Composition

Abstract

The present invention addresses the problem of providing a composition which has good storage stability and exhibits excellent adhesiveness even after an alkali hot water treatment without using an epoxy resin. As a means for solving the problem, the present invention provides a composition which contains (A) an organic polymer that has a crosslinkable silicon group, (B) a compound that has two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound that has a glycidyl group and a crosslinkable silicon group.

Description

composition

[0001] The present invention relates to a composition, and in particular to a composition containing (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group.

[0002]

[0003] Conventionally, compositions containing organic polymers having crosslinkable silicon groups have been used outdoors, such as adhesives for attaching architectural finishing materials, and are required to have alkali resistance, water resistance, heat resistance, etc. Up until now, these resistances have been imparted to the composition by blending an epoxy resin. For example, two-component reactive curing adhesives consisting of component A (main component: organic polymer having crosslinkable silicon groups) and component B (main component: epoxy resin) have been known, but these two-component reactive curing adhesives have room for improvement due to the complicated process of measuring and mixing components A and B, and the need to discard any excess adhesive after mixing.

[0003] One way to solve these problems is to develop a one-component adhesive. For example, Patent Documents 1 and 2 disclose adhesives that use an oxyalkylene polymer having a crosslinkable silicon group, an epoxy resin, and ketimine as a latent curing agent. This adhesive is a one-component reactive curing type that can produce an adhesive with excellent adhesiveness.

[0004] Japanese Patent Laid-Open No. 3-263421 Japanese Patent Laid-Open No. 2003-128756

[0005] The techniques of Patent Documents 1 and 2 use latent curing agents such as ketimine, which have better storage stability than amine-based curing agents mainly used for epoxy resins, but have been found to deteriorate when stored for a long period of time.

[0006] The problem to be solved by the present invention is to provide a composition which does not use an epoxy resin, has good storage stability, and exhibits excellent adhesiveness even after treatment with alkaline hot water.

[0007] The inventors conducted extensive research to solve the above problems and discovered that the above problems can be solved by combining specific components having crosslinkable silicon groups, leading to the completion of the present invention. Specifically, the present invention provides the following compositions: [Item 1] A composition containing (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group. [Item 2] The composition according to Item 1, wherein the content of (B) the compound having two or more crosslinkable silicon groups and a secondary amino group is 1.5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of (A) the organic polymer having a crosslinkable silicon group. [Item 3] The composition according to Item 1 or 2, which is an adhesive for attaching architectural finishing materials. [Item 4] The composition according to item 1 or 2, wherein the content of the compound having a glycidyl group and a crosslinkable silicon group (C) is 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the organic polymer having a crosslinkable silicon group (A). [Item 5] The composition according to item 4, which is an adhesive for attaching a building finishing material.

[0008] The present invention provides a composition that does not use an epoxy resin, has good storage stability, and exhibits excellent adhesiveness even after treatment with alkaline hot water. The composition is useful as an adhesive for use outdoors or in locations exposed to water, and as an adhesive for attaching architectural finishing materials.

[0009] Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and should be understood to include various modifications that are implemented within the scope of the present invention.

[0010] [(A) Organic Polymer Having Crosslinkable Silicon Groups] The composition of the present invention contains (A) an organic polymer having crosslinkable silicon groups. The organic polymer having crosslinkable silicon groups (A) is not particularly limited as long as its main chain is composed of various organic polymers and it has crosslinkable silicon groups in its side chains or at its terminals.

[0011] <(A) Main Chain of Organic Polymer Having Crosslinkable Silicon Group> The main chain skeleton of (A) organic polymer having a crosslinkable silicon group is not particularly limited, as long as it contains carbon atoms in the main chain of the repeating unit of the organic polymer and is the main chain skeleton of an organic polymer other than a polysiloxane-based polymer in which the main chain of the repeating unit is solely made up of siloxane bonds (—SiO—). For example, polyoxypropylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymers and other polyoxyalkylene polymers; ethylene-propylene copolymers, polyisobutylene, polyisoprene, polybutadiene, hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; condensation of dibasic acids such as adipic acid with glycols, or polyester polymers obtained by ring-opening polymerization of lactones; (meth)acrylic polymers obtained by radical polymerization of (meth)acrylic acid ester monomers such as ethyl (meth)acrylate, butyl (meth)acrylate; (meth)acrylic polymers obtained by radical polymerization of monomers such as acrylic acid ester monomers, vinyl acetate, acrylonitrile, and styrene; graft polymers obtained by polymerizing vinyl monomers in polymers; polyurethane polymers; polysulfide polymers; polyamide polymers; polycarbonate polymers; diallyl phthalate polymers, and the like. These skeletons may be contained alone in the (A) organic polymer having a crosslinkable silicon group, or two or more types may be contained in a block or random configuration. Among these, polyoxyalkylene polymers, saturated hydrocarbon polymers (polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, etc.), (meth)acrylic polymers, and polyurethane polymers are preferably used as the main chain skeleton because they have a relatively low glass transition temperature and the resulting cured product has excellent cold resistance, etc. Furthermore, polyoxyalkylene polymers and (meth)acrylic polymers are particularly preferred because they have high moisture permeability and excellent deep curing properties when made into a one-component reactive curing composition.

