WO2023145711A1 - Composition durcissable et son utilisation - Google Patents

Composition durcissable et son utilisation Download PDF

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WO2023145711A1
WO2023145711A1 PCT/JP2023/002025 JP2023002025W WO2023145711A1 WO 2023145711 A1 WO2023145711 A1 WO 2023145711A1 JP 2023002025 W JP2023002025 W JP 2023002025W WO 2023145711 A1 WO2023145711 A1 WO 2023145711A1
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meth
weight
hydrolyzable silyl
group
curable composition
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Japanese (ja)
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翔大 神谷
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株式会社カネカ
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a curable composition and its cured product.
  • curable compositions containing organic polymers having hydrolyzable silyl groups have been used as sealants and the like.
  • Such curable compositions are often blended with aluminum hydroxide for the purpose of imparting flame retardancy.
  • Patent Document 1 discloses an organic polymer (A) having a hydrolyzable silyl group, a specific amount of aluminum hydroxide (B) having a sodium oxide content of 1000 ppm or less, and a specific amount of divalent tin.
  • a moisture-curable resin composition containing a compound (C) is disclosed.
  • curable compositions containing aluminum hydroxide tend to have poor adhesion, and there is room for improvement in this respect.
  • an object of the present invention is to provide a curable composition in which aluminum hydroxide is blended to improve flame retardancy and which has improved adhesiveness.
  • the present inventors have made intensive studies to solve the above problems, and as a result, a curable composition containing an organic polymer having a hydrolyzable silyl group was subjected to specific processing (specifically, The present inventors have found for the first time that the adhesivity can be improved by blending aluminum hydroxide (B) surface-treated with titanate, and have completed the present invention.
  • one aspect of the present invention contains an organic polymer (A) having a hydrolyzable silyl group, an aluminum hydroxide surface-treated with titanate (B), and a silanol condensation catalyst (C), It is a curable composition (hereinafter referred to as "this curable composition").
  • the present inventors have made intensive studies on the curable composition containing aluminum hydroxide from the viewpoint of improving adhesiveness, and as a result, contain aluminum hydroxide (B) surface-treated with titanate. It was found for the first time that the adhesion can be improved by
  • the curable composition contains an organic polymer (A) having a hydrolyzable silyl group, an aluminum hydroxide surface-treated with titanate (B), and a silanol condensation catalyst (C). .
  • organic polymer (A) having a hydrolyzable silyl group is referred to as "(A) component
  • aluminum hydroxide (B) surface-treated with titanate is referred to as “(B) component”
  • Silanol condensation catalyst (C) as “(C) component”
  • hydrolyzable silyl group-containing ( The meth)acrylic ester-based copolymer (A2) may be referred to as the "(A2) component”.
  • the curable composition contains an organic polymer (A) having hydrolyzable silyl groups.
  • the organic polymer (A) having a hydrolyzable silyl group is a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) (hereinafter referred to as "(A1) component” ), and/or the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) (hereinafter sometimes referred to as "(A2) component”).
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) and converted to standard polystyrene.
  • component (A) the polymer precursor before the introduction of the hydrolyzable silyl group was measured according to the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method specified in JIS K 0070. It is also possible to directly measure the terminal group concentration by titration analysis based on the molecular weight obtained by considering the structure of the polymer (the degree of branching determined by the polymerization initiator used).
  • the terminal group-equivalent molecular weight of the polymer (A) is obtained by preparing a calibration curve of the number average molecular weight (Mn) obtained by general GPC measurement of the polymer precursor and the above-mentioned terminal group-equivalent molecular weight, and obtaining a hydrolyzable silyl group-containing It is also possible to convert the number-average molecular weight (Mn) of the polymer obtained by GPC into a terminal group-equivalent molecular weight.
  • the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) is a hydrolyzable silyl group-containing polymer in which the polymer portion (also referred to as “main chain”) is polyoxyalkylene.
  • the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) forms siloxane bonds between molecules to form a crosslinked product under specific conditions known to those skilled in the art.
  • the lower limit of the number average molecular weight (Mn) of the component (A1) is preferably 500 or more, more preferably 1,500 or more, even more preferably 5,000 or more, most preferably 10,000 or more. preferable.
  • the upper limit of the number average molecular weight of component (A1) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. If the number average molecular weight is within the above range, it is preferable from the viewpoint of ease of handling such as workability and adhesiveness.
  • the ratio (Mw/Mn; molecular weight distribution) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component (A1) is preferably 1.6 or less, and 1.5 or less. is more preferable, 1.4 or less is more preferable, 1.3 or less is particularly preferable, and 1.2 or less is particularly preferable. If the molecular weight distribution is within the above range, it is preferable from the viewpoint of ease of handling such as workability and adhesiveness.
  • hydrolyzable silyl group The structure of the hydrolyzable silyl group contained in component (A1) is not particularly limited. Hydrolyzable silyl groups commonly used in this technical field may be used.
  • the hydrolyzable silyl group of component (A1) is represented by the following general formula (1).
  • Two or more types of hydrolyzable silyl groups represented by general formula (1) may be contained in one polymer molecule.
  • R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms (if substituted, it may be substituted with a heteroatom-containing group).
  • the structures of the R 1 may be the same or different. Examples of R 1 include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms.
  • X represents a hydroxyl group or a hydrolyzable group.
  • hydrolyzable groups include hydroxyl groups, halogens, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups, and the like.
  • alkoxy groups such as methoxy group and ethoxy group are more preferred, methoxy group and ethoxy group are more preferred, and methoxy group is particularly preferred, since they are moderately hydrolyzable and easy to handle.
  • a is 1, 2 or 3; As a, 2 or 3 is preferable because a network structure is formed by condensation to obtain a cured product.
  • alkoxy groups with fewer carbon atoms have higher reactivity. That is, the reactivity decreases in the order of methoxy group, ethoxy group, and propoxy group.
  • the specific structure of the hydrolyzable silyl group can be appropriately determined depending on the production method and application of the component (A1).
  • hydrolyzable silyl groups include trimethoxysilyl, triethoxysilyl, triisopropoxysilyl, dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, (chloromethyl)dimethoxy
  • a silyl group and a (methoxymethyl)dimethoxysilyl group can be mentioned.
