added as a 28% methanol solution in an amount of 1.0 molar equivalent to the hydroxyl group of the obtained hydroxyl group-terminated polyoxypropylene. After methanol was distilled off by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added to the hydroxyl group of hydroxyl-terminated polyoxypropylene, and reaction was carried out at 130° C. for 2 hours. Thereafter, 0.28 molar equivalent of sodium methoxide in methanol was added to remove the methanol, and 1.79 molar equivalent of allyl chloride was added to convert the terminal hydroxyl group to an allyl group. 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred with 100 parts by weight of the unpurified allyl group-terminated polyoxypropylene obtained, and the water was removed by centrifugation. 300 parts by weight of water was further mixed and stirred, the water was removed by centrifugation again, and hexane was removed by vacuum devolatilization. As described above, polyoxypropylene having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. This polymer was found to have an average of 2.0 carbon-carbon unsaturated bonds introduced at one terminal site.
72 ppm of a platinum-divinyldisiloxane complex (3% by weight in terms of platinum in isopropanol solution) was added to 100 parts by weight of polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one end and stirred. 2.2 parts by weight of trimethoxysilane was slowly added dropwise. After the mixed solution was reacted at 90° C. for 2 hours, unreacted trimethoxysilane was distilled off under reduced pressure. A linear reactive silicon group-containing polyoxypropylene polymer (A-1) having an average of 3.2 trimethoxysilyl groups and a number average molecular weight of 28,500 was thus obtained.

(Synthesis example 2)
Polyoxypropylene triol with a number average molecular weight of about 3,000 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 26,200 (terminal group equivalent molecular weight of 17,440). A polyoxypropylene triol was obtained.
Subsequently, a methanol solution of 1.2 equivalents of NaOMe is added to the hydroxyl group of the hydroxyl-terminated polyoxypropylene triol to distill off the methanol, and 1.5 equivalents of 3-chloro-1-propene is added. to convert the terminal hydroxyl group to an allyl group.
Next, 72 ppm of a platinum divinyldisiloxane complex (3% by weight of isopropyl alcohol solution in terms of platinum) was added to 100 parts by weight of the obtained allyl group-terminated polyoxypropylene polymer, and while stirring, 1.26 weight of trimethoxysilane was added. was slowly added dropwise and reacted at 90° C. for 2 hours, and then unreacted trimethoxysilane was distilled off under reduced pressure to give a terminal trimethoxysilyl group and an average of 1 silicon group per molecule. A branched-chain reactive silicon group-containing polyoxypropylene polymer (A-2) having a number average molecular weight of 26,200 was obtained.

(Synthesis Example 3)
A four-necked flask equipped with a stirrer was charged with 42.9 parts by weight of isobutanol, and the temperature was raised to 105° C. under a nitrogen atmosphere. Thereto are 65.0 parts by weight methyl methacrylate, 25.0 parts by weight 2-ethylhexyl acrylate, 10.0 parts by weight 3-methacryloxypropyltrimethoxysilane, 7.2 parts by weight 3-mercaptopropyltrimethoxysilane, and 2 parts by weight , 2′-azobis(2-methylbutyronitrile) dissolved in 16.4 parts by weight of isobutanol was added dropwise over 5 hours. Furthermore, a mixed solution of 0.7 parts by weight of 2,2'-azobis(2-methylbutyronitrile) dissolved in 6.3 parts by weight of isobutanol was added, and polymerization was carried out at 105°C for 2 hours. was 1.6 on average and the number average molecular weight was 2,300. The reactive silicon group equivalent weight of the solid content is 0.72 mmol/g.