[0012] The organic polymer (A) having a crosslinkable silicon group may be either linear or branched. Its number average molecular weight, as measured by GPC in terms of polystyrene, is, for example, 500 or more, preferably 1,000 or more, more preferably 3,000 or more, and for example, 100,000 or less, preferably 50,000 or less, more preferably 30,000 or less. If the number average molecular weight is less than 500, the elongation properties of the cured product of the composition tend to be poor, resulting in poor adhesiveness. If the number average molecular weight is more than 100,000, the viscosity tends to be high, resulting in poor workability.

[0013] <Crosslinkable silicon group> The crosslinkable silicon group of the (A) organic polymer having a crosslinkable silicon group is a group that has a hydroxyl group or a hydrolyzable group bonded to a silicon atom and can crosslink by forming a siloxane bond. As the crosslinkable silicon group, for example, a group represented by structural formula (I) is suitable.

[0014] -Si(R １ ) ３－ａ X ａ ...(I) In structural formula (I), R １ is a hydrocarbon group such as an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Among these, R １ is preferably a methyl group. １ When there are two or more R １ may be the same or different. In structural formula (I), X represents a hydroxyl group or a hydrolyzable group, and a is an integer of 1, 2, or 3. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms forming the crosslinkable silicon group may be one or two or more.

[0015] In structural formula (I), the hydrolyzable group represented by X is not particularly limited. Examples include halogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups. Among these, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, aminooxy groups, mercapto groups, and alkenyloxy groups are preferred, and alkoxy groups, amide groups, and aminooxy groups are more preferred. From the viewpoint of mild hydrolysis and ease of handling, alkoxy groups are particularly preferred. Among alkoxy groups, the reactivity decreases as the number of carbon atoms increases, in the order of methoxy group > ethoxy group > propoxy group. Although it can be selected depending on the purpose and application, methoxy groups and ethoxy groups are usually used.

[0016] <Polyoxyalkylene Polymer Having Crosslinkable Silicon Groups> The organic polymer (A) having crosslinkable silicon groups may have a polyoxyalkylene polymer main chain. The polyoxyalkylene polymer is, for example, a polymer essentially having a repeating unit represented by structural formula (II): -R ２ -O-...(II) In structural formula (II), R ２ is a linear or branched alkylene group having 1 to 14 carbon atoms, preferably a linear or branched alkylene group having 1 to 14 carbon atoms, and more preferably a linear or branched alkylene group having 2 to 4 carbon atoms. Specific examples of the repeating unit represented by structural formula (II) include, for example, —CH ２ O-, -CH ２ CH ２ O-, -CH ２ CH (CH ３ ) O—, —CH ２ CH(C ２ H ５ ) O—, —CH ２ C(CH ３ ) ２ O-, -(CH ２ ) ４ The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

[0017] The polyoxyalkylene polymer preferably contains a polar group such as a urethane bond or a urea bond in the main chain skeleton. The active hydrogen in the urethane bond and / or urea bond introduced into the main chain or side chain may be substituted with an organic group. Therefore, in the present invention, allophanate bonds also belong to the category of urethane bonds, and biuret bonds also belong to the category of urea bonds. Introducing such polar groups near crosslinkable reactive silicon groups is preferred because it further promotes crosslinking. The polyoxyalkylene polymers having crosslinkable silicon groups may be used alone or in combination of two or more.

[0018] Examples of methods for synthesizing polyoxyalkylene polymers include, but are not limited to, polymerization using an alkali catalyst such as KOH, polymerization using a double metal cyanide complex catalyst, etc. Polymerization using a double metal cyanide complex catalyst can produce a polyoxyalkylene polymer with a number average molecular weight of 6,000 or more and a high molecular weight with an Mw / Mn ratio of 1.6 or less, and a narrow molecular weight distribution.

