JP2005290037A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition using an acrylic polymer having a hydrolyzable silicon-containing group and excellent in weather resistance, heat resistance, etc. and extremely excellent in adhesiveness. <P>SOLUTION: The curable composition comprises a polymer, polymer fine particles dispersed in the polymer and a compatibilizer. The polymer has an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester unit on the main chain and the polymer has at least one hydrolyzable silicon-containing group per molecule. The polymer fine particles is obtained by three-dimensionally crosslinking a liquid rubber and has a hydrolyzable silicon-containing group. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition using a (meth) acrylic polymer having a hydrolyzable silicon-containing group.

  Polymers having hydrolyzable silicon-containing groups are used in curable compositions for applications such as sealants and adhesives because of their excellent curability at room temperature and ease of compounding design. In particular, polymers having an acrylic (including methacrylic, the same shall apply hereinafter) main chain (see, for example, Patent Documents 1 to 5) have weather resistance, heat resistance, oil resistance, and adhesion to various adherends. Because of its excellent properties, it is suitably used for applications such as sealing materials, sealing agents, potting agents, elastic adhesives, coating materials, lining materials, adhesives and the like in harsh environments. In addition, a polymer having an acrylic main chain synthesized by living radical polymerization is suitably used as a room temperature moisture-curable one-component composition because it has a relatively low viscosity and excellent handleability.

JP-A-9-272714 JP 11-43512 A JP-A-11-80249 JP 2000-154205 A JP 2003-96106 A

However, as a result of intensive studies by the inventor, the composition using the above-described polymer having an acrylic main chain and a hydrolyzable silicon-containing group has excellent adhesion to glass, but it does not adhere to stainless steel, aluminum, or the like. It was found that there was a problem of poor adhesion.
Accordingly, an object of the present invention is to provide a curable composition using an acrylic polymer having a hydrolyzable silicon-containing group, which is excellent in weather resistance, heat resistance, etc. and has excellent adhesion. .

  As a result of intensive studies to achieve the above object, the present inventor dispersed polymer fine particles obtained by three-dimensionally cross-linking liquid rubber in an acrylic polymer having a hydrolyzable silicon-containing group, and silane coupling. The present inventors have found that the adhesiveness can be remarkably improved without impairing the advantages such as weather resistance and heat resistance when an agent and a compatibilizing agent are contained.

  That is, the present invention provides the following (1) to (12).

(1) containing a polymer, polymer fine particles dispersed in the polymer, and a compatibilizing agent,
The polymer is a polymer in which the main chain includes an alkyl acrylate monomer unit and / or a methacrylic acid alkyl ester monomer unit, and has at least one hydrolyzable silicon-containing group per molecule;
The curable composition, wherein the polymer fine particles are polymer fine particles obtained by three-dimensionally cross-linking liquid rubber and having a hydrolyzable silicon-containing group.

  (2) The curable composition according to the above (1), wherein the polymer fine particles are polymer fine particles obtained by three-dimensional crosslinking by reaction of the functional group of the liquid rubber having a functional group capable of three-dimensional crosslinking.

  (3) The curable composition according to the above (1) or (2), wherein the polymer fine particles are polymer fine particles obtained by three-dimensionally crosslinking the liquid rubber with a crosslinking agent and / or a curing agent.

  (4) The curable composition according to any one of (1) to (3), wherein the liquid rubber is a diene rubber.

  (5) The above (1) to (4), wherein all or part of the hydrolyzable silicon-containing group of the polymer fine particle is introduced into the polymer fine particle by reaction with a silane coupling agent. The curable composition according to any one of the above.

  (6) The silane coupling agent is an aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with an epoxy resin or polyisocyanate. The curable composition as described in said (5).

  (7) The curable composition as described in said (5) or (6) whose quantity of the said silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers.

  (8) The curable composition according to any one of (1) to (7) above, containing 0.1 to 10 parts by mass of the compatibilizer with respect to 100 parts by mass of the polymer.

  (9) The curable composition according to any one of (1) to (8), further containing 50 to 400 parts by mass of calcium carbonate with respect to 100 parts by mass of the polymer.

  (10) The curable composition according to any one of (1) to (9), further containing 0.1 to 10 parts by mass of a hydrolyzable compound having a molecular weight of 1000 or less with respect to 100 parts by mass of the polymer. Stuff.

  (11) The curable composition according to any one of (1) to (10), further containing a tin catalyst and / or a titanium catalyst.

  (12) The curable composition according to any one of (1) to (11) above, containing 1 to 100 parts by mass of the polymer fine particles with respect to 100 parts by mass of the polymer.

  The curable composition of the present invention has equivalent excellent weather resistance, heat resistance, and the like as compared with a curable composition using an acrylic polymer having a conventional hydrolyzable silicon-containing group, and is bonded. Extremely excellent in properties.