  • the hydrolyzable silyl group is preferably a dialkoxysilyl group or a trialkoxysilyl group in consideration of the physical properties of the resulting cured product and the availability and ease of handling of the raw material compound. Further, in consideration of the curable composition and its excellent shape retention property during curing, a dialkoxysilyl group is preferable, and in consideration of a high cross-linking reaction rate, a trialkoxysilyl group is preferable.
  • the lower limit of the number of hydrolyzable silyl groups contained in one polymer molecule is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more.
  • the upper limit of the number of hydrolyzable silyl groups contained in one polymer molecule is preferably 5.0 or less, more preferably 4.0 or less. If the number of hydrolyzable silyl groups is within the above range, sufficient flexibility can be imparted to the cured product obtained by the condensation reaction of the silyl groups.
  • the distribution of hydrolyzable silyl groups may be random or block-shaped.
  • the distribution position of the hydrolyzable silyl group may be anywhere in the polymer molecule.
  • the distribution position of the hydrolyzable silyl group includes the terminal or the vicinity of the terminal of the polymer molecule. More preferably, the distribution position of the hydrolyzable silyl group is localized at or near the terminal of the polymer molecule.
  • "near the ends of the polymer molecule” refers to the region from each end of the polymer molecule to a specific position in the polymer molecule, and the weight of the region is the total weight of the polymer molecule.
  • the term "localized at or near the terminal of the polymer molecule” refers to the hydrolyzable silyl groups contained in the polymer molecule that are located at or near the terminal. It means that the number of things accounts for 70% or more, 80% or more, or 90% or more.
  • a known method may be employed for introducing a hydrolyzable silyl group into the polyoxyalkylene polymer.
  • the polyoxyalkylene structure in component (A1) may be linear or branched.
  • the polyoxyalkylene structure is a structure derived from polyoxypropylenediol or polyoxypropylenetriol.
  • the polyoxyalkylene polymer molecule may be composed of only one type of repeating unit, or may contain two or more types of repeating units.
  • One type of polyoxyalkylene-based polymer may be blended, or two or more types of polyoxyalkylene-based polymer may be blended.
  • Examples of the main chain structure of the polyoxyalkylene polymer include structures having repeating units represented by the following general formula (2).
  • R2 is a divalent alkylene group.
  • the structure represented by the general formula (2) preferably accounts for 50% by weight or more, more preferably 70% by weight or more, of the total weight of the polyoxyalkylene polymer in the component (A1). It is more preferable to account for more than % by weight.
  • R 2 is preferably an alkylene group having 1 to 14 carbon atoms, more preferably a linear or branched alkylene group having 2 to 4 carbon atoms.
  • repeating unit represented by formula (2) examples include -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 CH 2 CH 2 CH 2 O—.
  • -CH 2 CH(CH 3 )O- is preferred.
  • a polyoxyalkylene polymer containing —CH 2 CH(CH 3 )O— in a repeating unit can easily adjust the glass transition temperature (Tg) to 0° C. or lower.
  • the polyoxyalkylene polymer may contain a urethane bond or a urea bond in the main chain structure.
  • a commercially available product can also be used as the polyoxyalkylene polymer.
  • Examples of commercially available products include Kaneka MS Polymer (registered trademark) S810, S257, S327, S203H, and S303H (all manufactured by Kaneka Corporation); , SAX750 (all manufactured by Kaneka Corporation); Exester (registered trademark) ES-S2410, ES-S2420, ES-S3630 (all manufactured by AGC Corporation); GENIOSIL (registered trademark) STP-E10, STP-E15, Examples include STP-E-30 and STP-E-35 (both manufactured by Wacker).
  • Method for producing polyoxyalkylene polymer As a method for producing the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1), the following methods (I) to (III) can be used.
  • the production method using the method (I) is preferable because a wide range of aluminum hydroxide content can be obtained in which the effects of the present invention can be obtained.
  • hydroxyl-containing initiators used in methods (I) and (II) include ethylene glycol, propylene glycol, glycerin, pentaerythritol, low molecular weight polypropylene glycol, polyoxypropylene triol, allyl alcohol, methanol, ethanol, propanol, Examples include those having one or more hydroxyl groups, such as butanol, pentanol, hexanol, polypropylene monoallyl ether, and polypropylene monoalkyl ether.
  • Epoxy compounds used in methods (I) and (II) include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and allyl glycidyl ether. Among these, propylene oxide is preferred.
  • Examples of the carbon-carbon unsaturated group used in method (I) include a vinyl group, an allyl group, a methallyl group, a propargyl group, and the like. Among these, an allyl group is preferred.
  • a hydroxyl-terminated polymer is reacted with an alkali metal salt, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted. It is preferable to use the method of
  • Halogenated hydrocarbon compounds used in method (I) include vinyl chloride, allyl chloride, methallyl chloride, propargyl chloride, vinyl bromide, allyl bromide, methallyl bromide, propargyl bromide, vinyl iodide, and allyl iodide. , methallyl iodide, propargyl iodide and the like.
  • Hydrosilane compounds used in method (I) include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetoxysilane, dimethoxymethylsilane, (chloromethyl)dimethoxysilane, and (methoxymethyl)dimethoxysilane. , (N,N-diethylaminomethyl)dimethoxysilane, and the like can be used.
  • the hydrosilylation reaction used in method (I) is accelerated by various catalysts.
  • a known catalyst may be used as the hydrosilylation catalyst.
  • Examples of compounds having both a hydroxyl group-reactive group and a hydrolyzable silyl group that can be used in method (II) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxy isocyanate silanes such as silane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane and the like Mercaptosilanes; epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, and the
  • Polyisocyanate compounds that can be used in the method (III) include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate; aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate. can be mentioned.
  • aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate
  • aliphatic polyisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate.
  • Compounds having both an isocyanate group-reactive group and a hydrolyzable silyl group that can be used in method (III) include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyltriethoxy Silane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyldimethoxymethylsilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane Ethoxysilane, ⁇ -(N-phenyl)aminopropyltrimethoxysilane, ⁇ -(N-phenyl)aminopropyldimethoxymethylsilane, N-ethylaminoisobutyltrimethoxysilane,
  • a polyoxyalkylene polymer having a plurality of hydrolyzable silyl groups at one end can also be used as the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1).
