WO2014192914A1 - 硬化性組成物およびその硬化物 - Google Patents
硬化性組成物およびその硬化物 Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C09D143/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Definitions
- the present invention provides an organic polymer having a silicon group having a hydroxyl group or a hydrolyzable group on a silicon atom and capable of forming a siloxane bond (hereinafter also referred to as “reactive silicon group”). It is related with the curable composition containing and its hardened
- an organic polymer having a reactive silicon group reacts with moisture or the like even at room temperature, and is crosslinked by a siloxane condensation reaction of the reactive silicon group to obtain a rubber-like cured product.
- polyoxyalkylene having a reactive silicon group has a relatively low viscosity, and therefore has excellent workability when used.
- a cured product obtained from a polyoxyalkylene having a reactive silicon group has a good balance of performance such as mechanical properties, weather resistance, and dynamic durability, so that the polymer is a sealing material, an adhesive, a paint, etc. (Patent Document 1).
- the curable composition containing the reactive silicon group-containing polymer can adjust workability and various physical properties by blending various components such as a filler and a plasticizer.
- various components such as a filler and a plasticizer.
- Patent Document 3 discloses that a high-strength cured product can be obtained by a combination of a reactive silicon group-containing polyoxyalkylene and a poly (meth) acrylic acid ester having a trifunctional reactive silicon group.
- an object of the present invention is to provide a curable composition that provides a cured product having low strength and high strength and elongation.
- the high molecular weight plasticizer (C) does not have a high molecular weight plasticizer (C1) having no more than 1 and no more than 1 reactive silicon group on average in one molecule and no reactive silicon group
- the monomer constituting the polymer (B) contains the monomer (b1) whose homopolymer has a glass transition temperature of 80 ° C. or less in an amount of 40% by weight or more based on the total monomers [1] ]
- the monomer constituting the polymer (B) is a homopolymer having a glass transition temperature of ⁇ 25 ° C. or higher and a monomer (b2) having no reactive silicon group in all monomers.
- the curable composition of the present invention gives a cured product having high strength and elongation while having low viscosity.
- the above-mentioned polymer (A), polymer (B), high molecular weight plasticizer (C), and other components described later may be used alone. Two or more kinds may be used in combination. Hereinafter, each component will be described in order.
- the oxyalkylene polymer (A) has the following general formula (1): -SiR 1 a X 3-a (1)
- R 1 represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.
- X independently represents a hydroxyl group or a hydrolyzable group (preferably a hydrolyzable group). , 0 or 1) It has the reactive silicon group represented by these.
- R 1 in the general formula (1) is, for example, an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; ') Triorganosiloxy group represented by 3 (in the above formula, R' each independently represents an alkyl group (eg, a methyl group) or an aryl group (eg, a phenyl group)); a fluoromethyl group, Fluoroalkyl groups such as difluoromethyl groups; chloroalkyl groups such as chloromethyl groups and 1-chloroethyl groups; alkoxyalkyl groups such as methoxymethyl groups, ethoxymethyl groups, phenoxymethyl groups and 1-methoxyethyl groups; aminomethyl groups; Aminoalkyl groups such as N-methylaminomethyl group and N,
- Examples of the hydrolyzable group represented by X in the general formula (1) include known hydrolyzable groups.
- the hydrolyzable group means a group that reacts and decomposes in the presence of water.
- Examples of the hydrolyzable group include hydrogen, halogen, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, amino group, amide group, aminooxy group, mercapto group and the like.
- halogen, alkoxy group eg, methoxy group, ethoxy group
- alkenyloxy group eg, isopropenyloxy group (also known as isopropenoxy group)
- acyloxy group are preferable because of high activity, and hydrolyzable.
- a methoxy group and an ethoxy group are particularly preferable.
- the hydrolyzable group is an ethoxy group or an isopropenyloxy group
- the compounds eliminated by the hydrolysis reaction are ethanol and acetone, respectively. Therefore, from the viewpoint of safety, an ethoxy group and an isopropenyloxy group are preferable as the hydrolyzable group.
- the reactive silicon group represented by the general formula (1) may be one type, two or more types, and preferably one type.
- the reactive silicon group represented by the general formula (1) is preferably a hydrolyzable group, more preferably a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, or a triacetoxysilyl group.
- the oxyalkylene polymer (A) has a relatively low glass transition temperature, and the cured product obtained therefrom has excellent cold resistance.
- the oxyalkylene polymer (A) has high moisture permeability, and when the curable composition of the present invention is made into a one-component composition, it is excellent in deep-part curable and further excellent in adhesiveness of the cured product. It has the following characteristics.
- Examples of the main chain of the oxyalkylene polymer (A) include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene. Examples thereof include an oxyethylene-polyoxypropylene copolymer and a polyoxypropylene-polyoxybutylene copolymer.
- the main chain of the oxyalkylene polymer (A) may be composed of only one structural unit or may be composed of two or more structural units.
- an oxypropylene component unit is contained in an amount of 50% by weight or more, preferably 80% by weight or more in all the structural units. It is desirable to use a propylene polymer (A).
- a propylene polymer (A) is amorphous and has a relatively low viscosity.
- the polymer (A) may be linear or branched. Since a cured product having a high elongation is obtained, the polymer (A) is preferably linear. When the polymer (A) is branched, the number of branched chains is preferably 1 to 4, more preferably 1.
- a polyoxyalkylene containing no reactive silicon group can be produced by a ring-opening polymerization reaction of a cyclic ether compound using a polymerization catalyst in the presence of an initiator.
- the cyclic ether compound include ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these cyclic ether compounds, propylene oxide is preferable because an amorphous and relatively low viscosity polyoxyalkylene can be obtained.
- the initiator examples include ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, sorbitol and the like.
- alcohols include hydroxyl group-containing polyoxyalkylene having a number average molecular weight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene diol, and polyoxyethylene triol.
- the method for synthesizing polyoxyalkylene containing no reactive silicon group is not particularly limited.
- a polymerization method using an alkali catalyst such as KOH, and reacting an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623 a polymerization method using an alkali catalyst such as KOH, and reacting an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623.
- Polymerization method using transition metal compound-porphyrin complex catalyst such as complex obtained by the above, JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3427256, U.S. Pat. No. 3,427,334, U.S. Pat. No.
- a polymerization method using a double metal cyanide complex catalyst a polymerization method using a catalyst comprising a polyphosphazene salt exemplified in JP-A-10-273512, and JP-A-11 -Phosph exemplified in 060722 Polymerization method using a catalyst consisting of Zen compounds.
- a polymerization method using a double metal cyanide complex catalyst (for example, a zinc hexacyanocobaltate glyme complex catalyst) is preferable because of a production cost and a polymer having a narrow molecular weight distribution.
- the method for introducing a reactive silicon group into polyoxyalkylene is not particularly limited, and a known method can be used.
- Examples of the method for introducing a reactive silicon group include the following methods (i) and (ii).
- hydrosilane compound examples include halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, and (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, and trimethoxy.
- halogenated silanes such as trichlorosilane, dichloromethylsilane, dichlorophenylsilane, and (methoxymethyl) dichlorosilane; dimethoxymethylsilane, diethoxymethylsilane, and trimethoxy.
- Alkoxysilanes such as silane, triethoxysilane, (chloromethyl) dimethoxysilane, (methoxymethyl) dimethoxysilane; triisopropenyloxysilane, (chloromethyl) diisopropenyloxysilane, (methoxymethyl) diisopropenyloxysilane And isopropenyloxysilanes.
- a reactive group-containing polymer precursor polymer
- a silane coupling agent a compound having both a group to be formed (hereinafter also referred to as “reactive group”) and a reactive silicon group.
- the combination of the functional group of the precursor polymer and the reactive group of the silane coupling agent includes hydroxyl group and isocyanate group, hydroxyl group and epoxy group, amino group and isocyanate group, amino group and thioisocyanate group, amino group and epoxy group, amino group Groups and ⁇ , ⁇ -unsaturated carbonyl groups (reaction by Michael addition), carboxy groups and epoxy groups, unsaturated bonds and mercapto groups, and the like.
- silane coupling agent examples include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercapto, which react with an unsaturated bond.
- Mercaptosilanes such as methyltriethoxysilane and mercaptomethyldimethoxymethylsilane; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyldimethoxymethylsilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyltrimethoxysilane that react with hydroxyl groups , Isocyanate silanes such as isocyanate methyltriethoxysilane, isocyanate methyldimethoxymethylsilane; hydroxyl group, amino group or carboxy group 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, Epoxy silanes such as sidoxymethyldimethoxymethylsilane; 3-a
- the method (i) is advantageous in that the reaction is simple, the amount of reactive silicon groups introduced can be adjusted, and the physical properties of the resulting reactive silicon group-containing polymer (A) are stable. Have.
- the method (ii) has many reaction options and has the advantage that it is easy to increase the rate of introduction of reactive silicon groups. In addition, you may introduce
- the main chain of the polymer (A) is an ester bond or a general formula (3) as long as the effects of the present invention are not impaired.
- —NR 2 —C ( ⁇ O) — (3) (Wherein R 2 represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).
- a cured product obtained from a curable composition containing a polymer (A) containing an ester bond or an amide segment may have high hardness and strength due to the action of hydrogen bonding or the like.
- the polymer (A) containing an amide segment or the like may be cleaved by heat or the like.
- the curable composition containing the polymer (A) containing an amide segment or the like tends to have a high viscosity.
- polyoxyalkylene containing an amide segment or the like may be used as the polymer (A), or polyoxyalkylene containing no amide segment or the like may be used.
- Examples of the amide segment represented by the general formula (3) include a reaction between an isocyanate group and a hydroxyl group, a reaction between an amino group and a carbonate group, a reaction between an isocyanate group and an amino group, and a reaction between an isocyanate group and a mercapto group. And the like formed by, for example. Moreover, what is formed by reaction of the said amide segment containing an active hydrogen atom and an isocyanate group is also contained in the amide segment represented by General formula (3).
- a polyoxyalkylene having an active hydrogen-containing group at the terminal is reacted with an excess polyisocyanate compound to obtain a polymer having an isocyanate group at the terminal.
- the general formula (4) Z—R 3 —SiR 1 a X 3-a (4) (Wherein R 1 , X and a are the same as above.
- R 3 is a divalent organic group, preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.
- Z is a hydroxyl group, A carboxy group, a mercapto group, a primary amino group or a secondary amino group.
- the silicon compound represented by the general formula (4) is not particularly limited.
- JP-A-6-2111879 (US Pat. No. 5,364,955), JP-A-10-53637 (US Pat. No. 5,757,751), JP-A-10-204144 (EP0831108), JP-A 2000-169544, JP-A 2000-169545.
- Michael addition reaction products of various ⁇ , ⁇ -unsaturated carbonyl compounds and primary amino group-containing silanes, or various (meth) acryloyl group-containing silanes and primary amino group-containing compounds can also be used as the silicon compound represented by the general formula (4).
- the method of making the reactive silicon group containing isocyanate compound shown by react can be mentioned.
- the reactive silicon group-containing isocyanate compound represented by the general formula (5) is not particularly limited, and examples thereof include ⁇ -trimethoxysilylpropyl isocyanate, ⁇ -triethoxysilylpropyl isocyanate, ⁇ -methyldimethoxysilylpropyl isocyanate, ⁇ -Methyldiethoxysilylpropyl isocyanate, ⁇ - (methoxymethyl) dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxymethylsilylmethyl isocyanate, dimethoxymethylsilylmethyl isocyanate, diethoxymethylsilylmethyl isocyanate, (methoxymethyl) dimethoxy Examples thereof include silylmethyl isocyanate.
- the number (average value) of amide segments per molecule of the polymer (A) is preferably 1 to 10, more preferably 1.5 to 5, and more preferably 2 to 3 Particularly preferred. When this number is less than 1, the curability may not be sufficient. Conversely, when it is greater than 10, the polymer (A) has a high viscosity and may be difficult to handle. In order to reduce the viscosity of the curable composition and improve workability, the polymer (A) preferably does not contain an amide segment.
- the average number of the polymer (A) per molecule is more than 1, preferably 1.2 or more, more preferably 1.3 or more, and still more preferably 1.5 or more. It has a reactive silicon group represented by The upper limit of the number of reactive silicon groups (average value) in one molecule of the polymer (A) is preferably 6.0, more preferably 5.5, and even more preferably 5.0. When the number of reactive silicon groups is 1 or less, a high-strength cured product may not be obtained, and when the number of reactive silicon groups exceeds 6.0, a cured product with high elongation may not be obtained. is there.
- the number of reactive silicon groups (average value) in one molecule of the polymer (A) is an average value obtained by measuring and calculating protons on carbon directly bonded with reactive silicon groups by a high resolution 1 H-NMR method. It is defined as In the measurement and calculation of the number of reactive silicon groups, when the reactive silicon group was introduced into the precursor polymer, the precursor polymer in which the reactive silicon group was not introduced and the reactive silicon group obtained by the side reaction were introduced. A polymer which is not present is regarded as a part of the polymer (A), and is included in the parameter (number of molecules of the polymer (A)) when calculating the number of reactive silicon groups (average value).
- the polymer (A) may have an average of more than one reactive silicon group at one terminal site.
- a method for producing a polymer (A) having an average of more than one reactive silicon group at one terminal site for example, (A) reacting a polyoxyalkylene having a hydroxyl group at the terminal (precursor polymer) with an epoxy compound having an unsaturated bond, introducing an unsaturated bond and a hydroxyl group at the terminal of the precursor polymer, (B) A group that reacts with a hydroxyl group to form a bond (for example, a halogen atom) and a compound having an unsaturated bond are reacted with the resulting polymer to introduce a plurality of unsaturated bonds at the end of the polymer. , (C) A method in which a hydrosilane compound is added to a plurality of unsaturated bonds by a hydrosilylation reaction.