The present invention is described in detail below.
The curable composition of the present invention contains a polymer, polymer fine particles dispersed in the polymer, a silane coupling agent, and a compatibilizing agent, and the polymer has an alkyl acrylate ester in the main chain. A polymer containing a monomer unit and / or a methacrylic acid alkyl ester monomer unit and having at least one hydrolyzable silicon-containing group per molecule; The curable composition is a polymer fine particle.

First, the polymer will be described.
The polymer used in the present invention has a main chain containing an alkyl acrylate monomer unit and / or an alkyl methacrylate monomer unit and having at least one hydrolyzable silicon-containing group per molecule. It is. In the present invention, the hydrolyzable silicon-containing group may be present at the terminal in the molecule of the polymer, may be present in the side chain, or may be present in both.

Examples of the acrylic acid alkyl ester monomer unit include, for example, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t-butyl, and acrylic acid-n. -Hexyl, heptyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, lauryl acrylate, tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate, Biphenyl acrylate is mentioned.
Examples of the methacrylic acid ester monomer unit include, for example, methyl methacrylate, ethyl methacrylate, methacrylate-n-propyl, methacrylate-n-butyl, methacrylate-isobutyl, methacrylate-t-butyl, methacrylate- n-hexyl, heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, myristyl methacrylate, cetyl methacrylate, stearyl methacrylate, behenyl methacrylate And biphenyl methacrylate.
These may be used alone or in combination of two or more.

  The main chain of the polymer is not particularly limited as long as it contains an alkyl acrylate monomer unit and / or a methacrylic acid alkyl ester monomer unit, but the proportion of these monomer units is 50% by mass. It is preferable to exceed, and it is more preferable that it is 70 mass% or more.

The main chain of the polymer may contain, in addition to the acrylic acid alkyl ester monomer unit and / or the methacrylic acid alkyl ester monomer unit, a monomer unit having copolymerizability with these. For example, a monomer unit containing a carboxy group such as acrylic acid or methacrylic acid; a monomer unit containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, or N-methylolmethacrylamide; glycidyl acrylate, glycidyl Monomer units containing epoxy groups such as methacrylate; monomer units containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; polyoxyethylene acrylate, polyoxyethylene methacrylate, etc. are moisture A copolymerization effect can be expected in terms of curability and internal curability.
In addition, monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like can be mentioned.

The monomer composition of the polymer is appropriately selected depending on the application and purpose.
For example, when the alkyl chain of the alkyl ester part of the monomer is long, the glass transition temperature is low, and the physical properties of the cured product are soft rubbery elastic bodies. On the other hand, when it is short, the glass transition temperature becomes high and the physical properties of the cured product become hard.
On the other hand, the physical properties after curing largely depend on the molecular weight of the polymer.
Therefore, the monomer composition of the polymer may be appropriately selected according to the desired viscosity, physical properties after curing, and the like, taking into consideration the molecular weight.

The main chain of the polymer can be obtained by a controlled vinyl polymerization method or the like. For example, it can be obtained by performing a solution polymerization method, a bulk polymerization method or the like by a chain transfer agent method, a living radical polymerization method or the like, but is not particularly limited to these methods.
In the chain transfer agent method, it is also possible to obtain a polymer having a functional group at the terminal by performing polymerization using a chain transfer agent having a specific functional group.
In the living radical polymerization method, a polymer having a molecular weight almost as designed can be obtained by growing the polymerization growth terminal without causing a termination reaction or the like.
The chain transfer agent method is a free radical polymerization and thus has a wide molecular weight distribution and only a polymer having a high viscosity can be obtained. However, the living radical polymerization method has a narrow molecular weight distribution (Mw / Mn is 1) because a termination reaction is unlikely to occur. About 1.5 to 1.5), a polymer having a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. In the present invention, the method described in JP-A-2003-313397 is preferably used.
The reaction is usually carried out by mixing the above-mentioned monomer units, radical initiator, chain transfer agent, solvent and the like and reacting them at 50 to 150 ° C.

Examples of the radical initiator include azobisisobutyronitrile and benzoyl peroxide.
Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, lauryl mercaptan; and halogen-containing compounds.
Suitable examples of the solvent include non-reactive solvents such as ethers, hydrocarbons and esters.

  The hydrolyzable silicon-containing group has 1 to 3 hydroxy groups and / or hydrolyzable groups bonded to silicon atoms, and in the presence of moisture or a crosslinking agent, a catalyst or the like is used as necessary. It is a silicon-containing group that can be crosslinked by causing a condensation reaction to form a siloxane bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  The polymer has at least one hydrolyzable silicon-containing group per molecule. Further, the bonding position of the hydrolyzable silicon-containing group is preferably at the end of the main chain, and more preferably only at the end of the main chain.