(Example 1)
60 parts by weight of the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 and the (meth)acrylate copolymer (B-1) obtained in Synthesis Example 3 After the isobutanol solution was mixed so that the solid content was 40 parts by weight, the isobutanol was devolatilized by heating. To the resulting mixture, 1 part by weight of Nocrac CD (antioxidant, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) and 1 part by weight of ADEKA STAB AO-60 (antioxidant, manufactured by ADEKA Co., Ltd.) were added as stabilizers. (C) Mesamoll (alkyl sulfonic acid phenyl ester, manufactured by ADEKA Co., Ltd.) 11.6 parts by weight, CCR-S10 as a filler (colloidal calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.) 42.4 parts by weight, Asahi 0.05 parts by weight of thermal (carbon black, manufactured by Asahi Carbon Co., Ltd.) and 3 parts by weight of Crayvallac SL (fatty acid amide wax, manufactured by ARKEMA) as a rheology control agent were mixed using a planetary mixer, and then heated at 120°C for 1 hour. It was dehydrated by heating under reduced pressure for 1 hour. The obtained composition was cooled, and 3 parts by weight of A-171 (vinyltrimethoxysilane, manufactured by Momentive) as a dehydrating agent and KBM-603 (N-(2-aminoethyl)-3-aminopropyl Trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by weight, compound (C) Z6447 (dimethoxydiphenylsilane, manufactured by Dow Toray Co., Ltd.) 2 parts by weight, silanol condensation catalyst (G) Neostan U- 0.3 parts by weight of 810 (dioctyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) was mixed to obtain agent A.
Next, Acclaim 12200 (polypropylene glycol having a number average molecular weight of 14,600, manufactured by Covestro AG) as a plasticizer (D) 10.3 parts by weight, CCR-S10 (colloidal calcium carbonate, Shiraishi Kogyo ( Co., Ltd.) 3.2 parts by weight, AEROSIL R-202 (hydrophobic fumed silica, manufactured by Nippon Aerosil Co., Ltd.) 0.6 parts by weight, R-820 (titanium oxide, manufactured by Ishihara Sangyo Co., Ltd.) 2 parts by weight parts and 1.5 parts by weight of water (F) were mixed using a planetary mixer to obtain a B agent.

(Mixing method)
Agent A and Agent B prepared in Example 1 were added to a two-liquid mixing cartridge (NORDSON Co., Ltd. ) made). Using a static mixer with an element diameter of 10 mm and an element number of 24, the A agent and the B agent were mixed to obtain a mixture.

(Adhesiveness)
A PC/ABS alloy (manufactured by Sumitomo Bakelite Co., Ltd., trade name: Roa) used as an adherend was degreased with heptane. After the mixture was applied to one of the adherends, the other adherend was immediately attached so that the adhesion area was 25 mm×12.5 mm and the thickness was 0.5 mm. Using this lamination time as the start time, the laminate was allowed to stand for 7 days under conditions of 23° C. and 50% RH, and then the shear adhesive strength was measured at a test speed of 10 mm/min, and the breaking state was observed. The state of failure was visually confirmed using CF as cohesive failure (destruction at the adhesive portion) and AF as interfacial failure (peeling at the interface between the adhesive and the adherend). When both are mixed, the ratio of each is shown. For example, when the cohesive failure rate is 50% and the interfacial failure rate is 50%, it is described as C50A50. Table 1 shows the results.

(Example 2-8, Comparative Example 1-4)
Agents A and B were prepared and evaluated in the same manner as in Example 1, except that the formulations were changed to those shown in Table 1. Table 1 shows the results.

(Reference example 1)
Agent A was prepared in the same manner as in Example 1, except that the proportions were changed to those shown in Table 1, and evaluated as a one-component curable composition. Table 1 shows the results.

Each component in Table 1 is shown below.
(1): Antioxidant (Ouchi Shinko Chemical Industry Co., Ltd.)
(2): Antioxidant (ADEKA Co., Ltd.)
(3): Alkyl sulfonic acid phenyl ester (ADEKA Corporation)
(4): Diisononyl phthalate (J-Plus Co., Ltd.)
(5): Polypropylene glycol (Mitsui Chemicals, Inc.)
(6): Colloidal calcium carbonate (Shiraishi Industry Co., Ltd.)
(7): Carbon black (Asahi Carbon Co., Ltd.)
(8): Fatty acid amide wax (ARKEMA)
(9): Vinyltrimethoxysilane (Momentive Inc.)
(10): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
(11): Dimethoxydiphenylsilane (Dow Toray Industries, Inc.)
(12): Dimethoxydimethylsilane (Dow Toray Industries, Inc.)
(13): Methyltrimethoxysilane (Dow Toray Industries, Inc.)
(14): Phenyltrimethoxysilane (Dow Toray Industries, Inc.)
(15): Dioctyl tin dilaurate (Nitto Kasei Co., Ltd.)
(16): Polypropylene glycol (Covestro AG)
(17): Hydrophobic fumed silica (Nippon Aerosil Co., Ltd.)
(18): Titanium oxide (Ishihara Sangyo Co., Ltd.)