- Examples of the epoxy compound used in the reaction (a) include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, butadiene monoxide, 1,4-cyclopentadiene monoepoxide, and the like from the viewpoint of reactivity. Allyl glycidyl ether is preferred.
- “(meth) allyl” represents “allyl and / or methallyl”
- “(meth) acrylate” represents “acrylate and / or methacrylate”.
- the amount of the epoxy compound used in the reaction (a) can be appropriately set in consideration of the amount of unsaturated bonds introduced into the polyoxyalkylene (precursor polymer) having a hydroxyl group at the terminal and the reactivity.
- the amount used is preferably 0.2 mol or more, more preferably 0.5 mol or more, preferably 5.0 mol or less, more preferably 2.0 mol per mol of hydroxyl group in polyoxyalkylene. It is below the mole.
- the reaction temperature in the reaction (a) is preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 110 ° C. or higher and 140 ° C. or lower. If the reaction temperature is low, the reaction hardly proceeds. If the reaction temperature is too high, the polyoxyalkylene main chain may be decomposed.
- Examples of the compound having an unsaturated bond and a group that reacts with a hydroxyl group to be used in the reaction (b) include 3-chloro-1-propene and 3-chloro-2-methyl-1-propene.
- the amount of the compound used in the reaction (b) is preferably 1.1 mol or more, more preferably 1.2 mol or more, and preferably 1.4 mol, relative to 1 mol of the hydroxyl group in the polymer. In the following, it is more preferably a mole or less.
- R 5 and R 7 are each independently a divalent organic group having 1 to 10 carbon atoms which may contain an oxygen atom or a nitrogen atom.
- R 6 and R 8 are each independently And a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 10.
- Examples of the hydrosilane compound used in the reaction (c) include those exemplified by the method (i).
- the amount of the hydrosilane compound used in the reaction (c) is preferably 0.65 mol or more, more preferably 0.75 mol or more, preferably 1 mol or more per 1 mol of the unsaturated bond in the polymer. 1 mol or less, more preferably 1.2 mol or less.
- the average number of reactive silicon groups in the polymer (A) is preferably 0.5 or more, more preferably 1.0 or more, and 1.1 or more on one terminal site. More preferably, the number is 1.5 or more.
- the number average molecular weight of the polymer (A) is preferably 8,000 or more, more preferably 9,000 or more, still more preferably 10,000 or more, particularly preferably 15,000 or more, and most preferably 20,000 or more. Preferably, it is 50,000 or less, More preferably, it is 35,000 or less, More preferably, it is 30,000 or less.
- the number average molecular weight of the polymer (A) is small, the viscosity is low, so that the workability when using the curable composition is improved, but the obtained cured product tends to be hard and the elongation tends to decrease.
- the number average molecular weight of the polymer (A) is too large, the reactive silicon group concentration becomes too low, the curing rate may be slow, and the viscosity becomes too high, making handling difficult. Tend.
- the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer (A) is not particularly limited, but is preferably narrow, more preferably less than 2.0, and even more preferably 1.6 or less, 1.5 or less is particularly preferable, and 1.4 or less is most preferable.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer (A) are values measured by GPC (polystyrene conversion), and the detailed measurement method is described in Synthesis Example 1 described later.
- the measurement methods for the number average molecular weight (Mn) of other components are the same. If the number average molecular weight of the polymer (A) cannot be measured by GPC, titration analysis based on the principle of the hydroxyl value measurement method of JIS K 1557 and the iodine value measurement method defined in JIS K 0070.
- the terminal group concentration (the sum of the hydroxyl value and iodine value) is directly measured, and the number average molecular weight of the polymer (A) is determined in consideration of the number of terminal branches in the structure of the polymer (A).
- the polymer (A) preferably has an average of 1.2 to 6.0 dimethoxymethylsilyl groups or trimethoxymethyl groups as reactive silicon groups in a molecule and has a number average molecular weight of 10,000. Polyoxypropylene that is ⁇ 50,000.
- the polymer (A) more preferably has an average of 1.3 to 5.5 dimethoxymethylsilyl groups or trimethoxymethyl groups as reactive silicon groups in one molecule, and a number average molecular weight of 15, It is a polyoxypropylene having a molecular weight of 000-35,000.
- the polymer (A) more preferably has an average of 1.5 to 5.0 dimethoxymethylsilyl groups as reactive silicon groups in one molecule, and a number average molecular weight of 20,000 to 30,000. Is polyoxypropylene.
- the (meth) acrylic acid ester polymer (B) has the following general formula (2): -SiX 3 (2) (In the formula, each X independently represents a hydroxyl group or a hydrolyzable group (preferably a hydrolyzable group).)
- the reactive silicon group equivalent is 0.30 mmol / g or more.
- “(meth) acryl” means “acryl and / or methacryl”.
- the polymer (B) has a reactive silicon group represented by the general formula (2) (that is, three X (hydroxyl group or hydrolyzable group) on the silicon atom). It is necessary to have a silicon group).
- description of a hydrolysable group is the same as the description in a polymer (A).
- the reactive silicon group represented by the general formula (2) may be one type, two or more types, and preferably one type.
- Examples of the reactive silicon group represented by the general formula (2) include a trimethoxysilyl group, a triethoxysilyl group, a tris (2-propenyloxy) silyl group, a triacetoxysilyl group, and the like. Not. Among these, a trimethoxysilyl group is preferable because it exhibits high activity and a cured product having high strength and elongation can be obtained.
- the monomer constituting the (meth) acrylic acid ester polymer (B) includes (meth) acrylic acid ester (hereinafter also referred to as “monomer (b)”). That is, the polymer (B) includes a structural unit derived from the monomer (b) (hereinafter also referred to as “structural unit (b)”). In order to synthesize the polymer (B), only one type of monomer (b) may be used, or two or more types of monomers (b) may be used in combination.
- Examples of the monomer (b) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, 2-Methylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate , Hexadec
- other monomers showing copolymerizability with the monomer (b) may be used.
- examples of other monomers include styrene monomers such as styrene, vinyl toluene, ⁇ -methyl styrene, chlorostyrene, and styrene sulfonic acid; fluorine-containing vinyl such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
- maleic acid maleic anhydride, maleic acid monoalkyl ester, maleic acid dialkyl ester and other maleic acid and derivatives thereof; fumaric acid, fumaric acid monoalkyl ester, fumaric acid dialkyl ester and other fumaric acids and derivatives thereof;
- Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.
- Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Olefin monomers such as ethylene and propylene; Conjugated diene monomers such as butadiene and isoprene Body; (meth) acrylamide; (meth) acrylonitrile; vinyl monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, ethyl vinyl ether, butyl vinyl ether. Other monomers may use only 1 type and may use 2 or more types together.
- the monomer constituting the polymer (B) is a monomer having a homopolymer glass transition temperature of 80 ° C. or lower and having no reactive silicon group. It is preferable to contain (b1) in an amount of 40% by weight or more based on the total monomers. That is, the polymer (B1) has a homopolymer glass transition temperature of 80 ° C. or lower and a structural unit derived from the monomer (b1) having no reactive silicon group (hereinafter “structural unit (b1)”). It is preferable to contain 40 wt% or more of all structural units.
- the amount of monomer (b1) in all monomers is more preferably 50% by weight or more.
- the glass transition temperature of the homopolymer means the glass transition temperature of the homopolymer of the monomer (b1), and the numerical value is the homopolymer glass described in POLYMER HANDBOOK -FOURTH EDITION- (J. Brandrup et al.). Reference is made to the transition temperature.
- the monomer (b1) may be one type or two or more types.
- the upper limit of the amount of the monomer (b1) is not particularly limited, but the amount of the monomer (b1) in all monomers constituting the polymer (B) is preferably 90% by weight or less, more preferably Is 80% by weight or less.
- Examples of the monomer (b1) include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Isobutyl acrylate, s-butyl (meth) acrylate, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) N-octyl acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid Tridecyl, te
- the glass transition temperature of the homopolymer of the monomer (b1) is preferably ⁇ 100 ° C. to 50 ° C., more preferably ⁇ 100 ° C. to 80 ° C., further preferably It is -70 ° C to 50 ° C, particularly preferably -70 ° C to 40 ° C.
- an alkyl (meth) acrylate having 2 to 6 carbon atoms as the monomer (b1).
- the carbon number of alkyl in the alkyl (meth) acrylate means the carbon number of the alkyl group (R) of the alkoxycarbonyl group (RO—CO—).
- the monomer constituting the polymer (B) has a homopolymer glass transition temperature of ⁇ 25 ° C. or higher, and has no reactive silicon group (b2 ) Is preferably contained in an amount of 20% by weight or more based on the total monomers. That is, the polymer (B) has a structural unit derived from the monomer (b2) having a glass transition temperature of ⁇ 25 ° C. or higher and having no reactive silicon group (hereinafter “structural unit (b2)). It is preferable to contain 20% by weight or more of all structural units.
- the amount of monomer (b2) in all monomers is more preferably 30% by weight, still more preferably 40% by weight or more.
- the glass transition temperature of the homopolymer means the glass transition temperature of the homopolymer of the monomer (b2), and the numerical value is the homopolymer glass described in POLYMER HANDBOOK -FOURTH EDITION- (J. Brandrup et al.). Reference is made to the transition temperature.
- the monomer (b2) may be one type or two or more types.
- the upper limit of the amount of the monomer (b2) is not particularly limited, but the amount of the monomer (b2) in all monomers constituting the polymer (B) is preferably 80% by weight or less, more preferably Is 70% by weight or less.
- Examples of the monomer (b2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and s-butyl methacrylate.
- an alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms as the monomer (b2), methyl (meth) acrylate, ( More preferably, at least one selected from the group consisting of ethyl (meth) acrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate is used.
- the monomer having a homopolymer glass transition temperature of ⁇ 25 ° C. to 80 ° C. (hereinafter also referred to as “monomer (b1-b2)”) is the monomer (b1) and the monomer ( It is included in both concepts of b2).
- the amount of monomer (b1-b2) is included in both the amount of monomer (b1) and the amount of monomer (b2).
- the amount of the monomer (b1-b2) in all the monomers constituting the polymer (B) is preferably 5 to 80% by weight, more preferably 10 to 70% by weight.
- the amount of the structural unit derived from the alkyl (meth) acrylate of the polymer (B) is preferably 50% by weight or more, more preferably 70% in all the structural units. % By weight or more, preferably 98% by weight or less, more preferably 95% by weight or less.
- the monomer constituting the polymer (B) is an alkyl (meth) acrylate having 1 to 6 carbon atoms (hereinafter “monomer”). (B3) ”) and alkyl (meth) acrylate (hereinafter referred to as“ monomer (b4) ”) having 7 to 30 carbon atoms. That is, the polymer (B) includes a structural unit derived from the monomer (b3) (hereinafter also referred to as “structural unit (b3)”) and a structural unit derived from the monomer (b4) (hereinafter “structural unit”). (B4) ”is also preferably contained.
- the total amount of the monomer (b3) and the monomer (b4) in all monomers constituting the polymer (B) is preferably 50 to 95% by weight, more preferably 60 to 90% by weight.
- the structural unit (b4)) is preferably 95: 5 to 40:60, and more preferably 90:10 to 60:40.
- the polymer (B) can be obtained by various polymerization methods, and the polymerization method is not particularly limited, but a radical polymerization method is preferable from the viewpoint of versatility of the monomer and ease of control.
- Radical polymerization methods can be classified into “general radical polymerization methods” and “controlled radical polymerization methods”.
- the “general radical polymerization method” is simply a polymerization method using a polymerization initiator such as an azo compound or a peroxide, and is a simple polymerization method.
- the “controlled radical polymerization method” is a method capable of introducing a specific functional group at a controlled position such as a terminal.
- the “controlled radical polymerization method” can be further classified into a “chain transfer agent method” and a “living radical polymerization method”.
- the “chain transfer agent method” is characterized in that polymerization is carried out using a chain transfer agent having a specific functional group, and a vinyl polymer having a functional group at the terminal is obtained.
- the “living radical polymerization method” is characterized in that a polymer growth terminal grows without causing a side reaction such as a termination reaction, and a polymer having a molecular weight almost as designed can be obtained. In the present invention, any of these polymerization methods may be used.
- general radical polymerization method examples include a solution polymerization method and a bulk polymerization method in which a polymerization initiator, a chain transfer agent, a solvent and the like are added and polymerization is performed at 50 to 150 ° C.
- polymerization initiator examples include 2,2′-azobis (2-methylbutyronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 1,1 Azo compounds such as' -azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3 , 5,5-trimethylhexanoyl) peroxide and other diacyl peroxides; Ruperoxydicarbonate, di-sec-butylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate
- chain transfer agent examples include mercapto group-containing compounds such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan.
- mercapto group-containing compounds such as n-dodecyl mercaptan, tert-dodecyl mercaptan, and lauryl mercaptan.
- a reactive silicon group at the molecular chain terminal of the (meth) acrylic polymer for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylchloromethyldimethoxy
- a compound having a reactive silicon group and a mercapto group such as silane, 3-mercaptopropylmethoxymethyldimethoxysilane, (mercaptomethyl) dimethoxymethylsilane, and (mercaptomethyl) trimethoxysilane.
- the solvent examples include aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane, etc.