The method for introducing the hydrolyzable silicon-containing group into the main chain of the polymer is not particularly limited. For example, (i) the above monomer in the presence of a mercaptan containing a hydrolyzable silicon-containing group as a chain transfer agent. (Ii) a compound having a mercapto group and a reactive functional group other than a hydrolyzable silicon-containing group as a chain transfer agent (for example, acrylic acid). ) In the presence of a compound having a functional group capable of reacting with a hydrolyzable silicon-containing group and a Y group (for example, an isocyanate group and —Si (OCH _3). ) a compound having a group ₃₎ was reacted method of introducing a hydrolyzable silicon-containing group at the molecular ends, compounds containing (iii) a hydrolyzable silicon-containing group (e.g., azobisnitrile compound , Disulfide compounds) as initiators to polymerize the monomer units and introduce hydrolyzable silicon-containing groups at the molecular ends, and (iv) polymerize the monomer units by living radical polymerization to terminate the molecular ends. A method of introducing a hydrolyzable silicon-containing group into (v) a compound having a polymerizable unsaturated bond and a hydrolyzable silicon-containing group and the monomer unit, wherein the hydrolyzable silicon-containing group per molecule Examples thereof include a method of copolymerization by selecting polymerization conditions such as the use ratio of monomer units, the amount of chain transfer agent, the amount of radical initiator, and the polymerization temperature so that at least one monomer is introduced.

  Among these, it is one of the preferred embodiments that the polymer is produced by adding hydrosilane having a hydrolyzable silicon-containing group to a (meth) acrylic polymer having an alkenyl group at the terminal by hydrosilylation. .

The (meth) acrylic polymer having an alkenyl group at the end includes, for example, an organic halogen compound or a sulfonyl halide compound as an initiator and a catalyst as the group 8, 9, 10, or 11 of the periodic table. It can be produced by converting a terminal halogen group of a (meth) acrylic polymer obtained by polymerization using a metal complex having a group element as a central metal to an alkenyl group.
Here, a (meth) acrylic polymer having a halogen group at a terminal is conventionally polymerized using a halogen compound such as carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide as a chain transfer agent. Has been manufactured by.
However, with this method, it has been difficult to reliably introduce halogen to both ends of the polymer.

In contrast, JP-A-1-247403 discloses a method for producing an acrylic polymer having an alkenyl group at both ends by using dithiocarbamate or diallyl disulfide having an alkenyl group as a chain transfer agent. Has been described. Japanese Patent Application Laid-Open No. Hei 6-221922 discloses that an acrylic polymer having a hydroxyl group at the terminal is produced using a hydroxyl group-containing polysulfide or an alcohol compound as a chain transfer agent, and alkenyl at the terminal using a hydroxyl group reaction. A method for producing an acrylic polymer having a group is described.
However, in these methods, it is usually difficult to reliably introduce an alkenyl group at the end of the polymer.

On the other hand, as a method for obtaining a (meth) acrylic polymer having a hydrolyzable silicon-containing group without passing through an alkenyl group, Japanese Patent Publication No. 3-14068 discloses a (meth) acrylic monomer containing hydrolyzable silicon. A method of polymerizing in the presence of a radical polymerization initiator having a group-containing mercaptan, a hydrolyzable silicon-containing group-containing disulfide and a hydrolyzable silicon-containing group is described. Japanese Patent Publication No. 4-55444 discloses a method of polymerizing an acrylic monomer in the presence of a hydrolyzable silicon-containing group-containing hydrosilane compound or a tetrahalosilane compound. Further, in JP-A-5-97921, an acrylic monomer is anionically polymerized using a stable carbanion having a hydrolyzable silicon-containing group as an initiator, and the terminal of the polymerization is reacted with a bifunctional electrophilic compound. Describes a method for producing an acrylic polymer having a hydrolyzable silicon-containing group.
However, these methods have problems such as introduction of a functional group into the side chain. That is, it was difficult to reliably introduce a hydrolyzable silicon-containing group at the terminal. In addition, the polymers obtained by these radical polymerizations have a problem that the molecular weight distribution is wide and the viscosity is high.

Therefore, in recent years, living radical polymerization has attracted attention as a method for reliably introducing a functional group to the terminal of an acrylic polymer. Living radical polymerization is described in JP-A-9-272714.
In particular, JP 2000-154205 A and JP 2000-178456 A detail the atom transfer radical polymerization method among the living radical polymerization methods. Here, an organic halide or a sulfonyl halide compound having a particularly highly reactive carbon-halogen bond is used as the initiator, and a periodic table, group 8, group 9, group 10 or group 11 is used as the catalyst. A metal complex having the above metal as a central metal is used. Further, in order to obtain a (meth) acrylic polymer having a functional group at the terminal, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator.