  • a method for synthesizing a polyoxyalkylene polymer having a plurality of hydrolyzable silyl groups at one end for example, (i) using a double metal cyanide complex catalyst, an epoxy compound is polymerized with an initiator having a hydroxyl group.
  • the hydrolyzable silyl group-containing (meth)acrylate copolymer (A2) is a hydrolyzable silyl group-containing polymer in which the polymer portion is a (meth)acrylate copolymer. Under specific conditions known to those skilled in the art, the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) forms siloxane bonds between molecules to form a crosslinked product.
  • the lower limit of the number average molecular weight (Mn) of component (A2) is preferably 500 or more, more preferably 1,500 or more, even more preferably 5,000 or more, most preferably 10,000 or more. preferable.
  • the upper limit of the number average molecular weight of component (A2) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 45,000 or less. If the number average molecular weight is within the above range, it is preferable from the viewpoint of ease of handling such as workability and adhesiveness.
  • the ratio (Mw/Mn; molecular weight distribution) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the component (A2) is preferably 1.6 or less, and 1.5 or less. is more preferable, 1.4 or less is more preferable, 1.3 or less is particularly preferable, and 1.2 or less is particularly preferable. If the molecular weight distribution is within the above range, it is preferable from the viewpoint of ease of handling such as workability and adhesiveness.
  • hydrolyzable silyl group The hydrolyzable silyl group in the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) is the hydrolyzable sexual silyl group] section is incorporated.
  • (Meth)acrylic acid esters contain structural units derived from (meth)acrylic monomers.
  • (meth)acryl means acryl and/or methacryl.
  • the (meth)acrylate structure in component (A2) may be linear or branched.
  • the (meth)acrylic acid ester molecule may consist of only one type of repeating unit, or may contain two or more types of repeating units. One type of (meth)acrylic acid ester may be blended, or two or more types of (meth)acrylic acid ester may be blended.
  • Examples of the (meth)acrylic acid ester structure include structures represented by the following general formula (3).
  • R3 is a hydrogen atom or a methyl group
  • R4 is a group having 1 or more carbon atoms.
  • the carbon number of R 4 can be, for example, 1-22.
  • R4 can be an alkyl group, a cycloalkyl group or an aryl group.
  • R4 may be substituted with halogen, hydroxy group, alkoxy group, amino group and the like.
  • the structure represented by general formula (3) is obtained by polymerizing a (meth)acrylic monomer.
  • (meth)acrylic monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate.
  • (meth)acrylic monomers one selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and stearyl acrylate
  • the above is preferable.
  • the main chain structure composed of these monomers facilitates adjusting the glass transition temperature (Tg) to 0° C. or lower.
  • a commercially available product can also be used as the (meth)acrylic acid ester.
  • Examples of commercially available products include XMAP (registered trademark) SA100S, SA110S, SA120S, SA310S, SA410S (all manufactured by Kaneka Corporation); ARUFON (registered trademark) US-6100, US-6110, US-6120, US-6130 , US-6140, US-6150, US-6170, US-6180, US-6190 (all manufactured by Toagosei Co., Ltd.); Actflow NE-1000 (registered trademark) (manufactured by Soken Chemical Co., Ltd.); Joncryl (registered trademark) (manufactured by BASF).
  • the (meth)acrylic acid ester preferably contains an XY diblock structure or an XYX triblock structure in the molecule.
  • the X block is a block having a relatively large content of hydrolyzable silyl groups.
  • a Y block is a Y block having a relatively low content of hydrolyzable silyl groups.
  • the structure of the entire molecule of the (meth)acrylic acid ester is not particularly limited as long as it contains an XY diblock structure or an XYX triblock structure, and may be, for example, an XYXY tetrablock structure.
  • the "XYX triblock structure” means the "ABA triblock structure" generally called by those skilled in the art.
  • the number of repeating units derived from the hydrolyzable silyl group-containing monomer contained in the X block is more than 1.0 on average, preferably 1.5 or more, and more preferably 1.7 or more.
  • the repeating unit derived from the hydrolyzable silyl group-containing monomer contained in the X block is preferably more than 3% by weight, more preferably 4.5% by weight or more, based on the weight of all repeating units contained in the X block. Preferably, 5% by weight or more is more preferable.
  • the (meth)acrylic acid ester is an XYX triblock polymer, and the blocks (X blocks) constituting the terminal portion of the (meth)acrylic acid ester each contain a hydrolyzable silyl group. It is preferred to have more than one.
  • the repeating unit derived from a hydrolyzable silyl group-containing monomer contained in the Y block is 0 to 3% by weight, preferably 0 to 2% by weight, based on the weight of all repeating units contained in the Y block. ⁇ 1 wt% is more preferred.
  • the repeating unit derived from the hydrolyzable silyl group-containing monomer is localized in the region near the end (near one end or both ends).
  • the (meth)acrylic acid ester can be produced by a known polymerization method (radical polymerization method, cationic polymerization method, anionic polymerization method, etc.).
  • hydrolyzable silyl group-containing (meth)acrylate copolymer (A2) As a preferred method for producing the hydrolyzable silyl group-containing (meth)acrylate copolymer (A2), the following methods (IV) to (VI) can be used.
  • (V) A method of copolymerizing a monomer having a (meth)acrylic structure in the presence of a compound having a hydrolyzable silyl group and a mercapto group as a chain transfer agent.
  • a compound having a polymerizable unsaturated group and a hydrolyzable silyl group is covalently mixed with a monomer in the presence of a mercaptan having a hydrolyzable silyl group as a chain transfer agent. It is also possible to adopt a method of polymerization.
  • the living polymerization method (VI) is preferable because it can introduce a functional group to the end of the polymer molecule and synthesize a (meth)acrylic acid ester with a narrow molecular weight distribution.