- aromatic compounds such as toluene, xylene, styrene, ethylbenzene, paradichlorobenzene, di-2-ethylhexyl phthalate, di-n-butyl phthalate; hexane, heptane, octane, cyclohexane, methylcyclohexane, etc.
- Hydrocarbon compounds carboxylic acid ester compounds such as butyl acetate, n-propyl acetate and isopropyl acetate; ketone compounds such as methyl isobutyl ketone and methyl ethyl ketone; dialkyl carbonate compounds such as dimethyl carbonate and diethyl carbonate; n-propanol and 2-propanol And alcohol compounds such as n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol.
- 1 or more types selected from a dialkyl carbonate compound and an alcohol compound from points, such as an odor and an environmental load are preferable.
- GEV Global Emission Control Reelte Ferry Gewerkstoffe Ave
- GEV GEV Specification and Classification Criteria Dimethyl carbonate
- n-propanol, 2-propanol, n-butanol, 2-butanol, isobutanol, and tert-butanol are more preferable from the viewpoint of suppressing the release of all volatile organic compounds from the composition.
- 2-propanol and isobutanol are more preferred.
- the polymer (B) it is possible to polymerize the monomer of the polymer (B) together with the polymer (A), a precursor compound thereof, a plasticizer described later, and the like.
- the “chain transfer agent method” is a polymerization method capable of quantitatively introducing a functional group to the polymer terminal as compared with the “general radical polymerization method”.
- the radical polymerization using a chain transfer agent is not particularly limited.
- a halogen-terminated polymer is obtained using a halogenated hydrocarbon as disclosed in JP-A-4-132706 as a chain transfer agent.
- the “living radical polymerization method” can obtain a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity, and a monomer having a specific functional group. This is a polymerization method that can be introduced at almost any position of the polymer.
- living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. It also includes pseudo-living polymerization that grows in an equilibrium state.
- the “living radical polymerization method” uses, for example, a cobalt porphyrin complex as shown in Journal of American Chemical Society (1994), Vol. 116, page 7943. J. Am. Chem. Soc. Initiators, those using nitrooxide radicals as shown in JP-A-2003-500388, organic halides or sulfonyl halides as shown in JP-A-11-130931, etc. And atom transfer radical polymerization (Atom Transfer Radical Polymerization: ATRP method) using a transition metal complex as a catalyst. Further, in the present invention, so-called reverse atom transfer radical polymerization, that is, a normal atom transfer radical polymerization catalyst as shown in Macromolecules, 1999, Vol.
- a general radical initiator such as a peroxide is allowed to act on Cu (II) when Cu (I) is used as a catalyst, resulting in an atom transfer radical as a result.
- Polymerization methods that produce an equilibrium state similar to polymerization are also included in the atom transfer radical polymerization method.
- an acrylic polymer is prepared using a metallocene catalyst as disclosed in JP-A-2001-040037 and a thiol compound having at least one reactive silicon group in the molecule.
- a vinyl monomer as shown in JP-A-57-502171, JP-A-59-006207, JP-A-60-511992 using a stirred tank reactor It is also possible to use a high temperature continuous polymerization method in which continuous polymerization is performed.
- the method for introducing the reactive silicon group into the (meth) acrylic acid ester polymer is not particularly limited.
- the following methods (I) to (IV) can be used.
- (I) A method of copolymerizing a compound having a polymerizable unsaturated bond and a reactive silicon group together with a (meth) acrylic acid ester.
- (II) A method of copolymerizing a (meth) acrylic acid ester in the presence of the above-mentioned compound having a reactive silicon group and a mercapto group as a chain transfer agent.
- (III) Copolymerizing a compound having a polymerizable unsaturated bond and a reactive functional group (Z group) (for example, acrylic acid, 2-hydroxyethyl acrylate) together with a (meth) acrylic acid ester having no Z group And then reacting a compound having a functional group that reacts with the reactive silicon group and the Z group (for example, an isocyanate silane compound).
- Z group for example, acrylic acid, 2-hydroxyethyl acrylate
- Z group for example, acrylic acid, 2-hydroxyethyl acrylate
- the method (IV) is preferable because a polymer having an arbitrary molecular weight, a narrow molecular weight distribution, and a low viscosity can be obtained.
- Examples of the compound having a reactive silicon group and a mercapto group include 3-mercaptopropyltrimethoxysilane, mercaptomethyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, and the like.
- Examples of the compound having a polymerizable unsaturated bond and a reactive silicon group include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and (meth) acryloxymethyltrimethoxy.
- Compounds having (meth) acryloxy groups and reactive silicon groups such as silane, 3- (meth) acryloxypropyldimethoxymethylsilane, (meth) acryloxymethyldimethoxymethylsilane; vinyltrimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include a compound having a vinyl group and a reactive silicon group. These may be used alone or in combination of two or more.
- the reactive silicon group of the polymer (B) may be introduced at either the molecular chain end or the side chain, but is preferably introduced at both the molecular chain end and the side chain from the viewpoint of adhesion. .
- the number of reactive silicon groups in one molecule of the polymer (B) is preferably 1.0 or more, more preferably 1.3 or more, even more preferably on average. Is 1.5 or more, preferably 8.0 or less, more preferably 7.0 or less, and even more preferably 6.0 or less.
- the reactive silicon group equivalent of the polymer (B) is preferably 0.30 mmol / g or more, more preferably 0.35 mmol / g or more, further preferably 0.40 mmol / g or more, preferably 3.0 mmol / g. g or less, more preferably 2.5 mmol / g or less, still more preferably 2.0 mmol / g or less.
- the reactive silicon group equivalent means the amount of reactive silicon group (mmol) contained per weight (g) of the polymer (B), and is based on the amount of the monomer having a reactive silicon group. Can be calculated.
- the molecular weight of the polymer (B) is not particularly limited. In order to obtain a cured product having higher strength, the polymer (B) preferably has a high molecular weight.
- its number average molecular weight is preferably 4,000 or more, more preferably 6,000 or more, further preferably 8,000 or more, in terms of polystyrene by GPC. Preferably it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 30,000 or less.
- the monomer for synthesizing the polymer is not particularly limited, but in order to obtain a curable composition having a low viscosity, a monomer having a low glass transition temperature. Is preferably used.
- the high molecular weight polymer (B1) preferably has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.30 to 3.0 mmol / g, and a number average molecular weight of 4,
- the total amount of the monomer (b3) and the monomer (b4) in all monomers constituting the polymer (B) is 50 to 95% by weight,
- the high molecular weight polymer (B1) has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.35 to 2.5 mmol / g, and a number average molecular weight of 6
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, Poly (meth) acrylic acid ester having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40.
- the high molecular weight polymer (B1) more preferably has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.40 to 2.0 mmol / g, and a number average molecular weight of 8
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, Poly (meth) acrylic acid ester having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40.
- the polymer (B) preferably has a low molecular weight.
- its number average molecular weight is preferably 400 or more, more preferably 500 or more, further preferably 1,000 or more, particularly preferably 1,500 in terms of polystyrene by GPC. It is above, Preferably it is less than 4,000, More preferably, it is 3,000 or less.
- the monomer constituting the low molecular weight polymer (B2) is a monomer (b2) having a glass transition temperature of -25 ° C. or higher of the homopolymer, preferably 20% by weight or more of all monomers.
- the content is preferably 30% by weight or more, more preferably 40% by weight or more.
- the amount of the monomer having a glass transition temperature of the homopolymer of less than ⁇ 25 ° C. is large, the strength of the resulting cured product may be insufficient.
- the low molecular weight polymer (B2) preferably has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.30 to 3.0 mmol / g, and has a number average molecular weight of 1,
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is from 50 to 95% by weight, Poly (meth) acrylic acid ester having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 95: 5 to 40:60.
- the low molecular weight polymer (B2) more preferably has a trimethoxymethyl group as a reactive silicon group, a reactive silicon group equivalent of 0.35 to 2.5 mmol / g, and a number average molecular weight of 1 500 to 3,000, and the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, Poly (meth) acrylic acid ester having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40.
- the low molecular weight polymer (B2) more preferably has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.40 to 2.0 mmol / g, and a number average molecular weight of 1 500 to 3,000, and the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, Poly (meth) acrylic acid ester having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40.
- the weight ratio of the polymer (A) and the polymer (B) is not particularly limited, but the polymer (A): polymer (B) is preferably 90:10 to 30:70, and 85:15 to 40:60 is more preferable, and 80:20 to 50:50 is even more preferable.
- the total content of the polymer (A) and the polymer (B) in the curable composition is preferably 30 to 90% by weight, more preferably 50 to 80% by weight.
- the curable composition of the present invention contains a high molecular weight plasticizer (C) having an average of 0 to 1 reactive silicon group in one molecule.
- a high molecular weight plasticizer (C) having an average of 0 to 1 reactive silicon group in one molecule.
- the curable composition of the present invention may contain a low molecular weight plasticizer in addition to the high molecular weight plasticizer (C).
- a low molecular weight plasticizer in addition to the high molecular weight plasticizer (C).
- the high molecular weight plasticizer (C) means a plasticizer having a number average molecular weight of 500 or more
- the low molecular weight plasticizer means a plasticizer having a number average molecular weight of less than 500.
- the number average molecular weight of the high molecular weight plasticizer (C) is preferably not less than 500, more preferably not less than 1,000, still more preferably not less than 1,500, particularly preferably not less than 2,000, in terms of polystyrene by GPC. Preferably it is 15,000 or less, More preferably, it is 10,000 or less, More preferably, it is 8,000 or less. If the number average molecular weight is too low, the high molecular weight plasticizer (C) flows out of the cured product over time due to heat or rain, and the initial physical properties cannot be maintained over a long period of time. Moreover, when this number average molecular weight is too high, the viscosity of a curable composition will become high and workability
- the molecular weight distribution (Mw / Mn) of the high molecular weight plasticizer (C) is not particularly limited, but is preferably narrow, more preferably less than 1.80, even more preferably 1.70 or less, and even more preferably 1.60 or less. 1.50 or less is even more preferable, 1.40 or less is particularly preferable, and 1.30 or less is most preferable.
- Examples of the high molecular weight plasticizer (C) include polyoxyalkylenes; (meth) acrylic acid ester polymers; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; sebacic acid, Polyester obtained from dibasic acids such as adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; the hydroxyl group of polyether polyol is urethanized Polyether (for example, trade name: LBU-25 (manufactured by Sanyo Kasei Co., Ltd.)), polyether esterified with carboxylic acid, polyether etherified at the end; polystyrene, poly Polystyrene such as ⁇ - methylstyrene; polybutadiene, polybutene, polyisobutylene
- the high molecular weight plasticizer (C) those compatible with the polymer (A) and the polymer (B) are preferable. From this point, the high molecular weight plasticizer (C) is preferably an oxyalkylene polymer or a (meth) acrylic acid ester polymer. The description of the oxyalkylene polymer and the (meth) acrylic acid ester polymer is the same as that described for the polymer (A) and the polymer (B).
- an oxyalkylene polymer is used as the high molecular weight plasticizer (C), the surface curability and the deep curability are improved, and the curing delay after storage does not occur.
- the oxyalkylene polymers polyoxypropylene is more preferable. It is preferable to use an oxyalkylene polymer that does not have a hydroxyl group at the terminal, because strength reduction due to the addition of a plasticizer can be suppressed.
- a (meth) acrylic acid ester polymer as the high molecular weight plasticizer (C).
- the (meth) acrylic acid ester polymers poly (meth) acrylic acid alkyl is more preferable.
- the synthesis method of the (meth) acrylic acid ester polymer is preferably the living radical polymerization method and more preferably the atom transfer radical polymerization method because the molecular weight distribution is narrow and the viscosity can be lowered. Also preferred is a method (so-called SGO process) in which alkyl (meth) acrylate described in JP-A-2001-207157 is continuously bulk polymerized at high temperature and high pressure.
- the high molecular weight plasticizer (C) may be a high molecular weight plasticizer (C1) having an average of more than 0 and no more than 1 reactive silicon group per molecule.
- a molecular weight plasticizer (C2) or a mixture thereof may be used.
- As a reactive silicon group the reactive silicon group represented by General formula (1) can be mentioned, for example.
- the reactive silicon groups of the polymer (A) and the high molecular weight plasticizer (C) may be different, but are preferably the same because a cured product having good elongation can be obtained.
- the high molecular weight plasticizer (C) has a reactive silicon group
- the average number of reactive silicon groups in one molecule is preferably 0.3 or more, more preferably 0.5 or more, and still more preferably 0.8.
- the number of reactive silicon groups is less than 0.3, there is a possibility that the effect of the reactive silicon groups, that is, increasing the strength of the cured product, cannot be obtained sufficiently. On the other hand, if the number of reactive silicon groups is larger than 1, a cured product having a high elongation may not be obtained.
- the high molecular weight plasticizer (C) having a reactive silicon group is prepared by synthesizing a polymer exemplified by the polymer (A) and the polymer (B), a method for introducing a reactive silicon group, and other known methods. Can be manufactured by.
- the content of the high molecular weight plasticizer (C) is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). 20 to 100 parts by weight is particularly preferable. If this content is less than 5 parts by weight, the effect of the high molecular weight plasticizer (C) may not be sufficiently exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product may be insufficient.
- the high molecular weight plasticizer (C) is a high molecular weight plasticizer (C1) having an average of more than 0 and no more than 1 reactive silicon group in one molecule
- the content of the polymer (C1) The total content of A) and the polymer (B) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 20 parts by weight or more, preferably 200 parts by weight or less with respect to 100 parts by weight. More preferably, it is 150 parts by weight or less, and still more preferably 100 parts by weight or less.