  Japanese Patent Laid-Open No. 2003-96106 discloses radical polymerization of (meth) acrylate monomers using 2,2′-azobis (dimethylvaleronitrile) as an initiator and n as a chain transfer agent. -Dodecyl mercaptan, t-dodecyl mercaptan and the like are described. Here, when 2-propanol, isobutanol or the like is used as a polymerization solvent, since it has a hydrogen atom bonded to a tertiary carbon atom, it also acts as a chain transfer agent and reduces the amount of chain transfer agent used. It is described that it is preferable in that it can be produced, and that the molecular weight distribution can be controlled more narrowly than in the case of using an aromatic solvent.

  As described above, the polymer produced from the (meth) acrylic polymer obtained by any of the polymerization methods has a molecular weight distribution of 2.0 (meth) acrylic polymer obtained by ordinary polymerization. On the other hand, since it can be controlled to be as narrow as 1.5 or less, the viscosity is low and the functional group introduction rate at the terminal is extremely high.

  The molecular weight of the polymer is not particularly limited, but those having a number average molecular weight in terms of polystyrene of 500 to 100,000 in gel permeation chromatography (GPC) are difficult to polymerize, compatible, and handling viscosity. This is preferable. Among them, those having a number average molecular weight of 1,000 to 50,000 are preferable from the viewpoint of balance between strength and viscosity, and those having a number average molecular weight of 2,000 to 30,000 are points such as ease of handling such as workability and adhesiveness. And more preferable.

  A polymer is used individually or in mixture of 2 or more types.

  A well-known thing can be used as a polymer. Specific examples include SMAP (Kaneka Telechelic Polyacrylate) SA100S, SA110S, SA120S, SA200SX manufactured by Kaneka Chemical Industry Co., Ltd .; Kaneka MS Polymer S943 manufactured by Kaneka Chemical Industry Co., Ltd.

Next, polymer fine particles will be described.
The polymer fine particles used in the present invention are polymer fine particles obtained by three-dimensionally cross-linking liquid rubber, and are dispersed in the above-described polymer.

The liquid rubber is not particularly limited, and examples thereof include diene rubber and non-diene rubber.
Examples of the diene rubber include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber (CR), ethylene-propylene- Examples include diene rubber (EPDM).
Examples of the non-diene rubber include butyl rubber (IIR), halogenated butyl rubber, ethylene-propylene rubber (EPM), chlorosulfonated polyethylene rubber, chlorinated polyethylene, urethane rubber, acrylic rubber, silicone rubber, and polysulfide.
Of these, diene rubber is preferable, and isoprene rubber and butadiene rubber are more preferable.
These may be used alone or in combination of two or more.

The liquid rubber preferably has a functional group having an acid anhydride in the molecule. Thereby, adhesiveness will become more excellent.
The functional group having an acid anhydride is not particularly limited, and examples thereof include a functional group having maleic anhydride.
A liquid rubber having a functional group having an acid anhydride in the molecule reacts, for example, a compound having a functional group having an acid anhydride with the main chain of the liquid rubber having no functional group having an acid anhydride in the molecule. It can obtain by the method of making it. It can also be obtained by a method of copolymerizing a diene monomer and a vinyl monomer having a functional group having an acid anhydride.

  The molecular weight of the liquid rubber is not particularly limited.

The polymer fine particles are formed by three-dimensionally cross-linking the liquid rubber described above. The mode of three-dimensional crosslinking is not particularly limited.
For example, as one aspect, when the liquid rubber has a functional group capable of three-dimensional crosslinking, an aspect in which the liquid rubber is three-dimensionally cross-linked by the reaction of the functional group. Specifically, when a functional group having an acid anhydride such as maleic anhydride is introduced into the double bond portion of the diene rubber, three-dimensional crosslinking can be performed by the reaction of the acid anhydride.
At this time, a functional group curing agent, a catalyst, or the like may be used. A conventionally well-known thing can be used as a hardening | curing agent and a catalyst. For example, in the case of a functional group having maleic anhydride, an oxazolidine compound and water for hydrolyzing it can be used as a curing agent. In this example, water hydrolyzes the oxazolidine compound to form a secondary amine, which opens the maleic anhydride and performs three-dimensional crosslinking. In addition, water can also be supplied by adding a filler such as calcium carbonate described later in an undried state.

  Another embodiment includes an embodiment in which the liquid rubber is three-dimensionally crosslinked with a crosslinking agent and / or a curing agent. A conventionally well-known thing can be used as a crosslinking agent. For example, an organic peroxide and a sulfur type compound are mentioned.

The polymer fine particles are dispersed in the polymer described above. The dispersion method is not particularly limited, but a liquid rubber having low compatibility with the polymer is added to the polymer, stirred, dispersed by phase separation, and then the liquid rubber can be cross-linked three-dimensionally. A method of three-dimensional crosslinking by a functional group reaction or a crosslinking agent is preferred.
Further, when the compatibility between the liquid rubber and the polymer is not low, it is also preferable to disperse the mixture by stirring at a high speed and then perform three-dimensional crosslinking in the same manner as described above. In order to stir at high speed, for example, a stirrer having a vibro mixer, a gyro mixer, a high speed disper, etc. can be used.