  • Compounds having a polymerizable unsaturated group and a hydrolyzable silyl group used in (IV) include 3-(dimethoxymethylsilyl)propyl (meth)acrylate, (dimethoxymethylsilyl)methyl (meth)acrylate, (meth) ) (diethoxymethylsilyl)methyl acrylate, 3-((methoxymethyl)dimethoxysilyl)propyl (meth)acrylate, and the like.
  • the compound having a hydrolyzable silyl group and a mercapto group used in (V) includes 3-mercaptopropyldimethoxymethylsilane, (mercaptomethyl)dimethoxymethylsilane, and the like.
  • Examples of the living polymerization method (VI) include a living radical polymerization method, a living cationic polymerization method, and a living anionic polymerization method, among which the living radical polymerization method is suitable for producing a (meth)acrylic acid ester.
  • Examples of living radical polymerization methods include the following. Atom Transfer Radical Polymerization (ATRP (see J. Am. Chem. Soc. 1995, 117, 5614; Macromolecules. 1995, 28, 1721)) ⁇ One electron transfer polymerization (Sigle Electron Transfer Polymerization; SET-LRP (J. Am. See Chem. Soc.
  • JP-A-2007-302749 introduces a hydrolyzable silyl group by converting the terminal functional group of a (meth)acrylic acid ester. Specifically, a hydrolyzable silyl group is introduced by converting the molecular terminal of the (meth)acrylic acid ester into a hydroxyl group, an alkenyl group, and a hydrolyzable silyl group in that order.
  • the method described in JP-A-2018-162394 introduces a hydrolyzable silyl group by copolymerization with a hydrolyzable silyl group-containing (meth)acrylate monomer.
  • hydrolyzable silyl introduce a group.
  • the hydrolyzable silyl group-containing (meth)acrylic acid esters obtained by these methods have locally hydrolyzable silyl groups at or near the ends of the molecule.
  • the upper limit of the glass transition temperature (Tg) of the (meth)acrylic acid ester in the component (A2) is preferably 100°C or less, more preferably 50°C or less, even more preferably 0°C or less, and most preferably -10°C or less.
  • the lower limit of the glass transition temperature (Tg) of the (meth)acrylic acid ester is not particularly limited, it is preferably ⁇ 80° C. or higher, more preferably ⁇ 70° C. or higher.
  • the glass transition temperature of the (meth)acrylic acid ester can be substantially regarded as the glass transition temperature of the component (A2) itself.
  • the (A) component can be used by mixing the low-viscosity (A1) component and the high-viscosity (A2) component.
  • A1 component and A2 component are used together, there is an advantage that the adhesiveness is further improved and the workability is improved as compared with the case where each component is used alone.
  • the viscosity of component (A1) is not particularly limited, but is preferably 1 Pa ⁇ s to 100 Pa ⁇ s, more preferably 5 Pa ⁇ s to 80 Pa ⁇ s, and even more preferably 10 Pa ⁇ s to 70 Pa ⁇ s. This configuration has the advantage that the resulting curable composition has a low viscosity.
  • the viscosity of component (A2) is not particularly limited, but is preferably 6.0 Pa ⁇ s to 1000 Pa ⁇ s, more preferably 50 Pa ⁇ s to 750 Pa ⁇ s, and even more preferably 100 Pa ⁇ s to 500 Pa ⁇ s. This configuration has the advantage of improving the adhesiveness of the resulting curable composition and the tensile elongation of the cured product.
  • the weight ratio (A1):(A2) of the (A1) component and the (A2) component is preferably 5:95 to 50:50. Within this range, a cured product exhibiting flexibility and high shear adhesive strength can be obtained. Further, (A1):(A2) is preferably 20:80 to 50:50 from the viewpoint of achieving both high rigidity and flexibility.
  • the curable composition comprises a titanate surface treated aluminum hydroxide (B).
  • the present curable composition can improve the adhesion of the curable composition containing component (A) by including aluminum hydroxide (B) surface-treated with titanate.
  • the component (B) is not particularly limited as long as it is aluminum hydroxide surface-treated with titanate.
  • Examples of component (B) include Hygilite (registered trademark) H-42T (manufactured by Showa Denko KK), BF013T, BX053T, B103T, BW53T, and BW153T (all of which are manufactured by Nippon Light Metal Co., Ltd.). These components (B) may be used alone or in combination of two or more.
  • component (B) contains at least one titanate surface-treated product, the product to be combined with it may be a surface-treated product other than titanate or a surface-untreated product. good.
  • the average particle diameter of aluminum hydroxide (B) is, for example, 0.1 to 200 ⁇ m, preferably 0.2 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m, and 0.4 to 20 ⁇ m. is more preferable, and 0.5 to 10 ⁇ m is particularly preferable.
  • the average particle size of aluminum hydroxide (B) is 0.1 to 200 ⁇ m, workability and mechanical properties can be adjusted in a well-balanced manner.
  • the average particle size is measured with a laser scattering particle size analyzer (Microtrac 9320HRA ( ⁇ 100) manufactured by Nikkiso Co., Ltd.).
  • the content of aluminum hydroxide (B) is preferably 30 to 320 parts by weight, more preferably 100 to 315 parts by weight, and more preferably 185 to 310 parts by weight, per 100 parts by weight of component (A). and particularly preferably 190 to 310 parts by weight.
  • the content of aluminum hydroxide (B) is 30 to 320 parts by weight, the adhesion is excellent, and when the content of aluminum hydroxide (B) is 190 to 310 parts by weight, the adhesion is even better.
  • the component (A) has at least one urethane bond or urea bond in one molecule, it may be 270 to 320 parts by weight per 100 parts by weight of the component (A). 275 to 300 parts by weight is particularly preferred.
  • the curable composition contains a silanol condensation catalyst (C).
  • the silanol condensation catalyst (C) is not particularly limited.