[0019] <Saturated Hydrocarbon Polymer Having Crosslinkable Silicon Groups> The organic polymer (A) having a crosslinkable silicon group may have a saturated hydrocarbon polymer main chain. A saturated hydrocarbon polymer is a polymer that contains substantially no carbon-carbon unsaturated bonds other than aromatic rings. The saturated hydrocarbon polymer forming the main chain can be obtained, for example, by (1) polymerizing an olefin compound having 2 to 6 carbon atoms, such as ethylene, propylene, 1-butene, or isobutylene, as the main monomer, or (2) homopolymerizing a diene compound, such as butadiene or isoprene, or copolymerizing a diene compound with an olefin compound and then hydrogenating the copolymer. Of these, isobutylene polymers and hydrogenated polybutadiene polymers are preferred because they allow easy introduction of functional groups, such as crosslinkable silicon groups, at the terminals, facilitate molecular weight control, and allow for a large number of functional groups, such as crosslinkable silicon groups, at the terminals. Isobutylene polymers are particularly preferred.

[0020] Examples of methods for producing saturated hydrocarbon polymers having crosslinkable silicon groups include cationic polymerization methods using a combination of an organic halogen compound that generates stable carbocations and a Friedel-Crafts acid catalyst as a polymerization initiator, such as the Inifer method disclosed in Japanese Patent Publication No. 4-69659.

[0021] <(Meth)acrylic Polymer Having Crosslinkable Silicon Groups> The organic polymer (A) having a crosslinkable silicon group may have a main chain of a (meth)acrylic polymer. The (meth)acrylic acid ester monomer constituting the (meth)acrylic polymer is not particularly limited. Examples include (meth)acrylic acid monomers such as (meth)acrylic acid; (meth)acrylic acid alkyl ester monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and stearyl (meth)acrylate; alicyclic (meth)acrylic acid ester monomers; aromatic (meth)acrylic acid ester monomers; (meth)acrylic acid ester monomers such as 2-methoxyethyl (meth)acrylate; silyl group-containing (meth)acrylic acid ester monomers such as 3-(methacryloyloxypropyl)trimethoxysilane and 3-(methacryloyloxypropyl)dimethoxymethylsilane; (meth)acrylic acid derivatives; and fluorine-containing (meth)acrylic acid ester monomers. In addition, styrene, maleic anhydride, vinyl acetate, (meth)acrylic acid, glycidyl (meth)acrylate, etc. may be used as a copolymerization monomer together with the (meth)acrylic acid ester monomer.

[0022] These monomers may be used alone or copolymerized in combination. In terms of the physical properties of the product, polymers composed of (meth)acrylic acid monomers are preferred. Furthermore, (meth)acrylic polymers using one or more (meth)acrylic acid alkyl ester monomers, optionally in combination with other (meth)acrylic acid monomers, are more preferred. Furthermore, the number of silicon groups in the (meth)acrylic polymer (A) can be controlled by using a silyl group-containing (meth)acrylic acid ester monomer in combination. Because of improved adhesiveness, it is particularly preferred to use a methacrylic acid ester polymer containing a methacrylic acid ester as a monomer as the main chain. Furthermore, when reducing viscosity, imparting flexibility, or imparting tackiness, it is preferable to use an acrylic acid ester monomer as appropriate. In this specification, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid. (Meth)acrylic polymers having crosslinkable silicon groups may be used alone or in combination of two or more.

[0023] (A) Examples of commercially available organic polymers having a crosslinkable silicon group include a large number of products sold as silicone resins or modified silicone resins, such as the Silyl series, MS Polymer series, MA series, SA series, OR series, and Epion series manufactured by Kaneka Corporation; the ES series manufactured by Asahi Glass Co., Ltd.; Bestplast 206 manufactured by Degussa Japan; the KC series, KR series, and X-40 series manufactured by Shin-Etsu Chemical Co., Ltd.; the XPR series manufactured by Toagosei Co., Ltd.; and the Actflow series manufactured by Soken Chemical & Engineering Co., Ltd.

[0024] The (A) organic polymer having a crosslinkable silicon group may be used alone or in combination of two or more. For example, a polymer obtained by blending two or more selected from the group consisting of a polyoxyalkylene polymer having a crosslinkable silicon group, a saturated hydrocarbon polymer having a crosslinkable silicon group, and a (meth)acrylic polymer having a crosslinkable silicon group can be used. In the present invention, one or more polyoxyalkylene polymers having a crosslinkable silicon group can be used, and a mixture of one or more polyoxyalkylene polymers having a crosslinkable silicon group with one or more saturated hydrocarbon polymers having a crosslinkable silicon group and / or one or more (meth)acrylic polymers having a crosslinkable silicon group can be used.