- the content is 100% by weight of the total content of the polymer (A) and the polymer (B). Part by weight, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, still more preferably 20 parts by weight or more, preferably 200 parts by weight or less, more preferably 150 parts by weight or less, still more preferably 100 parts by weight. Or less.
- a high molecular weight plasticizer (C1) having a reactive silicon group and a high molecular weight plasticizer (C2) having no reactive silicon group may be used in combination. Since a cured product excellent in workability and mechanical properties can be obtained, it is preferable to use a high molecular weight plasticizer having a reactive silicon group and a high molecular weight plasticizer not having a reactive silicon group in combination.
- the high molecular weight plasticizer (C) has a high molecular weight plasticizer (C1) having an average of more than 0 and no more than 1 reactive silicon group in one molecule, and a high molecular weight plasticizer having no reactive silicon group.
- the agent (C2) the total content is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, further preferably 20 parts by weight or more, preferably 200 parts by weight or less, more preferably 150 parts by weight.
- the weight ratio (high molecular weight plasticizer (C1): high molecular weight plasticizer (C2)) is preferably 90:10 to 20:80, and more preferably 85 parts by weight or less. : 15 to 40:60, more preferably 80:20 to 50:50.
- the high molecular weight plasticizer (C) is preferably a polyoxypropylene or polysiloxane having an average of 0.3 to 1 reactive silicon group in one molecule and a number average molecular weight of 500 to 15,000.
- High molecular weight plasticizer (C1) which is (meth) acrylic acid ester and / or polyoxypropylene or poly (meth) acrylic acid ester which has no reactive silicon group and has a number average molecular weight of 500 to 15,000 Is a high molecular weight plasticizer (C2).
- the high molecular weight plasticizer (C) is more preferably a polyoxy having an average of 0.5 to 1 reactive silicon group in one molecule and a number average molecular weight of 1,000 to 10,000.
- High molecular weight plasticizer (C1) which is propylene or poly (meth) acrylic acid ester, and / or polyoxypropylene or poly (which has no reactive silicon group and has a number average molecular weight of 1,000 to 10,000 It is a high molecular weight plasticizer (C2) which is a (meth) acrylic ester.
- the high molecular weight plasticizer (C) is more preferably a polyoxy having an average of 0.6 to 1 reactive silicon group per molecule and a number average molecular weight of 2,000 to 8,000.
- High molecular weight plasticizer (C1) which is propylene or poly (meth) acrylic acid ester, and polyoxypropylene or poly (meth) which has no reactive silicon group and has a number average molecular weight of 2,000 to 8,000
- the curable composition of this invention contains components (other components) other than the above-mentioned polymer (A), polymer (B) and high molecular weight plasticizer (C). May be.
- other components will be described.
- a low molecular weight plasticizer may be added to the curable composition of the present invention.
- the low molecular weight plasticizer include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), butyl benzyl phthalate, and the like; bis (2 -Ethylhexyl) -1,4-benzenedicarboxylate and other terephthalic acid ester compounds (specifically, trade name: EASTMAN168 (manufactured by EASTMAN CHEMICAL)); 1,2-cyclohexanedicarboxylic acid diisononyl ester and other non-phthalic acid esters Compound (specifically, trade name: Hexamol DINCH (manufactured by BASF)); dioctyl adipate, dioctyl sebacate, dibutyl
- a low molecular weight plasticizer When a low molecular weight plasticizer is used, its content is preferably 5 to 150 parts by weight, preferably 10 to 120 parts by weight, based on 100 parts by weight of the total content of the polymer (A) and the polymer (B). More preferred is 20 to 100 parts by weight. If this content is less than 5 parts by weight, the effect of the low molecular weight plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product tends to be insufficient. Only one type of low molecular weight plasticizer may be used, or two or more types may be used in combination. In addition, it is desirable not to use a low molecular weight plasticizer when it is desired that high strength is developed in the curable composition.
- a solvent or a diluent can be added to the curable composition of the present invention.
- a solvent and a diluent Aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon, halogenated hydrocarbon, alcohol, ester, ketone, ether etc. can be used.
- 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 said solvent or diluent may use only 1 type and may use 2 or more types together.
- a curing catalyst may be used for the purpose of curing the polymers (A) and (B).
- the curing catalyst include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, titanium tetrakis (acetylacetonate), bis (acetylacetonato) diisopropoxytitanium, diisopropoxytitanium bis (ethylacetocetate); Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methylmaleate), dibutyltin bis (ethylmaleate), dibutyltin bis ( Butyl maleate), dibutyl tin bis (octyl maleate), dibutyl tin bis (tridec
- a dibutyltin type compound, a dioctyl tin type compound, carboxylic acid tin, and carboxylic acid are preferable.
- Dioctyl tin compounds, tin carboxylates and carboxylic acids are more preferred because of their low toxicity.
- a curing catalyst When a curing catalyst is used, its content is preferably about 0.01 to 10 parts by weight, preferably 0.1 to 5 parts per 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part by weight is more preferred.
- the content is less than 1 weight part.
- a silane coupling agent, a reaction product of the silane coupling agent, or the like can be added as an adhesion promoter.
- silane coupling agent examples include ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane.
- Silanes containing isocyanate groups such as ⁇ -isocyanatomethyldimethoxymethylsilane; ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N - ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopro Lutriethoxysilane, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldiethoxysilane, ⁇ -ureidopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N-
- these partial condensates and derivatives thereof such as amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc. It can be used as a ring agent.
- silane coupling agents may use only 1 type and may use 2 or more types together.
- reaction product of the silane coupling agent a reaction product of isocyanate silane and a hydroxyl group-containing compound or an amino group-containing compound; a Michael addition reaction product of aminosilane; a reaction product of an aminosilane and an epoxy group-containing compound, an epoxy silane and a carboxy group
- examples thereof include a compound and a reaction product with an amino group-containing compound.
- the content thereof is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). 0.5 to 10 parts by weight is more preferable.
- adhesion imparting agent other than the silane coupling agent or the reaction product thereof are not particularly limited, and examples thereof include epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like.
- the said adhesion imparting agent may be used only by 1 type, and may use 2 or more types together. By adding these adhesion-imparting agents, the adhesion of the cured product to the adherend can be improved.
- silicate can be added to the curable composition of the present invention.
- This silicate acts as a cross-linking agent and has a function of improving the restorability, durability, and creep resistance of the cured product obtained from the curable composition of the present invention. Furthermore, it has the effect of improving the adhesiveness and water-resistant adhesiveness of the cured product, and the adhesive durability under high temperature and high humidity conditions.
- As the silicate tetraalkoxysilane and alkylalkoxysilane or partial hydrolysis condensates thereof can be used.
- silicates include tetramethoxysilane, tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, Examples thereof include tetraalkoxysilanes (tetraalkylsilicates) such as tetra-i-butoxysilane and tetra-t-butoxysilane, and partial hydrolysis condensates thereof.
- the partial hydrolysis-condensation product of tetraalkoxysilane is preferable because the effect of improving the restorability, durability, and creep resistance of the cured product is greater than that of tetraalkoxysilane.
- the partially hydrolyzed condensate of tetraalkoxysilane include a product obtained by adding water to tetraalkoxysilane and condensing it by partial hydrolysis.
- a commercially available product can be used as the partially hydrolyzed condensate of the organosilicate compound. Examples of such condensates include methyl silicate 51 and ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.).
- the content thereof is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 0.5 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). 10 parts by weight.
- fillers 1 type or 2 or more types of fillers can be mix
- the content thereof is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). .
- the filler examples include fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, aluminum hydroxide, carbon black, and hollow alumina silica fine particles (for example, trade name: PANSIL UltraSpheres (Manufactured by TOLSA)), heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, kaolinite, silitin, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, Examples thereof include resin powders such as flint powder, zinc oxide, activated zinc white, PVC powder and PMMA1 powder, fibrous fillers such as asbestos, glass fibers and filaments.
- heavy calcium carbonate means calcium carbonate produced by pulverization classification
- colloidal calcium carbonate means calcium carbonate produced by a carbon dioxide gas compounding method.
- the filler is uniformly mixed with a dehydrating agent such as calcium oxide, and then sealed in a bag made of an airtight material and allowed to stand for an appropriate time. It is also possible to dehydrate and dry in advance. By using such a dry filler, the storage stability of the one-component curable composition can be particularly improved.
- a dehydrating agent such as calcium oxide
- a polymer powder made from a polymer such as polymethyl methacrylate, Crystalline silica or the like can be used as a filler.
- a curable composition having high transparency can be obtained by using hydrophobic silica or the like, which is fine silicon dioxide powder having a hydrophobic group bonded to its surface, as a filler. You can get things.
- the surface of silicon dioxide fine powder generally has a silanol group (—SiOH), and (—SiO—hydrophobic group) was generated by reacting this silanol group with an organosilicon halide or alcohol.
- hydrophobic silica One is hydrophobic silica.
- hydrophobic silica examples include those obtained by reactively bonding dimethylsiloxane, hexamethyldisilazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, etc. to the silanol group present on the surface of the silicon dioxide fine powder.
- the silicon dioxide fine powder having silanol groups (—SiOH) on the surface is called hydrophilic silica fine powder.
- a filler selected from calcined clay, clay, titanium oxide, hollow alumina silica fine particles, kaolinite, silitin and activated zinc white.
- the content thereof is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- the average primary particle size is preferably smaller than 3 ⁇ m, more preferably smaller than 2 ⁇ m, and most preferably smaller than 1 ⁇ m.
- the average primary particle size is preferably 0.05 ⁇ m or more. This average primary particle diameter is an average value of 100 particles, and is a value measured by an electron microscope. The average primary particle diameter is an arithmetic average value of the major axis and minor axis of the primary particle, and is also called a biaxial average diameter.
- surface-treated calcium carbonate and non-surface-treated calcium carbonate may be used alone or in combination.
- the surface treatment is not performed or the surface treatment rate is low.
- Surface treatment agents for producing surface-treated calcium carbonate include palmitic acid, caprylic acid, capric acid, lauric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, etc.
- saturated fatty acids or unsaturated fatty acids, and carboxylic acids and esters thereof such as rosin acid compounds, silane compounds such as hexamethyldisilazane, chlorosilane, and aminosilane, paraffin compounds, and the like are included, but are not limited thereto. Do not mean.
- carboxylic acid when it is set as a curable silicone type resin composition, since it becomes difficult to produce hardening delay further, it is preferable.
- saturated fatty acids or unsaturated fatty acids are particularly preferable because they are more difficult to cause a delay in curing.
- colloidal calcium carbonate In order to obtain a cured product having high tear strength, it is preferable to use colloidal calcium carbonate.
- the balloon particle size is preferably 0.1 mm or less.
- the particle size of the balloon is preferably 5 to 300 ⁇ m.
- the particle size of the balloon is a value measured by an electron microscope.
- a balloon is a spherical body that is hollow inside.
- the balloon can be added for the purpose of reducing the weight (lowering the specific gravity) of the composition.
- the balloon include, but are not limited to, inorganic balloons such as glass, shirasu, and silica, and organic balloons such as phenol resin, urea resin, polystyrene, and saran.
- a composite balloon of an inorganic material and an organic material, or a balloon in which a plurality of layers are formed can be used.
- a balloon whose surface is processed or coated can also be used.
- the content thereof is preferably 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). Is more preferable. If the content is less than 0.01 part by weight, there is no effect of improving workability by the balloon, and if it exceeds 30 parts by weight, the elongation and breaking strength of the cured product tend to be low.
- an anti-slip agent as described in JP-A No. 2000-154368 and a surface of a cured product as described in JP-A No. 2001-164237 are used for matting.
- Primary and / or secondary amines, in particular primary and / or secondary amines with a melting point of 35 ° C. or higher can be added.
- Specific examples of the balloons are disclosed in JP-A-2-129262, JP-A-4-8788, JP-A-4-173867, JP-A-5-1225, JP-A-7-113033, JP-A-9-53063, JP-A-10-10. -251618, JP-A 2000-154368, JP-A 2001-164237, WO 97/05201, and the like.
- thermally expandable fine particle hollow body described in JP-A No. 2004-51701 or JP-A No. 2004-66749 can be used.
- a thermally expandable fine hollow body is a polymer outer shell material (for example, a vinylidene chloride copolymer, an acrylonitrile copolymer, or a vinylidene chloride-acrylonitrile copolymer), such as a hydrocarbon having 1 to 5 carbon atoms.
- the gas pressure in the shell of the thermally expandable fine particle hollow body increases, the polymer outer shell material softens, and its volume expands dramatically, The cured product adhered to the object can be peeled off.
- the curable composition of the present invention contains a cured product particle for a sealing material, it is possible to form irregularities on the surface of the resulting cured product and improve its design.
- preferred diameters, blending amounts, materials, and the like of the cured material particles for sealing material are as follows.
- the diameter is preferably about 0.1 mm to 1 mm, more preferably about 0.2 to 0.5 mm.
- the blending amount in the curable composition is preferably 5 to 100% by weight, more preferably 20 to 50% by weight.
- the material will not be limited if it is used for a sealing material, For example, a urethane resin, silicone, modified silicone, polysulfide rubber etc. can be mentioned, Among these, modified silicone is preferable.
- an anti-sagging agent may be added as necessary in order to prevent sagging and improve workability.
- the anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate.
- rubber powder having a particle size of 10 to 500 ⁇ m as described in JP-A-11-349916 or organic fiber as described in JP-A-2003-155389 is used as an anti-sagging agent, A curable composition having high thixotropy and good workability can be obtained.