  • dialkyltin oxides such as dibutyltin oxide and dioctyltin oxide with ester compounds such as dioctyl phthalate, diisodecyl phthalate and methyl maleate
  • dialkyltin oxides carboxylic acids and a tin compound obtained by reacting an alcohol compound, for example, a reaction product of a dialkyltin oxide such as dibutyltin bistriethoxysilicate or dioctyltin bistriethoxysilicate with a silicate compound, and an oxy derivative of these dialkyltin compounds (stannoxane compound) tetravalent tin compounds such as; Reactants and mixtures; monoalkyltins, such as monobutyltin compounds and monooctyltin compounds, such as monobutyltin trisoctoate and monobutyltin triisopropoxide; titanates such as ethylhexyl) titanate and is
  • aliphatic tertiary amines such as triamylamine, trihexylamine, trioctylamine; aliphatic unsaturated amines such as triallylamine, oleylamine; laurylaniline, stearylaniline, triphenylamine, etc.
  • amines such as monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, ethylenediamine, hexamethylene Diamine, N-methyl-1,3-propanediamine, N,N'-dimethyl-1,3-propanediamine, diethylenetriamine, triethylenetetramine, 2-(2-aminoethylamino)ethanol, benzylamine, 3-methoxy Propylamine, 3-lauryloxypropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-dibutylaminopropylamine, 3-morpholinopropylamine, 2-(1-piperazinyl)ethylamine, xylylenediamine, 2 , 4,6-tris(dimethylaminomethyl)
  • Reaction products and mixtures of amine compounds and organotin compounds such as reaction products or mixtures of laurylamine and tin octoate; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds.
  • silane coupling agents having an amino group such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, and aminosilylated silicones, which are modified derivatives thereof;
  • Catalysts further known silanol condensation catalysts such as fatty acids such as felzatic acid, other acidic catalysts such as organic acidic phosphoric acid ester compounds, basic catalysts, and the like can be exemplified.
  • silanol condensation catalyst (C) divalent tin is preferably used from the viewpoint of storage stability and durability.
  • the content of the silanol condensation catalyst (C) is, for example, preferably 0.5 to 20 parts by weight, more preferably 1.0 to 10 parts by weight, per 100 parts by weight of component (A). , 2.0 to 7.5 parts by weight. If the content of the silanol condensation catalyst (C) is from 0.5 to 20 parts by weight, there is an advantage that both curability and cost reduction are readily compatible.
  • this curable composition contains fillers, plasticizers, epoxy compounds, ultraviolet absorbers, light stabilizers, antioxidants, surface modifiers, solvents, anti-sagging agents, and physical property adjustment agents. Agents, adhesiveness-imparting agents, tackifiers, photo-curing substances, oxygen-curing substances, other resins, etc. may be added.
  • the curable composition may optionally contain diluents, silicates, curability modifiers, radical inhibitors, and metal deactivators. , antiozonants, phosphorus-based peroxide decomposers, lubricants, pigments, fungicides, flame retardants, foaming agents, and other additives may be added.
  • Fillers can be used in the curable composition. Since the filler is an inexpensive material, it enables cost reduction and adjustment of mechanical properties.
  • fillers include, but are not limited to, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, diatomaceous earth, calcined clay, clay, talc, barite, anhydrite, titanium oxide, bentonite, Organic bentonite, ferric oxide, fine aluminum powder, flint powder, zinc oxide, active zinc white, mica, zinc white, white lead, lithopone, zinc sulfide, carbon black, alumina, PVC powder, PMMA powder, glass fiber, filament etc. These fillers may be used alone or in combination of two or more.
  • the amount of the filler used is, for example, preferably 5 to 500 parts by weight, more preferably 10 to 250 parts by weight, and 20 to 150 parts by weight with respect to 100 parts by weight of component (A). is more preferred.
  • organic balloons or inorganic balloons may be added.
  • the balloon is made of a spherical filler and has a hollow interior.
  • materials for the balloon include inorganic materials such as glass and shirasu, and organic materials such as phenol resin, urea resin, polystyrene, and saran.
  • the amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the polymer (A).
  • plasticizer can be used in the curable composition.
  • plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl
  • polymer plasticizer can be used.
  • polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like.
  • reactive plasticizers can be used.
  • reactive plasticizers include polyoxyalkylene polymers, saturated hydrocarbon polymers, (meth) Examples include acrylic acid ester-based polymers and polyorganosiloxane-based polymers.
  • polyoxyalkylene-based polymers and (meth)acrylic acid ester-based polymers are preferred as the main chain skeleton of the reactive plasticizer.
  • the use of a reactive plasticizer can reduce the viscosity of the composition and suppress the bleed-out of the plasticizer compared to the use of a low-molecular-weight plasticizer.
  • the hydrolyzable silyl group in the reactive plasticizer may be at the molecular chain end, side chain, or both.
  • the hydrolyzable silyl group when the hydrolyzable silyl group is present at the end of the molecular chain, the molecular weight between cross-linking points becomes long, and a rubber-like cured product having good mechanical properties can be easily obtained, which is more preferable.
  • the average number of hydrolyzable silyl groups per molecule is 0.5 or more and less than 1.5, but the lower limit is preferably 0.6 or more from the viewpoint of mechanical properties during curing. Also, the upper limit is preferably less than 1.0 in order to efficiently lower the modulus of the cured product.
  • the reactive plasticizer may have a terminal olefin group and/or an internal olefin group in addition to the hydrolyzable silyl group, and may not have a terminal olefin group and/or an internal olefin group.
  • the total number of hydrolyzable silyl groups, terminal olefinic groups and internal olefinic groups may be 1.0 or less per terminal structure on average.
  • the polymer that is the reactive plasticizer preferably has a number average molecular weight of 3,000 or more and less than 15,000 in terms of polystyrene by GPC. If the number average molecular weight is 3,000 or more, sufficient mechanical properties can be obtained. Further, if the number average molecular weight is 15,000 or less, the viscosity is low and a sufficient dilution effect can be obtained.
  • the molecular weight distribution of the reactive plasticizer is not particularly limited, it is preferably less than 2.0, more preferably 1.6 or less, even more preferably 1.4 or less, particularly preferably 1.3 or less, and particularly preferably 1.2 or less. preferable.
  • the main chain structure of the reactive plasticizer may be a linear or branched structure, or a structure having multiple hydrolyzable silyl groups at one end. Among them, a straight-chain polymer having a hydrolyzable silyl group introduced at only one end is more preferable. Moreover, the main chain structure does not have to be a single one, and the respective polymers may be separately produced and mixed, or may be produced simultaneously so as to obtain an arbitrary polymer.