[0025] [(B) Compound Having Two or More Crosslinkable Silicon Groups and a Secondary Amino Group] The composition of the present invention contains (B) a compound having two or more crosslinkable silicon groups and a secondary amino group. Here, the secondary amino group is an —NH— group in a Ra-NH-Rb structure (Ra and Rb are each hydrocarbon groups having 20 or less carbon atoms, and each may have a functional group), in which two hydrogen atoms in ammonia are bonded to a hydrocarbon group. The crosslinkable silicon group is the same as the crosslinkable silicon group described above in (A) Organic Polymer Having a Crosslinkable Silicon Group. (B) Compound having two or more crosslinkable silicon groups and a secondary amino group may further have a functional group, such as an OH group (hydroxyl group) or a —C(═O)—O— group (ester bond), that is not bonded to a silicon atom.

[0026] (B) Examples of compounds having two or more crosslinkable silicon groups and a secondary amino group include bis(trimethoxysilylpropyl)amine, bis(triethoxysilylpropyl)amine, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldiethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, and N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine.

[0027] Furthermore, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group can be produced by methods such as: (a) reacting a compound having a crosslinkable silicon group and a glycidyl group with a compound having a crosslinkable silicon group and a primary amino group; (b) reacting a compound having a crosslinkable silicon group and a glycidyl group with a compound having two or more primary amino groups; (c) reacting a compound having a crosslinkable silicon group and a primary amino group with a compound having two or more glycidyl groups; (d) reacting a compound having a crosslinkable silicon group and a primary amino group with a compound having a crosslinkable silicon group and a (meth)acrylic group; or (e) reacting a compound having a crosslinkable silicon group and a primary amino group with a compound having two or more (meth)acrylic groups.

[0028] Examples of compounds having a crosslinkable silicon group and a glycidyl group that can be used include those listed below in "(C) Compounds having a glycidyl group and a crosslinkable silicon group." Examples of compounds having a crosslinkable silicon group and a primary amino group include one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane.

[0029] Examples of the compound having a crosslinkable silicon group and a (meth)acrylic group include one or more selected from the group consisting of (meth)acrylic silane coupling agents such as (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane, (meth)acryloxymethylmethyldimethoxysilane, (meth)acryloxymethyldimethylmethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, and 3-(meth)acryloxypropyldimethylmethoxysilane.

[0030] Examples of compounds having two or more glycidyl groups include compounds containing two or more glycidyl groups in the molecule, such as glycidyl ether type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins in which amines are epoxidized, epoxy resins having heterocycles, urethane-modified epoxy resins having urethane bonds, and glycidyl ester type epoxy resins. Examples of compounds having two or more (meth)acrylic groups include polyfunctional (meth)acrylic compounds. Examples of polyfunctional (meth)acrylic compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, pentadecaethylene glycol di(meth)acrylate, pentacontahexaethylene glycol di(meth)acrylate, 1,3-butylene di(meth)acrylate, allyl (meth)acrylate (allyl methacrylate, allyl acrylate), trimethylolpropane tri(meth)acrylate, and pentaerythritol tetraacrylate. Among these, ethylene glycol di(meth)acrylate (ethylene glycol dimethacrylate) and allyl (meth)acrylate (allyl methacrylate, allyl acrylate) are preferred. These polyfunctional (meth)acrylic compounds may be used alone or in combination of two or more.

[0031] The content of (B) the compound having two or more crosslinkable silicon groups and a secondary amino group in the composition is not particularly limited. It is, for example, 1.5 parts by mass or more, preferably 2 parts by mass or more, and for example, 15 parts by mass or less, preferably 12 parts by mass or less, relative to 100 parts by mass of (A) the organic polymer having a crosslinkable silicon group. If the content of (B) the compound having two or more crosslinkable silicon groups and a secondary amino group is less than 1.5 parts by mass, the crosslink density may decrease, resulting in a decrease in adhesiveness. If the content of (B) the compound having two or more crosslinkable silicon groups and a secondary amino group exceeds 20 parts by mass, the curing rate of the composition increases, making it difficult to ensure sufficient working time.

[0032] [(C) Compound Having a Glycidyl Group and a Crosslinkable Silicon Group] The composition of the present invention contains (C) a compound having a glycidyl group and a crosslinkable silicon group, wherein the crosslinkable silicon group is the same as the crosslinkable silicon group described above in (A) Organic Polymer Having a Crosslinkable Silicon Group.