- These anti-sagging agents may be used alone or in combination of two or more.
- its content is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- antioxidant antioxidant
- cured material can be improved.
- antioxidant include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants, with hindered phenolic antioxidants being particularly preferred. Specific examples of the antioxidant are also described in JP-A-4-283259 and JP-A-9-194731.
- an antioxidant when an antioxidant is used, its content is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts per 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part by weight is more preferred.
- a light stabilizer can be used.
- Use of a light stabilizer can prevent photooxidation degradation of the cured product.
- Examples of light stabilizers include benzotriazole light stabilizers, hindered amine light stabilizers, and benzoate light stabilizers, with hindered amine light stabilizers (HALS) being particularly preferred.
- HALS hindered amine light stabilizers
- its content is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts per 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part by weight is more preferred.
- a photocurable material for example, an unsaturated acrylic compound
- a photocurable material for example, an unsaturated acrylic compound
- HALS hindered amine light stabilizer
- a tertiary amine-containing hindered amine light stabilizer it is preferable to use a tertiary amine-containing hindered amine light stabilizer in order to improve the storage stability of the curable composition.
- Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144; CHIMASSORB 119FL (manufactured by Ciba Japan Co., Ltd.); Adekastab LA-57, LA-62, LA-67, LA-63P (all of which are stocks) Examples include Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.).
- an ultraviolet absorber can be used.
- an ultraviolet absorber When an ultraviolet absorber is used, the weather resistance of the cured product surface can be enhanced.
- the UV absorber include benzophenone UV absorbers, benzoate UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, substituted tolyl UV absorbers and metal chelate UV absorbers. Of these, benzotriazole ultraviolet absorbers and benzoate ultraviolet absorbers are preferred.
- Examples of the benzotriazole-based ultraviolet absorber include commercially available names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571 (manufactured by BASF).
- 2- (2H-1,2,3-benzotriazol-2-yl) -phenolic compounds are particularly preferred.
- the benzoate-based ultraviolet absorber include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (trade name: Sumisorb 400).
- a phenolic antioxidant and / or a hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber and / or a benzoate ultraviolet absorber in combination.
- the ultraviolet absorber When the ultraviolet absorber is used, its content is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts per 100 parts by weight of the total content of the polymer (A) and the polymer (B). Part by weight is more preferred.
- additives may be added as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
- additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, Examples include solvents and fungicides.
- flame retardants include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents.
- solvents and fungicides include solvents and fungicides.
- these additives may be used alone or in combination of two or more. Specific examples of the additive are described in, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and the like. Yes.
- the curable composition of the present invention can also be prepared as a one-component composition in which all the ingredients are pre-blended and then stored in a sealed state and cured by moisture in the air after construction.
- the curable composition of the present invention is prepared by separately preparing a curing agent containing components such as a curing catalyst, a filler, a plasticizer, and water, and mixing the curing agent and the curable composition before use. It can also be prepared as a two-component composition to be used. From the viewpoint of workability, a one-component composition is preferable.
- the curable composition is a one-component composition
- the water-containing ingredients are used after being dehydrated and dried in advance or by reducing the pressure during compounding and kneading. It is preferable to dehydrate.
- the curable composition is a two-component composition, it is not necessary to add a curing catalyst to the main component containing the polymer having a reactive silicon group, so that the compounding component contains some moisture. However, there is little concern about gelation, but when long-term storage stability is required, it is preferable to dehydrate and dry the ingredients.
- a heat drying method is suitable when the compounding component is a solid such as a powder, and when the compounding component is a liquid, a vacuum dehydration method, or synthetic zeolite, activated alumina, silica gel, A dehydration method using quick lime, magnesium oxide or the like is preferable. Further, a small amount of an isocyanate compound may be added to the blending component, and the isocyanate group and water may be reacted to dehydrate.
- an oxazolidine compound such as 3-ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine may be added to the blending component, and the oxazolidine compound and water may be reacted to dehydrate.
- a dehydrating agent for example, a silicon compound capable of reacting with water such as vinyltrimethoxysilane
- its content in the curable composition is the total content of the polymer (A) and the polymer (B).
- 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight, and 0.5 to 10 parts by weight is more preferable.
- a physical property modifier for adjusting the tensile properties of the cured product to be produced may be added as necessary.
- a physical property modifier for example, alkyl alkoxysilanes, such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane Arylalkoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, ⁇ -glycidoxypropylmethyldiisopropenoxysilane, and other alkylisopropenoxysilanes; tris (trimethylsilyl) borate, tris (triethyl) And trialkylsilyl borates such as silyl) borate;
- the hardness of the resulting cured product can be increased, or conversely, the hardness of the cured product can be decreased and the elongation at break can be improved. Only one type of physical property modifier may be used, or two or more types may be used in combination.
- a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
- Particularly preferred are compounds that produce trimethylsilanol.
- Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
- derivatives of alkyl alcohols such as hexanol, octanol, decanol, etc., which generate R 3 SiOH such as trimethylsilanol by hydrolysis, trimethylolpropane, glycerin described in JP-A-11-241029,
- R 3 SiOH such as trimethylsilanol by hydrolysis
- a compound that is a derivative of a polyhydric alcohol having 3 or more hydroxyl groups such as pentaerythritol or sorbitol and that generates R 3 SiOH such as trimethylsilanol by hydrolysis.
- polyoxypropylene derivative as described in JP-A-7-258534 which can generate R 3 SiOH such as trimethylsilanol by hydrolysis, can also be mentioned.
- polyoxyalkylene having a crosslinkable hydrolyzable silicon group described in JP-A-6-279893 and a silicon group that generates monosilanol by hydrolysis can also be used.
- a tackifying resin can be added as necessary in order to enhance the adhesion and adhesion to the substrate.
- tackifying resin There is no restriction
- tackifying resins include terpene resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenol resins obtained by copolymerizing terpenes with phenols, phenol resins, modified phenol resins, xylene-phenols.
- Resin cyclopentadiene-phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, xylene resin, low molecular weight polystyrene resin, styrene copolymer and its hydrogenated product, petroleum resin (for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.), hydrogenated petroleum resin, DCPD resin and the like.
- petroleum resin for example, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc.
- SBS styrene-butadiene-styrene block copolymer
- SIS styrene-isoprene-styrene block copolymer
- SIBS styrene-ethylenebutylene- Examples thereof include a styrene block copo
- terpene-phenol resins are preferred because they are highly compatible with the polymer (A) and the polymer (B) and can provide a high adhesion effect.
- petroleum resin is preferable.
- the content thereof is preferably 2 to 100 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B), and 5 to 50 parts by weight. More preferably, it is 5 to 30 parts. If this content is less than 2 parts by weight, it is difficult to obtain adhesion and adhesion effects to the substrate, and if it exceeds 100 parts by weight, the viscosity of the curable composition becomes too high and handling may be difficult. is there.
- An epoxy compound can be used in the curable composition of the present invention.
- the restorability of the cured product can be improved.
- the epoxy compound include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof.
- E-PS is particularly preferred.
- the content thereof is preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- a photocurable material can be used in the curable composition of the present invention.
- a photocurable material is used, a film of a photocurable material 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.
- a photocurable substance is a substance that cures (crosslinks) by the action of light.
- a photocurable substance a monomer, an oligomer resin, or a composition containing them is known.
- a commercial item can be used as a photocurable substance.
- Representative photocurable materials include unsaturated (meth) acrylic compounds, polyvinyl cinnamates, azido resins, and the like.
- Unsaturated (meth) acrylic compounds include monomers, oligomers or mixtures thereof having a plurality of (meth) acryloyl groups, including propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, ethylene glycol Examples thereof include monomers such as di (meth) acrylate and neopentyl glycol di (meth) acrylate, or oligoesters or polyesters having a molecular weight of 10,000 or less composed of the monomers.
- Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245 having two (meth) acryloyl groups in one molecule
- Aronix M-400 having an acryloyl group all Aronix is a product of Toa Gosei Chemical Co., Ltd.
- a compound containing an acryloyl group is preferable, and a compound containing an average of 3 or more acryloyl groups in one molecule is preferable.
- polyvinyl cinnamates examples include a polyvinyl cinnamate derivative and a photosensitive resin having a cinnamoyl group obtained by esterifying polyvinyl alcohol with cinnamic acid.
- An azide resin is a photosensitive resin having an azide group.
- the photo-curable substance may be used alone or in combination with a sensitizer and / or an accelerator as necessary.
- a sensitizer include ketones and nitro compounds
- examples of the accelerator include amines.
- the content thereof is preferably 0.1 to 20 parts by weight, more preferably 0, with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). .5 to 10 parts by weight. If the content is less than 0.1 parts by weight, there is no effect of improving the weather resistance. If the content is more than 20 parts by weight, the cured product tends to be too hard and tends to crack.
- An oxygen curable substance can be used for the curable composition of the present invention.
- the oxygen curable substance include unsaturated compounds that can react with oxygen in the air.
- the oxygen curable substance reacts with oxygen in the air to form a cured film in the vicinity of the surface of the cured product, and has actions such as preventing stickiness of the surface and adhesion of dust and dust to the surface of the cured product.
- oxygen curable substance examples include dry oils such as drill oil and linseed oil; alkyd resins obtained by modifying dry oils; acrylic polymers modified with dry oils, epoxy resins, silicone resins; butadiene, Liquid diene polymers such as 1,2-polybutadiene, 1,4-polybutadiene, C5 to C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as chloroprene, isoprene and 1,3-pentadiene; acrylonitrile A liquid copolymer such as NBR and SBR obtained by copolymerizing a diene compound with a diene compound such as styrene and a diene compound as a main component; Examples thereof include modified products of curable substances (maleinized modified products, boiled oil modified products, and the like).
- drill oil and liquid diene polymer are preferable.
- an oxygen curable substance when used in combination with a catalyst or metal dryer that promotes the oxidative curing reaction, the effect of the oxygen curable substance may be enhanced.
- these catalysts or metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amidine compounds.
- the content thereof is preferably 0.1 to 20 parts by weight, more preferably 0 with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). .5 to 10 parts by weight.
- the content is less than 0.1 part by weight, the improvement of the contamination of the cured product surface is not sufficient, and when the content exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired.
- the oxygen curable substance is preferably used in combination with a photocurable substance.
- An epoxy resin can be added to the curable composition of the present invention.
- the curable composition to which an epoxy resin is added is particularly preferable as an adhesive, particularly as an adhesive for exterior wall tiles.
- the epoxy resin include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, alicyclic epoxy resin, N , N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, poly
- the weight ratio of the total of the polymer (A) and the polymer (B) to the epoxy resin ((polymer (A) and polymer (B)) / epoxy resin) is preferably 1 / 100 to 100/1.
- this weight ratio is less than 1/100, it becomes difficult to obtain an impact strength and toughness improvement effect by the epoxy resin, and when this weight ratio exceeds 100/1, the strength of the cured product tends to be insufficient. is there.
- the preferable content of the epoxy resin in the curable composition of the present invention varies depending on the use of the curable resin composition and the like, and thus cannot be determined unconditionally.
- the content is preferably 1 with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- the amount is from 200 parts by weight, more preferably from 5 to 100 parts by weight.
- curing agent for epoxy resins when using an epoxy resin, you may use the hardening
- curing agent for epoxy resins generally used can be used.
- Secondary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine and their salts; polyamide resins; imidazole; dicyandiamide; boron trifluoride complex compounds, phthalic anhydride, hexahydro Carboxylic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride; alcohols; phenols; carboxylic acids; aluminum or zirconium Diketone complex compounds, and the like, but the present invention is not limited thereto.
- curing agent for epoxy resins may use only 1 type, and may use 2 or more types together.
- the amount used is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.
- Ketimine can be used as a curing agent for epoxy resin. Ketimine is stably present in the absence of moisture, and is decomposed into a primary amine and a ketone by moisture, and the resulting primary amine acts as a room temperature curable epoxy resin curing agent. When ketimine is used, a one-component composition can be obtained. Such ketimines can be obtained by a condensation reaction between an amine and a carbonyl compound. For the synthesis of ketimine, known amines and carbonyl compounds may be used.
- amines include ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p- Diamines such as phenylenediamine and p, p'-biphenylenediamine; polyvalent amines such as 1,2,3-triaminopropane, triaminobenzene, tris (2-aminoethyl) amine and tetra (aminomethyl) methane; diethylenetriamine Polyalkylene polyamines such as triethylenetriamine and tetraethylenepentamine; polyoxyalkylene polyamines; ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxy
- Examples of the carbonyl compound include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic ketones such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone; Aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate ⁇ -dicarbonylation of
- the imino group When an imino group is present in the ketimine, the imino group may be reacted with styrene oxide; glycidyl ether such as butyl glycidyl ether or allyl glycidyl ether; glycidyl ester or the like. Only 1 type may be used for ketimine and it may use 2 or more types together. When ketimine is used, the amount used varies depending on the type of epoxy resin and ketimine, but is, for example, 1 to 100 parts by weight per 100 parts by weight of epoxy resin.
- a flame retardant such as a phosphorus plasticizer such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite can be added to the curable composition of the present invention.
- a flame retardant may use only 1 type and may use 2 or more types together.
- the content thereof is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B). It is.
- the polymer (A) has an average of 1.2 to 6.0 dimethoxymethylsilyl groups or trimethoxymethyl groups as reactive silicon groups, and a number average molecular weight of 10,000 to 50, 000 is polyoxypropylene
- the polymer (B) has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.30 to 3.0 mmol / g, and a number average molecular weight of 4,000 to 100,000.