  • the hydrolyzable silyl group contained in the reactive plasticizer can be arbitrarily selected, but if it has the same hydrolyzable silyl group as the component (A) of the present invention, the physical properties of the cured product such as hardness and skinning time can be adjusted. It is particularly preferable because it is easy to clean.
  • a plasticizer may be used individually and may use 2 or more types together.
  • the amount of plasticizer used is, for example, 5 to 150 parts by weight, preferably 10 to 120 parts by weight, more preferably 12 to 100 parts by weight, per 100 parts by weight of component (A).
  • Epoxy compound can be used in the present curable composition. The use of these can improve the restorability of the cured product.
  • epoxy compounds include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate , epoxy butyl stearate and the like. Epoxy resins such as bisphenol A type epoxy resins and novolac type epoxy resins can also be used as epoxy compounds.
  • the amount of the epoxy compound used is, for example, preferably 1 to 100 parts by weight, more preferably 2 to 75 parts by weight, and 5 to 50 parts by weight with respect to 100 parts by weight of component (A). is more preferred.
  • a UV absorber can be used in the present curable composition.
  • the use of an ultraviolet absorber can enhance the surface weather resistance of the cured product.
  • Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds.
  • Benzotriazole compounds include, for example, commercial names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (manufactured by BASF). These ultraviolet absorbers may be used alone or in combination of two or more.
  • the amount of the ultraviolet absorber used is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 8.0 parts by weight, and 0.3 to 6.0 parts by weight, per 100 parts by weight of component (A). Parts by weight are more preferred.
  • a light stabilizer can be used in the curable composition.
  • the use of a light stabilizer can prevent photo-oxidative deterioration of the cured product.
  • Examples of light stabilizers include benzotriazole-based, hindered amine-based, and benzoate-based compounds. Hindered amine compounds are particularly preferred. These light stabilizers may be used alone or in combination of two or more.
  • the amount of light stabilizer used is, for example, 0.1 to 10 parts by weight, preferably 0.2 to 8.0 parts by weight, and 0.3 to 6.0 parts by weight, per 100 parts by weight of component (A). Parts by weight are more preferred.
  • antioxidant antioxidant agent
  • An antioxidant can be used in the present curable composition.
  • the use of an antioxidant can improve the heat resistance and weather resistance of the cured product.
  • antioxidants include hindered phenol-based, monophenol-based, bisphenol-based, and polyphenol-based compounds. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731. These antioxidants may be used alone or in combination of two or more.
  • the amount of antioxidant used is, for example, 0.1 to 2.0 parts by weight, preferably 0.2 to 1.8 parts by weight, and 0.3 to 1 part by weight, per 100 parts by weight of component (A). .6 parts by weight is more preferred.
  • a surface modifier can be used in the present curable composition.
  • surface modifiers include long-chain alkylamines such as laurylamine, 2,2′-methylenebis(4,6-di-t-butylphenyl)sodium phosphate, tris(2,4-di-t- Phosphorus compounds such as butylphenyl)phosphite, oxazolidine compounds, 1,1,1-trimethylolpropane triacrylate and the like. These surface modifiers may be used alone or in combination of two or more.
  • the amount of the surface modifier used is, for example, 1.0 to 10.0 parts by weight, preferably 1.5 to 7.5 parts by weight, and 2.0 to 10.0 parts by weight per 100 parts by weight of component (A). 5.0 parts by weight is more preferred.
  • Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers.
  • the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. .
  • the above solvents or diluents may be used alone or in combination of two or more.
  • An anti-sagging agent may be added to the present curable composition as necessary to prevent sagging and improve workability.
  • the anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.
  • the amount of anti-sagging agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of component (A).
  • a physical property modifier for adjusting the tensile properties of the cured product may be added to the present curable composition.
  • the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, and trimethylmethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxy Alkylisopropenoxysilanes such as propylmethyldiisopropenoxysilane; trialkylsilylborates such as tris(trimethylsilyl)borate and tris(triethylsilyl)borate; silicone varnishes; and polysiloxanes.
  • the physical property modifier By using the physical property modifier, it is possible to increase the hardness when the composition according to the present embodiment is cured, or conversely decrease the hardness and increase the elongation at break.
  • the physical property modifiers may be used alone, or two or more of them may be used in combination.
  • a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without exacerbating the stickiness of the surface of the cured product.
  • Compounds that generate trimethylsilanol are particularly preferred.
  • Compounds that generate compounds having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monools.
  • a silicon compound to be generated can be mentioned. Specific examples include tris((trimethylsiloxy)methyl)propane.
  • the amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, per 100 parts by weight of component (A).
  • An adhesion imparting agent can be added to the present curable composition.
  • a silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ - Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatomethyltrimethoxysilane, ⁇ -isocyan
  • reaction products of various silane coupling agents can also be used.
  • the reactants include isocyanate silane and a hydroxyl group-containing compound, isocyanate silane and an amino group-containing compound; reaction products of aminosilane and an acrylic group-containing compound, and a methacrylic group-containing compound (Michael addition reaction product); aminosilane and an epoxy group.
  • Examples include a reaction product with a containing compound, a reaction product with an epoxysilane and a carboxylic acid group-containing compound, and an amino group-containing compound.
  • silane coupling agents such as isocyanate silane and aminosilane, aminosilane and (meth)acrylic group-containing silane, aminosilane and epoxysilane, aminosilane and acid anhydride-containing silane can also be used.
  • adhesion imparting agents other than silane coupling agents are not particularly limited, but include epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like.
  • the adhesiveness-imparting agent may be used alone or in combination of two or more. Addition of these adhesion-imparting agents can improve adhesion to adherends.
  • the amount of adhesion-imparting agent used is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention.
  • a tackifying resin can be added to the present curable composition for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes.
  • the tackifier resin there is no particular limitation and any commonly used one can be used.
  • terpene-based resins aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.
  • petroleum resins e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C
  • the amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, even more preferably 5 to 30 parts by weight, per 100 parts by weight of component (A). If the amount is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and if the amount exceeds 100 parts by weight, the viscosity of the composition becomes too high and handling may become difficult.