[0033] The compound (C) having a glycidyl group and a crosslinkable silicon group is not particularly limited as long as it has a glycidyl group and a crosslinkable silicon group, and examples thereof include one or more compounds selected from the group consisting of 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0034] The content of the (C) compound having a glycidyl group and a crosslinkable silicon group in the composition is not particularly limited. It is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, relative to 100 parts by mass of the (A) organic polymer having a crosslinkable silicon group. If the content of the (C) compound having a glycidyl group and a crosslinkable silicon group is less than 0.1 parts by mass, the effect as an adhesion promoter may be reduced, resulting in a decrease in adhesiveness. If the content of the (C) compound having a glycidyl group and a crosslinkable silicon group exceeds 20 parts by mass, the crosslink density of the composition may be reduced, resulting in a decrease in adhesiveness.

[0035] [(D) Other Components] In addition to the essential components of (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group, the composition of the present invention may optionally contain (D) other components. Examples of (D) other components include fillers, plasticizers, curing catalysts, antioxidants, colorants, diluents, moisture absorbents, flame retardants, silane coupling agents, tackifiers, thixotropic agents, anti-sagging agents, and mildew inhibitors. These (D) other components may be used alone or in combination of two or more. Of these (D) other components, the composition of the present invention preferably contains at least a filler, a plasticizer, and a curing catalyst.

[0036] <Filler> The composition of the present invention may contain a filler. As the filler, one or more types selected from the group consisting of inorganic fillers and organic fillers can be used.

[0037] The inorganic filler is not particularly limited. Examples thereof include calcium carbonate (colloidal calcium carbonate, heavy calcium carbonate, light calcium carbonate, etc.), silica (silica sand, fumed silica, precipitated silica, silicic anhydride, hydrated silicic acid, etc.), alumina, magnesium oxide, aluminum hydroxide, carbon black, magnesium hydroxide, calcium hydroxide, calcium oxide, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolin, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc oxide, lightweight aggregates (glass balloons, fly ash balloons, shirasu balloons, etc.), and inorganic fibers. Examples of organic fillers include polyolefin resin powder, acrylic resin powder, polyamide resin powder, polyester resin powder, polyurethane resin powder, polyvinyl chloride resin powder, polystyrene resin powder, lightweight aggregates (synthetic resin foam beads) formed by expanding synthetic resins to form hollow structures, and the like.

[0038] The composition of the present invention may contain calcium carbonate as a filler. The inclusion of calcium carbonate can impart thixotropy to the composition, improve application workability, impart a reinforcing effect to the cured product (cured film) of the composition, and improve the compression set of the cured product (cured film) of the composition. The calcium carbonate is not particularly limited, and for example, one or more types selected from the group consisting of colloidal calcium carbonate, heavy calcium carbonate, and minor calcium carbonate can be used. Surface-treated calcium carbonate may also be used. The composition of the present invention preferably contains one or more types of heavy calcium carbonate. Furthermore, the composition of the present invention may contain a mixture of heavy calcium carbonate and colloidal calcium carbonate.

[0039] When the composition of the present invention contains a filler, the content thereof is not particularly limited. The total amount of (A) the organic polymer having a crosslinkable silicon group, (B) the compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) the compound having a glycidyl group and a crosslinkable silicon group is taken as 100 parts by mass, and the content can be, for example, 600 parts by mass or less, preferably 550 parts by mass or less, and more preferably 500 parts by mass or less. If the content of the filler exceeds 600 parts by mass, the viscosity of the composition increases, the fluidity decreases, and the coating workability may decrease.

[0040] <Plasticizer> The composition of the present invention may contain a plasticizer. By containing a plasticizer, the physical properties such as rubber elasticity and viscosity of the composition can be adjusted.

[0041] Examples of the plasticizer include phthalate ester-based plasticizers such as dioctyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and diisoundecyl phthalate; aliphatic dibasic acid ester-based plasticizers such as dioctyl adipate, isodecyl succinate, dioctyl sebacate, and dibutyl adipate; glycol ester-based plasticizers such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and pentaerythritol ester; aliphatic ester-based plasticizers such as butyl oleate and methyl acetylricinoleate; phosphate ester-based plasticizers such as tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tributyl phosphate, and tricresyl phosphate; epoxy-based plasticizers such as epoxidized soybean oil, epoxidized linseed oil, and epoxy benzyl stearate; polyester-based plasticizers such as polyesters of dibasic acids and dihydric alcohols; polypropylene glycol (PPG), polyethylene glycol (PEG), and tetraethylene glycol diethyl polyether-based plasticizers such as ethers, copolymers of propylene oxide (PO) and ethylene oxide (EO); polyoxyethylene alkyl ether-based plasticizers such as polyoxyethylene dimethyl ether having one or more polyalkylene ether repeating units, such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol ethyl methyl ether, and tetraethylene glycol diethyl ether; polystyrene-based plasticizers such as poly-α-methylstyrene and polystyrene; hydrocarbon oligomer-based plasticizers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and process oil; chlorinated paraffin-based plasticizers;Examples of suitable plasticizers include one or more selected from the group consisting of (meth)acrylic polymer-based plasticizers, which are polymers of unsaturated monomers containing at least one of acrylic and methacrylic compounds, such as (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylonitrile, and (meth)acrylamide. Furthermore, the plasticizer may or may not have less than one crosslinkable silicon group per molecule. In the present invention, it is preferable to use, as the plasticizer, a compound having the same structure as the main chain of the (A) organic polymer having a crosslinkable silicon group, from the viewpoint of compatibility, etc.;