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 50 to 95% by weight, and the monomer (b3) and the monomer A poly (meth) acrylic acid ester (B1) in which the weight ratio of the body (b4) (monomer (b3): monomer (b4)) is 95: 5 to 40:60, or trimethyl as a reactive silicon group It has a methoxymethyl group, has a reactive silicon group equivalent of 0.30 to 3.0 mmol / g, has a number average molecular weight of 1,000 or more and less than 4,000, and comprises all the units constituting the polymer (B).
- the total amount of the monomer (b3) and the monomer (b4) in the monomer is 50 to 95% by weight.
- the high molecular weight plasticizer (C) has an average of 0.3 to 1 reactive silicon group in one molecule and a polyoxypropylene or poly (meth) having a number average molecular weight of 500 to 15,000.
- High molecular weight plasticizer (C1) which is an acrylic ester and / or polyoxypropylene or poly (meth) acrylic ester which does not have a reactive silicon group and has a number average molecular weight of 500 to 15,000
- a molecular weight plasticizer (C2) The total content of the polymer (A) and the polymer (B) in the curable composition is 30 to 90% by weight, The weight ratio of the polymer (A) to the polymer (B) (polymer (A): polymer (B)) is 90:10 to 30:70, The content of the high molecular weight plasticizer (C) is 5 to 200 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- the polymer (A) has an average of 1.3 to 5.5 dimethoxymethylsilyl groups or trimethoxymethyl groups as reactive silicon groups in a molecule, and a number average molecular weight of 15,000 to 35, 000 is polyoxypropylene,
- the polymer (B) has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.35 to 2.5 mmol / g, and a number average molecular weight of 6,000 to 50,000.
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, and the monomer (b3) and the single amount A poly (meth) acrylic acid ester (B1) in which the weight ratio of the body (b4) (monomer (b3): monomer (b4)) is 90:10 to 60:40, or trimethyl as a reactive silicon group
- the total amount of monomer (b3) and monomer (b4) in the body is 60 to 90% by weight, Poly (meth) acrylic acid ester (B2) having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40 And
- the high molecular weight plasticizer (C) has an average of 0.5 to 1 reactive silicon group in one molecule and has a number average molecular weight of 1,000 to 10,000.
- High molecular weight plasticizer (C1) which is a (meth) acrylic acid ester and / or polyoxypropylene or poly (meth) acrylic acid having no reactive silicon group and a number average molecular weight of 1,000 to 10,000
- a high molecular weight plasticizer (C2) which is an ester;
- the total content of the polymer (A) and the polymer (B) in the curable composition is 50 to 80% by weight,
- the weight ratio of the polymer (A) to the polymer (B) (polymer (A): polymer (B)) is 85:15 to 40:60,
- the content of the high molecular weight plasticizer (C) is 10 to 150 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- the polymer (A) has an average of 1.5 to 5.0 dimethoxymethylsilyl groups as reactive silicon groups in a molecule, and has a number average molecular weight of 20,000 to 30,000.
- Propylene has a trimethoxymethyl group as a reactive silicon group, has a reactive silicon group equivalent of 0.40 to 2.0 mmol / g, and a number average molecular weight of 8,000 to 30,000.
- the total amount of the monomer (b3) and the monomer (b4) in all the monomers constituting the polymer (B) is 60 to 90% by weight, and the monomer (b3) and the single amount A poly (meth) acrylic acid ester (B1) in which the weight ratio of the body (b4) (monomer (b3): monomer (b4)) is 90:10 to 60:40, or trimethyl as a reactive silicon group
- the total amount of monomer (b3) and monomer (b4) in the body is 60 to 90% by weight, Poly (meth) acrylic acid ester (B2) having a weight ratio of monomer (b3) to monomer (b4) (monomer (b3): monomer (b4)) of 90:10 to 60:40
- the high molecular weight plasticizer (C) has an average of 0.6 to 1 reactive silicon group in one molecule and has a number average molecular weight of 2,000 to 8,000.
- a high molecular weight plasticizer (C1) which is a (meth) acrylic acid ester, and a polyoxypropylene or poly (meth) acrylic acid ester having no reactive silicon group and a number average molecular weight of 2,000 to 8,000.
- high molecular weight plasticizer (C2) It is a certain high molecular weight plasticizer (C2), and the weight ratio of the high molecular weight plasticizer (C1) and the high molecular weight plasticizer (C2) (high molecular weight plasticizer (C1): high molecular weight plasticizer (C2)) is 80:20.
- the total content of the polymer (A) and the polymer (B) in the curable composition is 50 to 80% by weight
- the weight ratio of the polymer (A) to the polymer (B) is 80:20 to 50:50
- the content of the high molecular weight plasticizer (C) is 20 to 100 parts by weight with respect to 100 parts by weight of the total content of the polymer (A) and the polymer (B).
- the production method of the curable composition of the present invention is not particularly limited.
- the curable composition of the present invention is prepared by blending the above components and kneading them at room temperature or under heating using a mixer, roll, kneader, or the like, or by dissolving and mixing the above components in a small amount of solvent. Can be manufactured.
- the curable composition of the present invention is a pressure-sensitive adhesive, a sealing material for buildings, ships, automobiles, roads, etc., an adhesive, a mold preparation, a vibration damping material, a vibration damping material, a soundproof material, a foam material, a paint, and a spraying material. It can be used in coating waterproofing agents.
- the curable composition of the present invention has a low viscosity and is excellent in workability.
- cured material obtained from the curable composition of this invention has the characteristics that intensity
- the curable composition of the present invention includes an electrical / electronic component material such as a solar cell back surface sealing material, an electrical insulating material such as an insulating coating material for electric wires and cables, an elastic adhesive, a contact adhesive, and a spray seal.
- the curable composition of the present invention alone or the mixture of the curable composition of the present invention and a primer can adhere to a wide range of substrates such as glass, porcelain, wood, metal, and resin molded product
- the curable composition can also be used as various types of sealing and adhesive compositions.
- the curable composition of the present invention is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, vehicle panel adhesives, electrical / electronic / precision equipment assembly adhesives, direct glazing sealants, double glazing sealants, SSG sealants, or building working joint sealants It can be used.
- the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyoxypropylene diol and the polymer (A-1) are as follows: Tosoh HLC-8120GPC It is a value measured using Tosoh TSK-GEL H type, THF as a solvent, and polystyrene as a standard. The same applies to Mn, Mw and Mw / Mn described later.
- polymerization was carried out at 105 ° C. for 2 hours, and an average of 1.8 trimethoxysilyl groups (reactive silicon groups) per molecule, and the reactive silicon group equivalent was 0.75 mmol / g.
- the reactive silicon group equivalent of the polymer (B-1) is a value calculated from the addition amount of the monomer having a reactive silicon group. The same applies to reactive silicon group equivalents described later.
- MMA Methyl methacrylate
- BA n-butyl acrylate
- 2-EHA 2-ethylhexyl acrylate
- SMA stearyl methacrylate
- TSMA 3-methacryloxypropyltrimethoxysilane
- T-MSi 3-mercapto Propyltrimethoxysilane
- DSMA 3-methacryloxypropyldimethoxymethylsilane
- trimethoxysilane was added to 100 parts by weight of the resulting allyl group-terminated polyoxypropylene while stirring by adding 36 parts by weight of platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum).
- the terminal is a trimethoxysilyl group
- the average number of silicon groups per molecule is 0.7
- the number average molecular weight is 7,000
- the molecular weight distribution (Mw A linear polyoxypropylene (high molecular weight plasticizer (C-2)) having a / Mn of 1.2 was obtained.
- Example 1 60.0 parts by weight of the polymer (A-1) obtained in Synthesis Example 1 and 66.7 parts by weight of the isobutanol solution of the polymer (B-1) obtained in Synthesis Example 4 were mixed to obtain isobutanol.
- 30 parts by weight of the high molecular weight plasticizer (C-1) obtained in Synthesis Example 8 was added and kneaded to obtain a curable composition.
- viscosity The viscosity of the curable composition (not including the dehydrating agent, the adhesion-imparting agent and the catalyst shown in Table 2) at 23 ° C. and 50% relative humidity was measured using an E-type viscometer (manufactured by Tokyo Keiki, measuring cone: 3 ° C. ⁇ R 14 ). The results are shown in the table below.
- the obtained composition was filled in a polyethylene mold having a thickness of 3 mm so as not to contain bubbles, and cured at 23 ° C. and a relative humidity of 50% for 3 days, and further at 50 ° C. for 4 days to obtain a cured product.
- a No. 7 dumbbell was punched in accordance with JIS K 6251, a tensile test (a tensile speed of 200 mm / min, 23 ° C., a relative humidity of 50%) was performed, and a modulus at 50% elongation (M50), The strength at break (TB) and the elongation at break (EB) were measured. The results are shown in the table below.
- Examples 2 to 12, Comparative Examples 1 to 5 The following types and amounts of polymer (A), polymer (B), polymer (P), high molecular weight plasticizer (C), low molecular weight plasticizer, dehydrating agent, adhesion-imparting agent and catalyst are used.
- a curable composition was prepared and evaluated.
- the viscosity measured the viscosity of the curable composition which does not contain the dehydrating agent, adhesion imparting agent, and catalyst which are shown in the following table
- the curable composition containing the polymer (A), the polymer (B) and the high molecular weight plasticizer (C) has a low viscosity. It can be seen that the resulting cured product is excellent in tensile properties. Furthermore, from the comparison between Example 1 and Example 2, when the polymer (A) and the high molecular weight plasticizer (C) have the same reactive silicon group, curing excellent in elongation at break (EB). It turns out that things are obtained.
- Example 8 From a comparison between Example 8 and Examples 9 to 11, as the high molecular weight plasticizer (C), a high molecular weight plasticizer (C1) having a reactive silicon group (ie, high molecular weight plasticizer (C-1)) and By using a high molecular weight plasticizer (C2) having no reactive silicon group (ie, LBU-25, UP-1061 or UP-1080), the elongation at break while maintaining the strength at break (TB) It can be seen that (EB) can be improved.
- C1 high molecular weight plasticizer having a reactive silicon group
- C2 high molecular weight plasticizer having no reactive silicon group
- Example 13 60 parts by weight of the polymer (A-3) obtained in Synthesis Example 3 and 66.7 parts by weight of the isobutanol solution of the polymer (B-3) obtained in Synthesis Example 6 were mixed, and the isobutanol was reduced in pressure. Distillation off gave a polymer mixture in which the weight ratio of polymer (A-3) / polymer (B-3) was 60/40.
- viscosity The viscosity of the curable composition was measured at 23 ° C. and a relative humidity of 50% using a BH viscometer and rotor No. 6 (manufactured by Toki Sangyo Co., Ltd.) when the rotor rotational speed was 2 rpm or 20 rpm. The results are shown in the table below.
- the curable composition was filled in a polyethylene mold having a thickness of 3 mm so as not to contain bubbles, and cured at 23 ° C. and a relative humidity of 50% for 3 days, and further at 50 ° C. for 4 days to obtain a cured product. From the obtained cured product, a No. 7 dumbbell was punched in accordance with JIS K 6251, a tensile test (a tensile speed of 200 mm / min, 23 ° C., a relative humidity of 50%) was performed, and a modulus at 50% elongation (M50), The strength at break (TB) and the elongation at break (EB) were measured. The results are shown in the table below.
- Example 14 to 20 Polymer (A-3), polymer (B-3), high molecular weight plasticizer (C-1), filler, ultraviolet absorber, hindered amine light stabilizer (HALS), in the amounts shown in Tables 4 and 5.
- a curable composition was prepared by mixing a dehydrating agent, an adhesion-imparting agent, and a catalyst (tin compound, amine, carboxylic acid), and evaluated in the same manner as in Example 13. The results are shown in the table below.
- the curable composition of the present invention can be suitably used in sealants, adhesives, waterproofing coatings, and the like.