  • a photocurable material can be used in the present curable composition.
  • a photocurable substance When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved.
  • Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.
  • unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one to several acrylic or methacrylic unsaturated groups, such as propylene (or butylene, ethylene) glycol di(meth)acrylate, neopentyl Monomers such as glycol di(meth)dimethacrylate and oligoesters having a molecular weight of 10,000 or less are exemplified.
  • Aronix M-210 for example, special acrylates (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (trifunctional) Aronix M305 , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (multifunctional) Aronix M-400, etc., especially compounds containing acrylic functional groups is preferred, and a compound containing 3 or more of the same functional groups on average in one molecule is preferred (Aronix is a product of Toagosei Kagaku Kogyo Co., Ltd.).
  • polyvinyl cinnamate examples include a photosensitive resin having a cinnamoyl group as a photosensitive group, which is obtained by esterifying polyvinyl alcohol with cinnamic acid, and many polyvinyl cinnamate derivatives.
  • Azidated resins are known as photosensitive resins having an azide group as a photosensitive group. Publishing, Printing Society Publishing Department, page 93 onwards, page 106 onwards, page 117 onwards), and these may be used singly or in combination, and if necessary, a sensitizer may be added. can be done. The effect may be enhanced by adding a sensitizer such as ketones or nitro compounds or an accelerator such as amines.
  • the photocurable substance is preferably used in the range of 0.1 to 20 parts by weight, more preferably in the range of 0.5 to 10 parts by weight, per 100 parts by weight of component (A). If it is less than 0.1 part by weight, there is no effect of improving the weather resistance, and if it is more than 20 parts by weight, the cured product becomes too hard and tends to crack.
  • oxygen-curable material can be used in the present curable composition.
  • oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust.
  • Specific examples of oxygen-curable substances include drying oils represented by paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins.
  • silicone resins 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
  • diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc.
  • liquid polymers These may be used alone or in combination of two or more.
  • the amount of the oxygen-curable substance used is preferably in the range of 0.1 to 20 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the polyoxyalkylene polymer (A) of the present invention. 10 parts by weight. If the amount is less than 0.1 part by weight, the improvement in staining resistance is not sufficient, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired. As described in JP-A-3-160053, the oxygen-curable substance is preferably used in combination with the photo-curable substance.
  • the curable composition can be used as a waterproofing material, an elastic sealing material for construction, a sealing material for siding boards, a sealing material for double glazing, a sealing material for vehicles, automobile parts, parts for large vehicles such as trucks and buses, and parts for train vehicles. , aircraft parts, marine parts, electrical parts, liquid sealing materials used in various machine parts, etc.
  • Architectural and industrial sealing materials, electrical and electronic component materials such as solar cell back sealing agents, electric wires and cables
  • Electrical insulating materials such as insulation coating materials, adhesives, adhesives, elastic adhesives, contact adhesives, tile adhesives, reactive hot melt adhesives, paints, powder coatings, coating materials, foams, can lids, etc.
  • sealing materials heat dissipation sheets, potting agents for electrical and electronic equipment, films, gaskets, marine deck caulking, casting materials, various molding materials, artificial marble, and rust prevention and waterproofing of wire glass and laminated glass edges (cut parts)
  • a cured product (hereinafter referred to as "main cured product") is provided by curing the present curable composition.
  • the cured product is formed by curing the curable composition. Therefore, the cured product has excellent flame retardancy.
  • the cured product is formed by curing the following curable composition.
  • the curing method is not particularly limited, and for example, it can be cured at an outside temperature or room temperature, or it can be cured by heating.
  • one aspect of the present invention includes the following. ⁇ 1> an organic polymer (A) having a hydrolyzable silyl group; aluminum hydroxide (B) surface-treated with titanate; A curable composition containing a silanol condensation catalyst (C). ⁇ 2>
  • the organic polymer (A) is a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and/or a hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) The curable composition according to ⁇ 1>.
  • ⁇ 3> The curable composition according to ⁇ 1> or ⁇ 2>, wherein the organic polymer (A) is a hydrolyzable silyl group-containing (meth)acrylate copolymer (A2).
  • the organic polymer (A) is a hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and a hydrolyzable silyl group-containing (meth)acrylate copolymer (A2).
  • ⁇ 1> or ⁇ 2> ⁇ 5>
  • the content of the aluminum hydroxide (B) is 30 to 300 parts by weight with respect to 100 parts by weight of the organic polymer (A), according to any one of ⁇ 1> to ⁇ 5>.
  • Curable composition. ⁇ 7> The weight ratio of the hydrolyzable silyl group-containing polyoxyalkylene polymer (A1) and the hydrolyzable silyl group-containing (meth)acrylic acid ester copolymer (A2) is 5:95 to The curable composition according to ⁇ 4>, which is 50:50.
  • ⁇ 8> Any one of ⁇ 1> to ⁇ 7>, wherein the content of the silanol condensation catalyst (C) is 0.5 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) A curable composition as described.
  • organic polymer Organic polymers (A-1), (A-2), (A-3) and (A-4) prepared according to the synthesis examples below were used.
  • test substrate width 25 mm, length 100 mm, thickness 3 mm
  • Primer No. manufactured by Yokohama Rubber Co., Ltd. 40 was applied with a brush and dried for about 30 minutes.
  • the obtained composition was applied in the form of a bead having a width of 10 mm, a thickness of 10 mm and a length of 80 mm, and cured at 23° C. and a relative humidity of 50% for 7 days.
  • the interface between the sealant and the base material was cut with a razor blade, and the sealant was pulled in a direction of 180 degrees to observe the breakage state.
  • CF was defined as a state where the sealant was destroyed
  • TCF was defined as a state in which a thin layer remained on the base material
  • AF was defined as a state in which no sealant remained on the base material.
  • test base material was used as the test base material.
  • SUS304 cold-rolled stainless steel plate (manufactured by Nippon Tact Co., Ltd.) Al: Anodized aluminum A5052P (manufactured by Engineering Test Service Co., Ltd.) Glass: Float glass (manufactured by TP Giken Co., Ltd.).