[0042] When the composition of the present invention contains a plasticizer, the content is the amount that allows the composition or its film (cured film) to have the desired hardness, rubber elasticity, etc., and is not particularly limited.When the total amount of (A) the organic polymer having a crosslinkable silicon group, (B) the compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) the compound having a glycidyl group and a crosslinkable silicon group is taken as 100 parts by mass, the content can be, for example, 300 parts by mass or less, preferably 150 parts by mass or less.If the content of the plasticizer exceeds 300 parts by mass, the film (cured film) of the composition may become brittle.

[0043] <Curing Catalyst> The composition of the present invention may contain a curing catalyst, which acts as a catalyst in the reaction of the crosslinkable silicon group, particularly in the moisture curing reaction.

[0044] Examples of the curing catalyst include tetravalent tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin oxide, dioctyltin dilaurate, dioctyltin maleate, dioctyltin diacetate, dioctyltin dineodecanoate (dioctyltin diversatate), dioctyltin oxide, a reaction product of dibutyltin oxide with a phthalate ester, and a reaction product of dibutyltin oxide with ethyl orthosilicate; and organic tin compounds such as divalent tin compounds such as tin dioctylate, tin dinaphthenate, tin distearate, and tin dineodecanoate (tin diversatate); tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanate, and titanium compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate; organic aluminum compounds such as bismuth tris(2-ethylhexanoate) and bismuth tris(neodecanoate) reactants with organic carboxylic acids or organic amines; chelate compounds such as zirconium tetraacetylacetonate; organic lead compounds such as lead octoate; organic iron compounds such as iron naphthenate; organic vanadium compounds; acidic phosphoric acid compounds; compounds having a fluorosilyl group; and boron halide compounds.

[0045] In addition to the tin catalyst and / or titanium catalyst, the composition of the present invention may also contain other curing catalysts in combination to the extent that the effects of the present invention are not impaired. Examples of other curing catalysts include organometallic compounds and amines.

[0046] When the composition of the present invention contains a curing catalyst, the content thereof is not particularly limited. It is, for example, 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of (A) the organic polymer having a crosslinkable silicon group, (B) the compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) the compound having a glycidyl group and a crosslinkable silicon group. If the content of the curing catalyst exceeds 15 parts by mass, the composition may cure too quickly, resulting in reduced workability and reduced storage stability of the composition.

[0047] <Antiaging Agent> The composition of the present invention may contain an antioxidant. By containing an antioxidant, deterioration of the composition and its film (coating film) due to ultraviolet rays, light, heat, etc. can be suppressed, and aging can be prevented. As the antioxidant, one or more selected from the group consisting of ultraviolet absorbers, antioxidants, etc. can be used. The antioxidant is used to prevent oxidation of the curable composition and improve weather resistance and heat resistance. Examples thereof include one or more selected from the group consisting of phenol-based, organic sulfur-based, hindered phenol-based, hindered amine-based, and organic phosphorus-based antioxidants. The ultraviolet absorber is used to prevent photodegradation of the curable composition and improve weather resistance. Examples thereof include one or more selected from the group consisting of benzotriazole-based, triazine-based, benzophenone-based, benzoate-based, salicylate-based, substituted tolyl-based, and metal chelate-based ultraviolet absorbers.

[0048] <Silane Coupling Agent> The composition of the present invention may contain a silane coupling agent to improve adhesion. Examples of the silane coupling agent include one or more selected from the group consisting of amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, ketimine group-containing silane coupling agents, isocyanate group-containing silane coupling agents, and (meth)acrylic group-containing silane coupling agents.