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Abstract
Description
[1] 一般式(1):
-SiR1 aX3-a (1)
(式中、R1は、炭素数1~20の置換または非置換の炭化水素基を表す。Xは、それぞれ独立に水酸基または加水分解性基(好ましくは加水分解性基)を表す。aは、0または1を示す。)
で表される反応性ケイ素基を1分子中に平均して1個より多く有するオキシアルキレン系重合体(A)、
一般式(2):
-SiX3 (2)
(式中、Xは、それぞれ独立に水酸基または加水分解性基(好ましくは加水分解性基)を表す。)
で表される反応性ケイ素基を有し、反応性ケイ素基当量が0.30mmol/g以上である(メタ)アクリル酸エステル系重合体(B)、および
反応性ケイ素基を1分子中に平均して0~1個有する高分子量可塑剤(C)
を含有する硬化性組成物。
[2] 重合体(A)が、反応性ケイ素基を1分子中に平均して1.2個以上有する前記[1]に記載の硬化性組成物。
[3] 重合体(A)の反応性ケイ素基が、ジメトキシメチルシリル基である前記[1]または[2]に記載の硬化性組成物。
[4] 高分子量可塑剤(C)が、反応性ケイ素基を1分子中に平均して0個より多く、且つ1個以下有する高分子量可塑剤(C1)である前記[1]~[3]のいずれか一つに記載に硬化性組成物。
[5] 高分子量可塑剤(C)が、反応性ケイ素基を有さない高分子量可塑剤(C2)である前記[1]~[3]のいずれか一つに記載の硬化性組成物。
[6] 高分子量可塑剤(C)が、反応性ケイ素基を1分子中に平均して0個より多く、且つ1個以下有する高分子量可塑剤(C1)および反応性ケイ素基を有さない高分子量可塑剤(C2)である前記[1]~[3]のいずれか一つに記載の硬化性組成物。
[7] 重合体(A)が有する反応性ケイ素基と高分子量可塑剤(C)が有する反応性ケイ素基とが同一である前記[4]または[6]に記載の硬化性組成物。
[8] 高分子量可塑剤(C)が、オキシアルキレン系重合体である前記[1]~[7]のいずれか一つに記載の硬化性組成物。
[9] 高分子量可塑剤(C)が、(メタ)アクリル酸エステル系重合体である前記[1]~[7]のいずれか一つに記載の硬化性組成物。
[10] 高分子量可塑剤(C)の数平均分子量が、1,000~15,000である前記[1]~[9]のいずれか一つに記載の硬化性組成物。
[11] 高分子量可塑剤(C)の含有量が、重合体(A)および重合体(B)の合計含有量100重量部に対して20~100重量部である前記[1]~[10]のいずれか一つに記載の硬化性組成物。
[12] 重合体(A)と重合体(B)の重量比(重合体(A):重合体(B))が90:10~30:70である前記[1]~[11]のいずれか一つに記載の硬化性組成物。
[13] 重合体(A)が、1つの末端部位に平均して1個より多い反応性ケイ素基を有する前記[1]~[12]のいずれか一つに記載の硬化性組成物。
[14] 重合体(B)を構成する単量体が、アルキルの炭素数が1~6であり、反応性ケイ素基を有さない(メタ)アクリル酸アルキル、およびアルキルの炭素数が7~30である(メタ)アクリル酸アルキルを含有する前記[1]~[13]のいずれか一つに記載の硬化性組成物。
[15] 重合体(B)を構成する単量体が、ホモポリマーのガラス転移温度が80℃以下である単量体(b1)を全単量体中40重量%以上で含有する前記[1]~[14]のいずれか一つに記載の硬化性組成物。
[16] 重合体(B)の数平均分子量が、4,000以上である前記[1]~[15]のいずれか一つに記載の硬化性組成物。
[17] 重合体(B)の数平均分子量が、1,000以上4,000未満である前記[1]~[15]のいずれか一つに記載の硬化性組成物。
[18] 重合体(B)を構成する単量体が、ホモポリマーのガラス転移温度が-25℃以上であり、反応性ケイ素基を有さない単量体(b2)を全単量体中40重量%以上で含有する前記[1]~[17]のいずれか一つに記載の硬化性組成物。
[19] 充填剤として、さらに平均一次粒子径が1μmより小さい重質炭酸カルシウムを含有する前記[1]~[18]のいずれか一つに記載の硬化性組成物。
[20] 充填剤として、さらに酸化チタンを含有する前記[1]~[19]のいずれか一つに記載の硬化性組成物。
[21] 充填剤として、さらに水酸化アルミニウムを含有する前記[1]~[20]のいずれか一つに記載の硬化性組成物。
[22] 前記[1]~[21]のいずれか一つに記載の硬化性組成物を含む塗膜防水剤。
[23] 前記[1]~[21]のいずれか一つに記載の硬化性組成物から得られる硬化物。
オキシアルキレン系重合体(A)は、以下の一般式(1):
-SiR1 aX3-a (1)
(式中、R1は、炭素数1~20の置換または非置換の炭化水素基を表す。Xは、それぞれ独立に水酸基または加水分解性基(好ましくは加水分解性基)を表す。aは、0または1を示す。)
で表される反応性ケイ素基を有する。
原料となるポリオキシアルキレン(以下、「前駆重合体」ともいう)に不飽和結合を導入し、この不飽和結合にヒドロシラン化合物をヒドロシリル化反応により付加させる方法が挙げられる。不飽和結合の導入方法には特に限定は無く、例えば、水酸基等の官能基を有する前駆重合体に、この官能基と反応して結合を形成する基および不飽和結合を有する化合物を反応させ、不飽和結合を含有する重合体を得る方法;不飽和結合を有する単量体を重合させる方法;等が挙げられる。
水酸基、アミノ基、不飽和結合等の官能基を有する前駆重合体と、その官能基と反応して結合を形成する基(以下、「反応性基」ともいう)および反応性ケイ素基の両方を有する化合物(シランカップリング剤)とを反応させる方法が挙げられる。前駆重合体の官能基とシランカップリング剤の反応性基の組合せとしては、水酸基とイソシアネート基、水酸基とエポキシ基、アミノ基とイソシアネート基、アミノ基とチオイソシアネート基、アミノ基とエポキシ基、アミノ基とα,β-不飽和カルボニル基(マイケル付加による反応)、カルボキシ基とエポキシ基、不飽和結合とメルカプト基等が挙げられるがこれに限らない。
-NR2-C(=O)- (3)
(式中、R2は炭素数1~10の有機基または水素原子を表す)で表されるアミドセグメントを含んでいてもよい。
Z-R3-SiR1 aX3-a (4)
(式中、R1、Xおよびaは、前記と同じである。R3は、2価の有機基、好ましくは炭素数1~20の2価の炭化水素基である。Zは、水酸基、カルボキシ基、メルカプト基、1級アミノ基または2級アミノ基である。)
で表されるケイ素化合物のZ基を、合成した重合体のイソシアネート基の全部または一部に反応させる方法を挙げることができる。
O=C=N-R3-SiR1 aX3-a (5)
(式中、R3、R1、Xおよびaは、前記と同じである。)
で示される反応性ケイ素基含有イソシアネート化合物を反応させる方法を挙げることができる。
(a)末端に水酸基を有するポリオキシアルキレン(前駆重合体)と不飽和結合を有するエポキシ化合物とを反応させて、前駆重合体の末端に不飽和結合および水酸基を導入し、
(b)水酸基と反応して結合を形成する基(例えばハロゲン原子)および不飽和結合を有する化合物と得られた重合体とを反応させて、重合体の末端に複数の不飽和結合を導入し、
(c)複数の不飽和結合にヒドロシラン化合物をヒドロシリル化反応により付加させる
方法が挙げられる。
で表される。
(メタ)アクリル酸エステル系重合体(B)は、以下の一般式(2):
-SiX3 (2)
(式中、Xは、それぞれ独立に水酸基または加水分解性基(好ましくは加水分解性基)を表す。)
で表わされる反応性ケイ素基を有し、反応性ケイ素基当量が0.30mmol/g以上である。なお本発明において「(メタ)アクリル」とは「アクリルおよび/またはメタクリル」を表わす。
(I)重合性不飽和結合と反応性ケイ素基を有する化合物を、(メタ)アクリル酸エステルとともに共重合する方法。
(II)連鎖移動剤として、上述の反応性ケイ素基とメルカプト基を有する化合物の存在下、(メタ)アクリル酸エステルを共重合する方法。
(III)重合性不飽和結合と反応性官能基(Z基)を有する化合物(例えば、アクリル酸、アクリル酸2-ヒドロキシエチル)を、Z基を有さない(メタ)アクリル酸エステルとともに共重合した後、反応性ケイ素基とZ基に反応する官能基を有する化合物(例えば、イソシアネートシラン化合物)を反応させる方法。
(IV)リビングラジカル重合法によって(メタ)アクリル酸エステルを重合した後、分子鎖末端に反応性ケイ素基を導入する方法。
なお、これらの方法は任意に組合せて用いてもよい。
本発明の硬化性組成物は、反応性ケイ素基を1分子中に平均して0~1個有する高分子量可塑剤(C)を含有する。高分子量可塑剤(C)の添加により、硬化性組成物の粘度や硬化物の伸びを調整できる。
本発明の効果を阻害しない限り、本発明の硬化性組成物は上述の重合体(A)、重合体(B)および高分子量可塑剤(C)以外の成分(その他の成分)を含有していてもよい。以下、その他の成分について説明する。
本発明の好ましい硬化性組成物では、
重合体(A)は、反応性ケイ素基としてジメトキシメチルシリル基またはトリメトキシメチル基を1分子中に平均して1.2~6.0個有し、数平均分子量が10,000~50,000であるポリオキシプロピレンであり、
重合体(B)は、反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.30~3.0mmol/gであり、数平均分子量が4,000~100,000であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が50~95重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が95:5~40:60であるポリ(メタ)アクリル酸エステル(B1)、または反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.30~3.0mmol/gであり、数平均分子量が1,000以上4,000未満であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が50~95重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が95:5~40:60であるポリ(メタ)アクリル酸エステル(B2)であり、
高分子量可塑剤(C)は、1分子中に平均して0.3~1個の反応性ケイ素基を有し、数平均分子量が500~15,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C1)、および/または反応性ケイ素基を有さず、数平均分子量が500~15,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C2)であり、
硬化性組成物中の重合体(A)および重合体(B)の合計含有量は、30~90重量%であり、
重合体(A)と重合体(B)の重量比(重合体(A):重合体(B))は、90:10~30:70であり、
高分子量可塑剤(C)の含有量は、重合体(A)および重合体(B)の合計含有量100重量部に対して5~200重量部である。
重合体(A)は、反応性ケイ素基としてジメトキシメチルシリル基またはトリメトキシメチル基を1分子中に平均して1.3~5.5個有し、数平均分子量が15,000~35,000であるポリオキシプロピレンであり、
重合体(B)は、反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.35~2.5mmol/gであり、数平均分子量が6,000~50,000であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が60~90重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が90:10~60:40であるポリ(メタ)アクリル酸エステル(B1)、または反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.35~2.5mmol/gであり、数平均分子量が1,500~3,000であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が60~90重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が90:10~60:40であるポリ(メタ)アクリル酸エステル(B2)であり、
高分子量可塑剤(C)は、1分子中に平均して0.5~1個の反応性ケイ素基を有し、数平均分子量が1,000~10,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C1)、および/または反応性ケイ素基を有さず、数平均分子量が1,000~10,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C2)であり、
硬化性組成物中の重合体(A)および重合体(B)の合計含有量は、50~80重量%であり、
重合体(A)と重合体(B)の重量比(重合体(A):重合体(B))は、85:15~40:60であり、
高分子量可塑剤(C)の含有量は、重合体(A)および重合体(B)の合計含有量100重量部に対して10~150重量部である。
重合体(A)は、反応性ケイ素基としてジメトキシメチルシリル基を1分子中に平均して1.5~5.0個有し、数平均分子量が20,000~30,000であるポリオキシプロピレンであり、
重合体(B)は、反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.40~2.0mmol/gであり、数平均分子量が8,000~30,000であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が60~90重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が90:10~60:40であるポリ(メタ)アクリル酸エステル(B1)、または反応性ケイ素基としてトリメトキシメチル基を有し、反応性ケイ素基当量が0.40~2.0mmol/gであり、数平均分子量が1,500~3,000であり、重合体(B)を構成する全単量体中の単量体(b3)および単量体(b4)の合計量が60~90重量%であり、単量体(b3)と単量体(b4)の重量比(単量体(b3):単量体(b4))が90:10~60:40であるポリ(メタ)アクリル酸エステル(B2)であり、
高分子量可塑剤(C)は、1分子中に平均して0.6~1個の反応性ケイ素基を有し、数平均分子量が2,000~8,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C1)、および反応性ケイ素基を有さず、数平均分子量が2,000~8,000であるポリオキシプロピレンまたはポリ(メタ)アクリル酸エステルである高分子量可塑剤(C2)であり、高分子量可塑剤(C1)および高分子量可塑剤(C2)の重量比(高分子量可塑剤(C1):高分子量可塑剤(C2))が80:20~50:50であり、
硬化性組成物中の重合体(A)および重合体(B)の合計含有量は、50~80重量%であり、
重合体(A)と重合体(B)の重量比(重合体(A):重合体(B))は、80:20~50:50であり、
高分子量可塑剤(C)の含有量は、重合体(A)および重合体(B)の合計含有量100重量部に対して20~100重量部である。