  • the flame retardancy of the curable composition was measured according to UL-94 rating. Specifically, the curable composition was made into a sheet-shaped specimen having a thickness of 3 mm, and was completely cured by placing it in a 23° C., 50% RH condition for 3 days and then in a 50° C. dryer for 4 days. Five specimens (length 125 mm ⁇ width 13 mm ⁇ thickness 3 mm) were cut out from this sheet.
  • the specimen was held vertically, and the flame of a gas burner was applied to the lower end of the specimen for 10 seconds. When the combustion stopped within 30 seconds, the flame of the gas burner was further applied to the lower end of the test piece for 10 seconds.
  • the number average molecular weight in the examples is the GPC molecular weight measured under the following conditions: Liquid delivery system: Tosoh HLC-8220GPC Column: TSK-GEL H type manufactured by Tosoh Solvent: THF Molecular weight: converted to polystyrene Measurement temperature: 40°C.
  • a pentamethyldiethylenetriamine complex of cuprous bromide was used as a catalyst to react terminal bromine groups of the polymer with 1,7-octadiene in an acetonitrile solvent to obtain a polyacrylic acid ester.
  • 1,7-octadiene was used in an amount of 60 molar equivalents with respect to the initiator.
  • unreacted 1,7-octadiene was devolatilized and recovered.
  • the resulting polymer was purified by adsorption, heated to about 190° C. for debromination, and purified again by adsorption to obtain a polyacrylic acid ester having alkenyl groups at both ends.
  • the resulting polyacrylate having alkenyl groups at both ends was treated with methyldimethoxysilane at 100° C. to the alkenyl groups of the polyacrylate using 300 ppm of an isopropanol solution containing 3 wt % platinum of a platinum-vinylsiloxane complex as a catalyst. was reacted for 1 hour. The reaction was carried out in the presence of methyl orthoformate, and 4 molar equivalents of methyldimethoxysilane relative to alkenyl groups were used.
  • organic polymer (A-1) methyldimethoxysilyl group-terminated polyacrylate
  • the obtained organic polymer had a number average molecular weight of 40,500, a molecular weight distribution of 1.3, and the number of silyl groups introduced per molecule was 2.0.
  • this polymer (Q-2) was added 50 ⁇ l of a platinum divinyldisiloxane complex solution (isopropanol solution of 3% by weight in terms of platinum), and 4.8 g of dimethoxymethylsilane was slowly added dropwise while stirring. After reacting at 100° C. for 2 hours, unreacted dimethoxymethylsilane is distilled off under reduced pressure to obtain a polyoxypropylene (organic polymer (A- 2)) was obtained. It was found that the organic polymer (A-2) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.6 dimethoxymethylsilyl groups per molecule.
  • organic polymer (A-2) had an average of 0.8 dimethoxymethylsilyl groups at one terminal and an average of 1.6 dimethoxymethylsilyl groups per molecule.
  • the unpurified polyoxypropylene thus obtained was mixed with n-hexane and water, and then the water was removed by centrifugation. Removed. As a result, polyoxypropylene (Q-3) having a plurality of carbon-carbon unsaturated bonds at the ends was obtained. Polymer (Q-3) was found to have an average of 1.50 carbon-carbon unsaturated bonds introduced at one end.
  • the obtained (Q-4) was mixed with 70 parts of the organic polymer (A-2) so that the solid content of the (meth)acrylic ester copolymer was 30 parts, and after mixing uniformly, the rotary IBA was removed by an evaporator to obtain an organic polymer (A-4).
  • Example 1 Organic polymer (A-1), aluminum hydroxide (B-2), calcium carbonate, plasticizer, epoxy compound-1, ultraviolet absorber, light stabilizer, antioxidant, surface A modifier was added in the amounts shown in Table 1, mixed using a twin-screw mixer, and dispersed to prepare a main agent.
  • a silanol condensation catalyst and a co-catalyst were mixed as a curing agent in the amounts shown in Table 1 (unit: parts by weight) using a spatula.
  • the prepared main agent and curing agent were sufficiently mixed, and uniformly kneaded and defoamed using a rotation/revolution mixer to prepare a curable composition. Adhesiveness and flame retardancy were evaluated by the method described in the section [Methods of measurement and evaluation] using the prepared curable composition. Table 1 shows the results.
  • the compounding amount of each component in Table 1 is shown in parts by weight.
  • Examples 2 to 11, Comparative Examples 1 to 3 A curable composition was prepared in the same manner as in Example 1, except that the amount of each component was changed as shown in Table 1. Adhesiveness and flame retardancy were evaluated by the method described in the section [Methods of measurement and evaluation] using the prepared curable composition. Table 1 shows the results.
  • Table 1 shows that the curable compositions of Examples 1 to 11 have excellent adhesion when cured. Moreover, it was shown that the curable compositions of Examples 1 to 11 are also excellent in flame retardancy. Furthermore, the curable composition of Example 3 in which the organic polymer (A-1) and the organic polymer (A-2) are used in combination, and the organic polymer (A-1) and the organic polymer (A-4) In the curable composition of Example 7, which was used in combination with, compared with the curable composition of Example 2, it was shown that the adhesiveness was further improved and the workability was excellent.
  • a curable composition having flame retardancy and adhesiveness can be provided, and thus can be suitably used as a sealant or the like.

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Abstract

Le but de la présente invention est de fournir une composition durcissable à laquelle de l'hydroxyde d'aluminium est ajouté de façon à améliorer l'ininflammabilité, et qui présente une adhésivité améliorée. À cet effet, on obtient une composition durcissable qui contient (A) un polymère organique ayant un groupe silyle hydrolysable, (B) de l'hydroxyde d'aluminium qui est traité en surface avec du titanate, et (C) un catalyseur de condensation de silanol.
PCT/JP2023/002025 2022-01-31 2023-01-24 Composition durcissable et son utilisation WO2023145711A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012879A (ja) * 2001-07-03 2003-01-15 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
WO2011089987A1 (fr) * 2010-01-20 2011-07-28 コニシ株式会社 Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012879A (ja) * 2001-07-03 2003-01-15 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
WO2011089987A1 (fr) * 2010-01-20 2011-07-28 コニシ株式会社 Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif

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