[0049] <Colorant> The composition of the present invention may contain a colorant. By containing a colorant, the composition can be given any color tone. Examples of colorants include one or more selected from the group consisting of inorganic pigments such as carbon black, red iron oxide, titanium dioxide, zinc oxide, and ultramarine, organic pigments such as azo pigments and phthalocyanine pigments, and dyes. When the composition of the present invention contains a colorant, the content thereof is an amount that results in a desired color tone and is not particularly limited.

[0050] <Diluent> The composition of the present invention may contain a diluent. By containing a diluent, physical properties such as viscosity can be adjusted, and coating workability can be adjusted. Examples of the diluent include one or more solvents selected from the group consisting of saturated hydrocarbon solvents, aromatic hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, and halogenated solvents.

[0051] <Moisture Absorbent> The composition of the present invention may contain a moisture absorbent. By containing a moisture absorbent, moisture during storage can be removed, thereby improving storage stability. Examples of the moisture absorbent include one or more selected from the group consisting of inorganic moisture absorbents such as alkoxysilane compounds, silica gel, zeolite, zinc oxide, and aluminum oxide.

[0052] <Flame Retardant> The composition of the present invention may contain a flame retardant. By containing a flame retardant, flame retardancy can be imparted to the composition. Examples of the flame retardant include one or more selected from the group consisting of phosphorus-based flame retardants such as red phosphorus and ammonium polyphosphate; metal oxide-based flame retardants such as antimony trioxide; bromine-based flame retardants; chlorine-based flame retardants, and metal hydroxide-based flame retardants such as aluminum hydroxide and magnesium hydroxide.

[0053] [Uses of the Composition] The composition of the present invention can be used for a variety of applications, including sealants, adhesives, surface preparation coating materials, pressure-sensitive adhesives, paints, sealants, insulating materials, films, and gaskets, and is not particularly limited thereto. Since the composition of the present invention has excellent adhesion between architectural finishing materials and substrates, it can be used as an adhesive for attaching architectural finishing materials, particularly as an adhesive for tiling. Examples of architectural finishing materials include tiles, bricks, stone / decorative materials, decorative panels, wooden interior materials, wall decorations, decorative films, wood panels, and boards used in building finishes. The substrate to which the architectural finishing material is attached is not particularly limited, and examples thereof include concrete substrates, ceramic siding, extruded cement boards, gypsum boards, calcium silicate boards, ALC panels, flexible boards, fiber-reinforced cement boards, and existing tiled walls.

[0054] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" in each example refers to "parts by mass." In addition, in Table 1, the numerical values ​​in the columns relating to each component represent the "amount (parts) blended."

[0055] [Synthesis Example] (B) Compound B1 as a compound having two or more crosslinkable silicon groups and a secondary amino group was synthesized as follows. 100 parts by mass of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) and 105 parts by mass of 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to a flask equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, a dropping device, and a reflux condenser, and the mixture was stirred at 50°C for 72 hours to obtain a reaction product containing compound B1 represented by the following structural formula (1) as a compound having two crosslinkable silicon groups and a secondary amino group. Compound B1:

[0056] [Examples 1 to 6, Comparative Examples 1 to 5] The materials shown in Table 1 were charged into a mixer in the mass ratios shown in Table 1 and stirred and mixed to prepare compositions according to Examples 1 to 6 and Comparative Examples 1 to 5. The resulting compositions of Examples 1 to 6 and Comparative Examples 1 to 5 were evaluated for adhesion after immersion in alkaline hot water and storage stability as described below. The results are also shown in Table 1.

[0057] The materials shown in Table 1 are as follows: Polymer A: crosslinkable silicon group-containing polyoxypropylene polymer ("EST280" manufactured by Kaneka Corporation) Compound B1: compound obtained in Synthesis Example 1 Compound C1: 3-glycidoxypropyltrimethoxysilane Epoxy resin: glycidyl ether type epoxy resin Ketimine compound: condensation reaction product of 3-aminopropyltrimethoxysilane and methyl isobutyl ketone Calcium carbonate 1: colloidal calcium carbonate ("CALFINE 500" manufactured by Maruo Calcium Co., Ltd.) Calcium carbonate 2: heavy calcium carbonate ("NN#500" manufactured by Nitto Funka Kogyo Co., Ltd.) Plasticizer: polyoxypropylene glycol-based plasticizer ("Actocol D3000" manufactured by Mitsui Chemicals, Inc.) Catalyst: dibutyltin diacetylacetonate

[0058] <Evaluation of Adhesion After Immersion in Warm Alkaline Water> A composition was applied to a mortar board (70 mm x 70 mm x 20 mm) using a 5 mm comb trowel, and a ceramic tile (45 mm x 45 mm x 7 mm) was attached. Any excess composition was quickly removed. The board was then cured for 14 days in an environment with a temperature of 23°C and a humidity of 50% RH, thereby carrying out standard curing. After standard curing, the board was immersed in a saturated aqueous solution of calcium hydroxide at 60°C for 7 days, thereby accelerating deterioration by immersion in warm alkaline water.