  In these methods, the liquid rubber is dispersed in the polymer under conditions where the polymer is not cured, that is, under moisture-blocking conditions, or without addition of a catalyst, a curing agent, etc. Three-dimensional crosslinking is performed by a crosslinking reaction of liquid rubber without curing the coalescence. As the cross-linking reaction proceeds, the fine polymer particles are uniformly dispersed in the polymer by stirring. At this time, the polymer does not participate in the reaction.

In the present invention, in consideration of the crosslinking reaction speed of liquid rubber, the stirring speed and temperature at the time of stirring, the phase separation energy between the polymer and the liquid rubber, etc., the size of the polymer fine particles can be adjusted. It can be uniformly dispersed in the polymer.
The preferred range of these physical properties (parameters) varies depending on the polymer used, liquid rubber, etc. and cannot be determined unconditionally. For example, the stirring speed (rotational speed) is 50 to 20,000 rpm. This is preferable in that the fine particles can be uniformly dispersed.

  When the liquid rubber is dispersed in the polymer and three-dimensionally crosslinked, various additives described later, for example, fillers such as calcium carbonate, process oil, and the like can be added. Since the process oil has low compatibility with the polymer and high compatibility with the liquid rubber, the process oil is taken into the polymer fine particles while stably performing the three-dimensional crosslinking of the liquid rubber.

In the present invention, the polymer fine particles have hydrolyzable silicon-containing groups. Since the polymer fine particles have hydrolyzable silicon-containing groups, when the hydrolyzable silicon-containing groups of the polymer are hydrolyzed and cured, the hydrolyzable silicon-containing groups of the polymer fine particles are simultaneously hydrolyzed and reacted. Therefore, a bond between the polymer and the polymer fine particles is formed, and the adhesiveness is extremely excellent.
The method for causing the polymer fine particles to have a hydrolyzable silicon-containing group is not particularly limited, but it is preferable that all or part of the polymer fine particles be introduced by reaction with a silane coupling agent. For example, when the liquid rubber has a functional group, a method of directly reacting a silane coupling agent having a functional group capable of reacting with the functional group and a hydrolyzable silicon-containing group can be mentioned. Moreover, the method of introduce | transducing these silane coupling agents into liquid rubber indirectly through an epoxy resin, polyisocyanate, etc. is also mentioned.

  The silane coupling agent is not particularly limited, but can be obtained by reacting aminosilane, vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, ketimine silane, or a mixture or reaction thereof, or an epoxy resin or polyisocyanate. It is preferable that it is a compound obtained.

Examples of aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, and bistriethoxysilylpropylamine. Bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, Examples thereof include N-2- (aminoethyl) -3-aminopropyltriethoxysilane and N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane.
Examples of the vinyl silane include vinyl trimethoxy silane, vinyl triethoxy silane, and tris- (2-methoxy ethoxy) vinyl silane.
Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyl. Examples include dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
Examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Examples of the isocyanate silane include isocyanate propyl triethoxysilane.
Examples of the ketimine silane include ketiminated propyltrimethoxysilane.
These may be used alone or in combination of two or more.

  It is preferable that the quantity of a silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers.

  In these methods, it is possible to react with a silane coupling agent after the production of polymer fine particles (that is, after the three-dimensional crosslinking of the liquid rubber), and during the production of polymer fine particles (that is, the reaction of the three-dimensional crosslinking of the liquid rubber) It can also be reacted with a silane coupling agent during the process.

  The polymer fine particles preferably have an average particle diameter of 0.01 to 100 μm, and preferably 0.1 to 50 μm, from the viewpoint of being uniformly dispersed in the polymer and having excellent adhesion. More preferred.

  Content of the polymer fine particle in the curable composition of this invention is 1-100 mass parts with respect to 100 mass parts of polymers mentioned above, Preferably it is 5-70 mass parts, More preferably, it is 10-40 mass parts. Within the above range, a curable composition having workability (for example, physical properties such as viscosity and thixotropic properties) and appearance characteristics (for example, color tone, gloss, etc.) equivalent to or higher than those of conventional curable compositions is obtained.

In one preferred embodiment, the curable composition of the present invention contains a compatibilizing agent. The compatibilizing agent is contained for various purposes. Examples of the purpose include generation of polymer fine particles, dispersion of polymer fine particles, and adjustment of physical properties after curing.
In general, for example, when the polymer A and the polymer B are in an incompatible mixed system, the copolymer of the polymer A monomer and the polymer B monomer is a surfactant. It plays such a role, and at the interface between the polymer A and the polymer B, functions such as lowering the interfacial tension, controlling the interface layer, and repelling action of the dispersion layer are exhibited. That is, the compatibilizing agent bears important functions such as fine dispersion and improved adhesion between the two at the interface.