As shown in Reference Example 1 in Table 1, a polyoxyalkylene polymer (A) having a reactive silicon group, and a (meth)acrylic acid ester copolymer (B) having a reactive silicon group When the agent A containing is used as a one-liquid curable composition for bonding plastic substrates, the failure state is cohesive failure (CF) and the adhesion is good, whereas as shown in Comparative Example 1, If a two-component curable composition in which the same agent A as in Reference Example 1 is combined with an auxiliary agent containing water is used for the same adhesion, interfacial failure (AF) occurs. From this, it can be seen that the two-component curable composition using a water-containing auxiliary has lower adhesiveness to plastic substrates than the one-component curable composition.

As shown in Examples 1 to 8, a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic acid ester copolymer (B) having a reactive silicon group, and a di A two-component curable composition containing at least one compound (C) selected from the group consisting of alkoxydialkylsilanes, dialkoxydiarylsilanes, and alkylsulfonate esters is a comparison containing no compound (C). It can be seen that the adhesiveness to the plastic substrate is better than the two-part curable composition of Examples 1 to 3 and Comparative Example 4 that does not contain the (meth)acrylic acid ester copolymer (B). .

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

Each component in Table 2 is shown below.
(1): Antioxidant (Ouchi Shinko Chemical Industry Co., Ltd.)
(2): Antioxidant (ADEKA Co., Ltd.)
(3): Alkyl sulfonic acid phenyl ester (ADEKA Corporation)
(4): Diisononyl phthalate (J-Plus Co., Ltd.)
(5): Polypropylene glycol (Mitsui Chemicals, Inc.)
(6): Colloidal calcium carbonate (Shiraishi Industry Co., Ltd.)
(7): Carbon black (Asahi Carbon Co., Ltd.)
(8): Fatty acid amide wax (ARKEMA)
(9): Vinyltrimethoxysilane (Momentive Inc.)
(10): N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)
(11): Dimethoxydiphenylsilane (Dow Toray Industries, Inc.)
(12): Dioctyl tin dilaurate (Nitto Kasei Co., Ltd.)

As shown in Table 2, in addition to the polyoxyalkylene polymer (A) having a reactive silicon group and the (meth) acrylic acid ester copolymer (B) having a reactive silicon group, the compound It can be seen that the A agent of Example 1 containing both an alkylsulfonic acid ester and a dialkoxydiarylsilane as (C) has a higher viscosity ratio than the A agents of Examples 3, 4, and 6. From this, the two-component curable composition of Example 1 has good dischargeability of the mixture obtained by mixing the main agent and the auxiliary agent, and good shape retention of the coating film obtained by applying the mixture to the substrate. It can be said that

Claims

A multi-component curable composition comprising agent A and agent B,
Agent A is a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylate polymer (B) having a reactive silicon group, dialkoxydialkylsilane, and dialkoxydiarylsilane. , and containing at least one compound (C) selected from the group consisting of alkylsulfonic acid esters,
Agent B is selected from the group consisting of a polyoxyalkylene polymer (A) having a reactive silicon group, a (meth)acrylic acid ester polymer (B) having a reactive silicon group, and a plasticizer (D). containing at least one compound, an inorganic filler (E), and water (F),
Either or both of the A agent and the B agent contain a silanol condensation catalyst (G),
A multicomponent curable composition, wherein the reactive silicon group is represented by the following general formula (1).
—SiR 1 3-a X a (1)
(Wherein, R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X represents a hydroxyl group or a hydrolyzable group; a is 2 or 3.)
The multicomponent curable composition according to claim 1, wherein the agent A contains a dialkoxydiarylsilane as the compound (C).
The multicomponent curable composition according to claim 1, wherein the agent A contains a dialkoxydiarylsilane and an alkylsulfonic acid ester as the compound (C).
4. Any one of claims 1 to 3, wherein the (meth)acrylic ester-based polymer (B) contains 40% by weight or more of the total monomers of an alkyl (meth)acrylate having 1 to 3 carbon atoms in the alkyl. 2. The multi-component curable composition according to item 1 or 2.
The multicomponent curable composition according to any one of claims 1 to 3, wherein agent A further contains an amino group-containing silane coupling agent (H).
The multi-component curable composition according to any one of claims 1 to 3, which is a two-component curable composition consisting of agent A and agent B.
A cured product obtained by curing the multicomponent curable composition according to any one of claims 1 to 3.