[0059] (Tensile Adhesion Strength After Immersion in Alkaline Hot Water) After the immersion in alkaline hot water, a tensile test was carried out at a tensile speed of 3 mm / min to measure the "tensile adhesion strength after immersion in alkaline hot water." The tensile adhesion strength was calculated by multiplying the maximum load (N) by the area of ​​the entire fracture surface [area of ​​the tile (45 mm x 45 mm)] (mm ２ ) and the figure was calculated by dividing it by .

[0060] (Cohesive failure rate after immersion in alkaline hot water) The state of failure during the measurement of the "tensile bond strength after immersion in alkaline hot water" was examined visually and by a cross-cut measurement method, and the area percentage (%) of each failure position was calculated. The total value (%) of the area percentages where cohesive failure (material failure of the tile, material failure of the adhesive, and material failure of the base material (mortar)) occurred was defined as the "cohesive failure rate after immersion in alkaline hot water."

[0061] (Evaluation of Adhesion After Immersion in Warm Alkaline Water) "Evaluation of Adhesion After Immersion in Warm Alkaline Water" was performed according to the following criteria. A is acceptable, and C is unacceptable. A: Tensile adhesive strength 0.40 N / mm ２ or more, and cohesive failure rate is 50% or more C: Tensile adhesive strength 0.40 N / mm ２ or cohesive failure rate less than 50%

[0062] <Storage Stability Evaluation> (Storage Stability TI Value Change Rate) After preparing each composition, it was left to stand for 1 day at 23°C and 50% RH. Using a Brookfield viscometer, viscosity was measured at a rotation speed of 10 RPM and at a rotation speed of 1 RPM, and the TI value before the storage stability test was calculated using the following formula (1). The composition placed in a sealed container was left to stand in air at 50°C for 28 days, and then left to stand for 1 day at 23°C and 50% RH. Using a Brookfield viscometer, viscosity was measured at a rotation speed of 10 RPM and at a rotation speed of 1 RPM, and the TI value after the storage stability test was calculated using the following formula (1). Next, the TI value change rate (%) after the storage stability test was calculated using the following formula (2). [TI value] = [viscosity at 1 RPM] / [viscosity at 10 RPM] Formula (1) [Storage stability TI value change rate] = ([TI value after storage stability test] / [TI value before storage stability test] × 100) - 100 Formula (2)

[0063] (Storage Stability Evaluation) The "storage stability evaluation" was performed according to the following criteria. A is pass, and C is fail. A: Storage stability TI value change rate exceeds -12%. C: Storage stability TI value change rate is -12% or less.

[0064]

[0065] As shown in Examples 1 to 6, compositions containing (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group, were excellent in the adhesion evaluation after immersion in hot alkaline water and had no practical problems. On the other hand, the composition of Comparative Example 4, which did not contain (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and the composition of Comparative Example 5, which did not contain (C) a compound having a glycidyl group and a crosslinkable silicon group, were inferior in the adhesion evaluation after immersion in hot alkaline water.

[0066] As shown in Examples 1 to 6, compositions containing (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group had the desired storage stability TI value change rate, were excellent in the storage stability evaluation, and presented no practical problems. On the other hand, as shown in Comparative Examples 1 to 3, compositions containing an epoxy resin but not (B) a compound having two or more crosslinkable silicon groups and a secondary amino group did not have the desired storage stability TI value change rate, and were poor in the storage stability evaluation.

[0067] Although the present invention has been described in detail above, various changes can be made in the above configuration without departing from the scope of the present invention. Accordingly, all matter contained in the above description or shown in the accompanying drawings should be interpreted as illustrative only.

Claims

1. A composition containing (A) an organic polymer having a crosslinkable silicon group, (B) a compound having two or more crosslinkable silicon groups and a secondary amino group, and (C) a compound having a glycidyl group and a crosslinkable silicon group.

2. The composition described in claim 1, wherein the content of the compound (B) having two or more crosslinkable silicon groups and a secondary amino group is 1.5 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group.

3. The composition according to claim 1 or 2, which is an adhesive for applying architectural finish materials.

4. A composition described in claim 1 or 2, wherein the content of the compound (C) having a glycidyl group and a crosslinkable silicon group is 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the organic polymer (A) having a crosslinkable silicon group.

5. The composition of claim 4 which is an architectural finish application adhesive.

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