  Examples of the compatibilizer include, for example, the same as the blend component; some of the other components compatible with the blend component are the same; a copolymer containing a monomer different from the polymer A and the polymer B, The solubility parameter value is the same or close; copolymer of another monomer that reacts with polymer A or polymer B and is compatible with other polymers; blend of polymer A and polymer B In the process, a part of the graft and / or block copolymer is formed by the reaction and acts as a compatibilizing agent.

The compatibilizing agent in the present invention has two or more substances having different chemical characteristics in the same molecule, and depending on its function, a surfactant, an admixture, an emulsifier, a solubilizer, a dispersant, etc. Called.
Suitable examples of the compatibilizer used in the present invention include nonionic surfactants such as polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.
The compatibilizing agent may be added after the production of the polymer fine particles (that is, after the three-dimensional crosslinking of the liquid rubber) or during the formation of the polymer fine particles (that is, during the progress of the three-dimensional crosslinking of the liquid rubber). It may be added before the production of polymer fine particles, and it is preferable to select a method as appropriate according to various conditions.

  Compatibilizers can be used alone or in combination of two or more. The ratio in the case of using 2 or more types in combination can be appropriately determined according to the use in which the curable composition of the present invention is used, the physical properties required for the curable composition of the present invention, and the like.

  The content of the compatibilizing agent is 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polymer described above.

In one preferred embodiment, the curable composition of the present invention contains calcium carbonate.
The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with a fatty acid, Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Whiteon 305 (heavy calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.), Hakusyo Hana CCR (manufactured by Shiroishi Kogyo Co., Ltd.), modified As calcium carbonate surface-treated with fatty acid, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Flour Industries Co., Ltd.), as calcium carbonate surface-treated with fatty acid ester, Sealets 200 (manufactured by Maruo Calcium Co., Ltd.), Snowlight SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) or the like is preferably used. Of these, those that have been surface-treated with fatty acids, modified fatty acids, fatty acid esters, higher alcohol-added isocyanate compounds, and the like are particularly preferred. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.

  The content of calcium carbonate is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the polymer.

In one preferred embodiment, the curable composition of the present invention contains a hydrolyzable compound having a molecular weight of 1000 or less. The hydrolyzable compound is effectively used to absorb moisture contained in the polymer, calcium carbonate, etc. and improve storage stability.
Examples of such hydrolyzable compounds include relatively low molecular weight silane coupling agents such as vinyl silane, oxime silane, amino silane, epoxy silane, and mercapto silane; methyl orthoformate, ethyl orthoformate, 2-phenyl-3- Examples include hydrolyzable compounds such as oxazolidineethanol and polyoxyalkylene-methylstearoxypolysiloxane copolymers.
These may be used alone or in combination of two or more.

  The content of the hydrolyzable compound having a molecular weight of 1000 or less is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer.

The curable composition of the present invention can contain the above-mentioned silane coupling agent separately from the one for introducing a hydrolyzable silicon-containing group into polymer fine particles.
The content of the silane coupling agent is preferably the above-mentioned range, which is the sum of the amount of the silane coupling agent and the amount of the silane coupling agent to be incorporated separately from that for introducing the hydrolyzable silicon-containing group.

The curable composition of the present invention preferably contains a tin catalyst and / or a titanium catalyst.
A conventionally well-known thing can be used for a tin catalyst and / or a titanium catalyst.
Examples of the tin catalyst include tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; reaction products of dibutyltin oxide and phthalate; dibutyltin diacetylacetonate.
Examples of the titanium catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate.
These may be used alone or in combination of two or more.

  The content of the tin catalyst and / or titanium catalyst is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the polymer.

The curable composition of this invention can contain another hardening | curing agent in the range which does not impair the objective of this invention.
For example, amine curing agents, acid or acid anhydride curing agents, basic active hydrogen compounds, imidazoles, polymercaptan curing agents, phenol resins, urea resins, melamine resins, isocyanate curing agents, latent curing agents, An ultraviolet curing agent is mentioned.

  The curable composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate, plasticizers, softeners, thixotropy imparting agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, and dispersions. Agents and solvents.

  As fillers other than calcium carbonate, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Fired clays; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, and fatty acid ester urethane compound treated products.

  Examples of the plasticizer or softener include diisononyl phthalate (DINP), dioctyl phthalate, dibutyl phthalate; dioctyl adipate, isodecyl succinate; diethylene glycol dipenzoate, pentaerythritol ester; butyl oleate, acetylricinoleic acid Examples include methyl; tricresyl phosphate, trioctyl phosphate; propylene glycol adipate polyester, butylene glycol polyester adipate; petroleum softeners such as paraffinic oil, naphthenic oil, and aroma oil.

Examples of the thixotropic property-imparting agent include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, and Teflon (registered trademark).
Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; organic pigments such as azo pigments and copper phthalocyanine pigments. It is done.

Examples of the antiaging agent include hindered phenol compounds and hindered amine compounds.
Examples of the antioxidant include butylhydroxytoluene (BHT) and butylhydroxyanisole (BHA).
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.

  The method for producing the curable composition of the present invention from each component as described above is not particularly limited. As described above, after forming polymer fine particles in the polymer, other components are reduced under reduced pressure or Examples thereof include a method in which the mixture is sufficiently kneaded and uniformly dispersed using a stirring apparatus such as a mixing mixer in an inert gas atmosphere such as nitrogen.

The curable composition of the present invention may be a one-component form or a two-component form. In the case of the two-component form, the main agent is other than the curing agent, and the main agent and the curing agent are mixed and used according to a conventional method before use.
When the curable composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silicon-containing group. In addition, the curing reaction can be advanced by appropriately supplying water.

  When using the curable composition of this invention as a sealing material etc., you may use it, after apply | coating a primer to a to-be-adhered body. A conventionally well-known thing can be used as a primer.

  The curable composition of the present invention is a sealing material, a sealing agent, a potting agent, an elastic adhesive, a coating material, a lining material, and an adhesive for civil engineering, concrete, wood, metal, glass, and plastic. It is suitably used for such applications.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.
(Example 1)
In 80 parts by mass of an acrylic polymer (SMAP SA100S, Kaneka Chemical Industry Co., Ltd.), 20 parts by mass of maleic anhydride-modified liquid polyisoprene rubber (LIR403, Kuraray Co., Ltd., number average molecular weight 30,000) and a method described later. 1 part by mass of the obtained oxazolidine compound (PHO-XDI) was added and stirred for 10 minutes to mix uniformly.
Next, 60 parts by mass of undried calcium carbonate 1 (modified fatty acid surface-treated heavy calcium carbonate, Ryton A-4, manufactured by Bihoku Powder Chemical Co., Ltd.) was added and stirred for 20 minutes to three-dimensionally crosslink the liquid polyisoprene rubber. Polymer fine particles were formed to obtain a dispersion mixture in which the polymer fine particles and calcium carbonate 1 were dispersed in an acrylic polymer.

Furthermore, 0.5 parts by mass of a silane coupling agent (aminosilane compound, KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.) and a compatibilizer (fatty acid ester, Rheodor TW-O320W, manufactured by Kao Corporation) 0.5 were added to the obtained dispersion mixture. Part by mass was added and stirred for 10 minutes to form polymer fine particles having hydrolyzable silicon-containing groups.
Thereafter, calcium carbonate 2 (surface-treated calcium carbonate, Calfine 200, manufactured by Maruo Calcium Co., Ltd.), diisononyl phthalate (DINP, manufactured by J Plus), epoxy resin (bisphenol A type epoxy resin, YD-128, Toto Kasei Co., Ltd.) ), UV absorber (Tinuvin 327, manufactured by Ciba Specialty Chemicals), amine compound (laurylamine, manufactured by Kao) and tin catalyst (divalent tin compound, Nikka Octin, manufactured by Nippon Kagaku Sangyo Co., Ltd.) Were added at a quantitative ratio (parts by mass) shown in Table 1 and mixed by stirring to obtain a curable composition.

<Synthesis of Oxazolidine Compound (PHO-XDI)>
The oxazolidine compound can be generally obtained by, for example, dehydrating condensation of an alkanolamine and a ketone or aldehyde. In this example, an oxazolidine compound (PHO-XDI) was synthesized as follows.
30.0 g of diethanolamine, 31.8 g of benzaldehyde, and 33.0 g of toluene were placed in a 1 L flask and subjected to dehydration reaction at 110 ° C. for 6 hours. Then, by reducing the pressure at 90 ° C., toluene and unreacted substances were removed to obtain 54.0 g of 2-phenyl-3- (2-hydroxyethyl) oxazolidine, which is a hydroxyalkyloxazolidine. 31.8 g of the obtained 2-phenyl-3- (2-hydroxyethyl) oxazolidine and 15.6 g of xylylene diisocyanate were mixed and reacted at 60 ° C. for 3 hours to obtain an oxazolidine compound (PHO-XDI). .

(Examples 2 and 3)
A curable composition was obtained in the same manner as in Example 1 except that the amount ratio (parts by mass) of the acrylic polymer and the maleic anhydride-modified liquid polyisoprene rubber was changed as shown in Table 1.

(Comparative Example 1)
A curable property was obtained in the same manner as in Example 1, except that the maleic anhydride-modified liquid polyisoprene rubber and the oxazolidine compound were not used and the amount ratio (parts by mass) of the acrylic polymer was changed as shown in Table 1. A composition was obtained.
(Comparative Example 2)
A curable composition was obtained in the same manner as in Example 1 except that no compatibilizer was used.
(Comparative Example 3)
A curable composition was obtained in the same manner as in Example 1 except that the silane coupling agent was not used.

  About the obtained curable composition, the physical property after hardening, adhesiveness, and weather resistance adhesiveness were evaluated as follows.

(1) Physical properties after curing The curable composition is made into a sheet, left for 3 days under conditions of 23 ° C. and 50% RH, and further cured for 4 days at 50 ° C. Was subjected to a tensile test at a tensile speed of 200 mm / min, and the tensile stress (T _B ) at break and the elongation (E _B ) at break were measured, and were set as “initial T _B ” and “initial E _B ”, respectively. .
For those that were left standing at 50 ° C. and then cured at 90 ° C. for 7 days, the tensile stress at break (T _B ) and the elongation at break (E _B ) were similarly determined. Measured to be “90 ° C. × 7 days later T _B ” and “90 ° C. × 7 days later E _B ”, respectively.
The results are shown in Table 1.

(2) Adhesiveness and weather-resistant adhesive A curable composition is placed in the form of a bead on the surface of a stainless steel plate, left under conditions of 23 ° C. and 50% RH for 3 days, and further allowed to stand at 50 ° C. for 4 days. After curing, a hand peeling test with a knife cut was performed, and the state of destruction was visually observed to evaluate “stainless steel adhesion”.
In addition, a curable composition was placed in a bead shape on the surface of a glass plate made of float glass specified in JIS R3202 having a thickness of 5 mm, and left for 3 days under conditions of 23 ° C. and 50% RH. After leaving to cure at 50 ° C. for 4 days, irradiation with a sunshine weatherometer was performed for 3000 hours from the side of the glass plate on which the curable composition was not placed. Thereafter, a hand peeling test using a knife cut was performed, and the state of destruction was visually observed to evaluate “glass weather resistance”.
The results are shown in Table 1. In Table 1, the state of failure was indicated by CF (cohesive failure) and TCF (thin layer cohesive failure).

As is clear from Table 1, the curable compositions of the present invention (Examples 1 to 3) have the same heat resistance and weather resistance as compared to the conventional curable composition (Comparative Example 1). While achieving better adhesion.
In addition, when it does not contain a compatibilizing agent (Comparative Example 2), it is inferior in heat resistance. Moreover, when a polymer microparticle does not have a hydrolysable silicon containing group (comparative example 3), it is inferior to adhesiveness and weather resistance adhesiveness.

Claims (12)

Containing a polymer, polymer fine particles dispersed in the polymer, and a compatibilizer,
The polymer is a polymer in which the main chain includes an alkyl acrylate monomer unit and / or a methacrylic acid alkyl ester monomer unit, and has at least one hydrolyzable silicon-containing group per molecule;
The curable composition, wherein the polymer fine particles are polymer fine particles obtained by three-dimensionally cross-linking liquid rubber and having a hydrolyzable silicon-containing group.   The curable composition according to claim 1, wherein the polymer fine particles are polymer fine particles obtained by three-dimensional crosslinking by a reaction of the functional group of the liquid rubber having a functional group capable of three-dimensional crosslinking.   The curable composition according to claim 1 or 2, wherein the fine polymer particles are fine polymer particles obtained by three-dimensionally crosslinking the liquid rubber with a crosslinking agent and / or a curing agent.   The curable composition according to claim 1, wherein the liquid rubber is a diene rubber.   The whole or part of the hydrolyzable silicon-containing group of the polymer fine particle is introduced into the polymer fine particle by a reaction with a silane coupling agent. Curable composition.   6. The silane coupling agent is aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof, or a compound obtained by reacting these with an epoxy resin or polyisocyanate. The curable composition according to 1.   The amount of the said silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers, The curable composition of Claim 5 or 6.   The curable composition according to any one of claims 1 to 7, comprising 0.1 to 10 parts by mass of the compatibilizer with respect to 100 parts by mass of the polymer.   Furthermore, the curable composition in any one of Claims 1-8 containing 50-400 mass parts calcium carbonate with respect to 100 mass parts of said polymers.   Furthermore, the curable composition in any one of Claims 1-9 containing the hydrolyzable compound of molecular weight 1000 or less of 0.1-10 mass parts with respect to 100 mass parts of said polymers.   Furthermore, the curable composition in any one of Claims 1-10 containing a tin catalyst and / or a titanium catalyst.   The curable composition according to any one of claims 1 to 11, comprising 1 to 100 parts by mass of the polymer fine particles with respect to 100 parts by mass of the polymer.