数平均分子量が約2,000のポリオキシプロピレンジオールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量28,500のポリオキシプロピレンジオールを得た。続いてこのポリオキシプロピレンジオールの水酸基1当量に対して1.2当量のNaOMeを含有するメタノール溶液を添加し、メタノールを留去した後、さらに1.5当量の3-クロロ-2-メチル-1-プロペンを添加して末端の水酸基をメタリル基に変換した。次に容器内を6体積%O2/N2で置換し、得られたメタリル基末端ポリオキシプロピレン100重量部に対して、硫黄(0.25重量%のヘキサン溶液)100重量ppm、白金ジビニルジシロキサン錯体(白金換算で3重量%のイソプロパノール溶液)100重量ppmを加え、撹拌しながら、ジメトキシメチルシラン2.30重量部をゆっくりと滴下した。その混合溶液を100℃で5時間反応させた後、未反応のジメトキシメチルシランを減圧下留去することにより、末端がジメトキシメチルシリル基であり、1分子あたりの反応性ケイ素基数が平均1.9であり、数平均分子量(Mn)が28,500であり、分子量分布(Mw/Mn)が1.2である直鎖状のポリオキシプロピレン(重合体(A-1))を得た。
数平均分子量が約3,000のポリオキシプロピレントリオールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量26,200のポリオキシプロピレントリオールを得た。続いてこのポリオキシプロピレントリオールの水酸基1当量に対して1.2当量のNaOMeを含有するメタノール溶液を添加し、メタノールを留去した後、さらに1.5当量の3-クロロ-1-プロペンを添加して末端の水酸基をアリル基に変換した。次に得られたアリル基末端ポリオキシプロピレン100重量部に対して白金ジビニルジシロキサン錯体(白金換算で3重量%のイソプロパノール溶液)36重量ppmを加え、撹拌しながら、TES(トリエトキシシラン)1.69重量部をゆっくりと滴下した。その混合溶液を90℃で2時間反応させた後、未反応のTESを減圧下留去した。さらにメタノール20重量部、HCl 12重量ppmを添加して末端のエトキシ基をメトキシ基に変換することにより、末端がトリメトキシシリル基であり、1分子あたりの反応性ケイ素基数が平均1.8であり、数平均分子量26,200であり、分子量分布(Mw/Mn)が1.3である、分枝鎖状のポリオキシプロピレン(重合体(A-2))を得た。
数平均分子量が約2,000のポリオキシプロピレンジオールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量約28,500のポリオキシプロピレンジオールを得た。続いてこのポリオキシプロピレンジオールの水酸基1当量に対して1.0当量のNaOMeを含有するメタノール溶液を添加してメタノールを留去し、続いて1.0当量のアリルグリシジルエーテルを添加して130℃で2時間反応を行った。その後、0.28当量のナトリウムメトキシドを含有するメタノール溶液を添加し、メタノールを除去した後、さらに1.79当量の3-クロロ-1-プロペンを添加して末端の水酸基をアリル基に変換した。以上により、1つの末端部位に炭素-炭素不飽和結合を平均2.1個有するポリオキシプロピレンを得た。次に得られた重合体100重量部に対して白金ジビニルジシロキサン錯体(白金換算で3重量%のイソプロパノール溶液)36重量ppmを加え、撹拌しながら、ジメトキシメチルシラン1.9重量部をゆっくりと滴下し、90℃で2時間反応させた後、未反応のジメトキシメチルシランを減圧下留去することにより、末端がジメトキシメチルシリル基であり、1分子当たりの反応性ケイ素基数が3.2であり、数平均分子量が28,500である直鎖状のポリオキシプロピレン(重合体(A-3))を得た。
攪拌機を備えた四口フラスコにイソブタノール48.6重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート65.0重量部、2-エチルヘキシルアクリレート25.0重量部、3-メタクリロキシプロピルトリメトキシシラン10.0重量部、3-メルカプトプロピルトリメトキシシラン8.0重量部、および2,2’-アゾビス(2-メチルブチロニトリル)2.5重量部をイソブタノール22.7重量部に溶解した混合溶液を5時間かけて滴下した。さらに105℃で2時間重合を行い、1分子中に平均して1.8個のトリメトキシシシリル基(反応性ケイ素基)を有し、反応性ケイ素基当量が0.75mmol/gであり、数平均分子量が2,400であるポリ(メタ)アクリル酸エステル(重合体(B-1))のイソブタノール溶液(固形分60重量%)を得た。
なお、重合体(B-1)の反応性ケイ素基当量は、反応性ケイ素基を有する単量体の添加量から計算した値である。後述の反応性ケイ素基当量も同様である。
攪拌機を備えた四口フラスコにイソブタノール26.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート56.0重量部、ステアリルメタクリレート32.0重量部、3-メタクリロキシプロピルトリメトキシシラン12.0重量部、および2,2’-アゾビス(2-メチルブチロニトリル)4.5重量部をイソブタノール43.1重量部に溶解した混合溶液を5時間かけて滴下した。さらに105℃で2時間重合を行い、1分子中に平均して2.8個のトリメトキシシシリル基(反応性ケイ素基)を有し、反応性ケイ素基当量が0.48mmol/gであり、数平均分子量が6,000であるポリ(メタ)アクリル酸エステル(重合体(B-2))のイソブタノール溶液(固形分60重量%)を得た。
攪拌機を備えた四口フラスコにイソブタノール26.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート20.0重量部、ブチルメタクリレート36.0重量部、ステアリルメタクリレート32.0重量部、3-メタクリロキシプロピルトリメトキシシラン12.0重量部、および2,2’-アゾビス(2-メチルブチロニトリル)4.5重量部をイソブタノール40.6重量部に溶解した混合溶液を5時間かけて滴下した。さらに105℃で2時間重合を行い、1分子中に平均して2.9個のトリメトキシシシリル基(反応性ケイ素基)を有し、反応性ケイ素基当量が0.48mmol/gであり、数平均分子量が6,500であるポリ(メタ)アクリル酸エステル(重合体(B-3))のイソブタノール溶液(固形分60重量%)を得た。
攪拌機を備えた四口フラスコにイソブタノール26.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート56.0重量部、ステアリルメタクリレート32.0重量部、3-メタクリロキシプロピルジメトキシメチルシシラン12.0重量部、および2,2’-アゾビス(2-メチルブチロニトリル)4.5重量部をイソブタノール43.1重量部に溶解した混合溶液を5時間かけて滴下した。さらに105℃で2時間重合を行い、1分子中に平均して2.8個のジメトキシメチルシリル基(反応性ケイ素)を有し、反応性ケイ素基当量が0.48mmol/gであり、数平均分子量が6,000である(メタ)アクリル酸エステル系重合体(重合体(P-1))のイソブタノール溶液(固形分60%)を得た。
攪拌機を備えた四口フラスコにイソブタノール26.7重量部を入れ、窒素雰囲気下、105℃まで昇温した。そこに、メチルメタクリレート27.0重量部、ブチルメタクリレート36.0重量部、ステアリルメタクリレート32.0重量部、3-メタクリロキシプロピルトリメトキシシラン5.0重量部、および2,2’-アゾビス(2-メチルブチロニトリル)4.5重量部をイソブタノール40.6重量部に溶解した混合溶液を5時間かけて滴下した。さらに105℃で2時間重合を行い、1分子中に平均して1.3個のトリメトキシシシリル基(反応性ケイ素基)を有し、反応性ケイ素基当量が0.20mmol/gであり、数平均分子量が6,500である(メタ)アクリル酸系エステル重合体(重合体(P-2))のイソブタノール溶液(固形分60重量%)を得た。
MMA:メタクリル酸メチル
BMA:メタクリル酸n-ブチル
BA:アクリル酸n-ブチル
2-EHA:アクリル酸2-エチルヘキシル
SMA:メタクリル酸ステアリル
TSMA:3-メタクリロキシプロピルトリメトキシシラン
T-MSi:3-メルカプトプロピルトリメトキシシラン
DSMA:3-メタクリロキシプロピルジメトキシメチルシラン
ブタノールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量7,000のポリオキシプロピレンを得た。続いてこの水酸基末端ポリオキシプロピレンの水酸基1当量に対して1.2当量のNaOMeを含有するメタノール溶液を添加し、メタノールを留去した後、さらに1.5当量の3-クロロ-1-プロペンを添加して末端の水酸基をアリル基に変換した。次に得られたアリル基末端ポリオキシプロピレン100重量部に対して白金ジビニルジシロキサン錯体(白金換算で3重量%のイソプロパノール溶液)36重量ppmを加え撹拌しながら、ジメトキシメチルシラン1.72重量部をゆっくりと滴下した。その混合溶液を90℃で2時間反応させることにより、末端がジメトキシメチルシリル基であり、1分子あたりの反応性ケイ素基数が平均0.7であり、数平均分子量が7,000であり、分子量分布(Mw/Mn)が1.2である直鎖状のポリオキシプロピレン(高分子量可塑剤(C-1))を得た。
ブタノールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量7,000のポリオキシプロピレンを得た。続いてこの水酸基末端ポリオキシプロピレンの水酸基1当量に対して1.2当量のNaOMeを含有するメタノール溶液を添加し、メタノールを留去した後、さらに1.5当量の3-クロロ-1-プロペンを添加して末端の水酸基をアリル基に変換した。次に得られたアリル基末端ポリオキシプロピレン100重量部に対して白金ジビニルジシロキサン錯体(白金換算で3重量%のイソプロパノール溶液)36重量ppmを加え撹拌しながら、トリメトキシシラン1.98重量部をゆっくりと滴下した。その混合溶液を90℃で2時間反応させることにより、末端がトリメトキシシリル基であり、1分子あたりのケイ素基が平均0.7個、数平均分子量が7,000であり、分子量分布(Mw/Mn)が1.2である直鎖状のポリオキシプロピレン(高分子量可塑剤(C-2))を得た。
数平均分子量が約3,000のポリオキシプロピレントリオールを開始剤として使用し、亜鉛ヘキサシアノコバルテートグライム錯体触媒にてプロピレンオキシドの重合を行い、数平均分子量16,400のポリオキシプロピレントリオールを得た。続いてこの水酸基末端ポリオキシプロピレントリオールの水酸基1当量に対して1.2当量のNaOMeを含有するメタノール溶液を添加し、メタノールを留去した後、さらに1.5当量の3-クロロ-1-プロペンを添加して末端の水酸基をアリル基に変換し、アリル基末端ポリオキシプロピレン(高分子量可塑剤(C-3))を得た。
合成例1で得られた重合体(A-1)60.0重量部と合成例4で得られた重合体(B-1)のイソブタノール溶液66.7重量部を混合して、イソブタノールを減圧留去し、重合体(A-1)/重合体(B-1)の重量比が60/40である重合体混合物を得た。この重合体混合物100重量部に対して、合成例8で得られた高分子量可塑剤(C-1)30重量部を添加および混練し、硬化性組成物を得た。
23℃、相対湿度50%で、硬化性組成物(表2に示す脱水剤、接着付与剤および触媒は含まない)の粘度をE型粘度計(東京計器製、測定コーン:3°C×R14)で測定した。その結果を下記表に示す。
重合体(A-1)および重合体(B-1)の合計含有量100重量部に対して、ビニルトリメトキシシラン(Momentive(株)製、商品名:A-171)1重量部、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名:KBM-603)2重量部、ジオクチル錫ジラウレート(日東化成(株)製、商品名:ネオスタンU-810)0.5重量部を添加した後、十分混合した。得られた組成物を厚み3mmのポリエチレン製の型枠に気泡が入らないよう充填し、23℃、相対湿度50%で3日間、さらに50℃で4日間養生することにより硬化物を得た。得られた硬化物から、JIS K 6251に準拠して7号ダンベルを打ち抜き、引張り試験(引張り速度200mm/分、23℃、相対湿度50%)を行い、50%伸張時のモジュラス(M50)、破断時強度(TB)、破断時伸び率(EB)を測定した。その結果を下記表に示す。
下記表に示す種類および量の重合体(A)、重合体(B)、重合体(P)、高分子量可塑剤(C)、低分子量可塑剤、脱水剤、接着付与剤および触媒を使用し、実施例1と同様にして、硬化性組成物を調製し、その評価を行った。なお、粘度は、下記表に示す脱水剤、接着付与剤および触媒を含まない硬化性組成物の粘度を測定した。その結果を下記表に示す。
また、上記表2~4中において商品名で示す各成分の物質名およびメーカーは以下の通りである。
LBU-25:ウレタン化ポリオキシプロピレン(三洋化成工業(株)、数平均分子量(Mn)4,100、分子量分布(Mw/Mn)1.2)
UP-1061:ポリ(メタ)アクリル酸エステル(東亜合成(株)、数平均分子量(Mn)870、分子量分布(Mw/Mn)1.7)
UP-1080:ポリ(メタ)アクリル酸エステル(東亜合成(株)、数平均分子量(Mn)2,700、分子量分布(Mw/Mn)2.1)
DINP:ジイソノニルフタレート((株)ジェイプラス、分子量418)
A-171:ビニルトリメトキシシラン(Momentive(株))
KBM-603:N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン(信越化学工業(株))
ネオスタンU-810:ジオクチル錫ジラウレート(日東化成(株))
合成例3で得られた重合体(A-3)60重量部と合成例6で得られた重合体(B-3)のイソブタノール溶液66.7重量部を混合して、イソブタノールを減圧留去し、重合体(A-3)/重合体(B-3)の重量比が60/40である重合体混合物を得た。この重合体混合物100重量部に対して、合成例8で得られた高分子量可塑剤(C-1)30重量部、脂肪酸処理炭酸カルシウム(白石工業(株)製、商品名:白艶華CCR)40重量部、紫外線吸収剤(住友化学(株)製、商品名:スミソーブ400)1重量部、ヒンダードアミン系光安定剤(HALS)((株)ADEKA製、商品名:アデカスタブLA-63P)1重量部を混合して、充分混練りした後、混合物を3本ペイントロールに3回通して、各成分を分散させた。この後、120℃で2時間減圧脱水を行い、脱水した混合物を50℃以下に冷却後、冷却した混合物に脱水剤としてビニルトリメトキシシラン(Momentive(株)製、商品名:A-171)3重量部、接着性付与剤としてN-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン(信越化学工業(株)製、商品名:KBM-603)5重量部、触媒としてジオクチル錫ジラウレート(日東化成(株)製、商品名:ネオスタンU-810)1重量部を加えて、実質的に水分の存在しない状態で混練した後、得られた組成物を防湿性のカートリッジ型容器に充填後に密封して、1成分型硬化性組成物を得た。
23℃、相対湿度50%で、硬化性組成物の粘度をBH型粘度計、ローターNo.6(東機産業社製)を用い、ローター回転数が2rpmまたは20rpmの時の粘度を測定した。その結果を下記表に示す。
硬化性組成物を厚み3mmのポリエチレン製の型枠に気泡が入らないよう充填し、23℃、相対湿度50%で3日間、さらに50℃で4日間養生することにより硬化物を得た。得られた硬化物から、JIS K 6251に準拠して7号ダンベルを打ち抜き、引張り試験(引張り速度200mm/分、23℃、相対湿度50%)を行い、50%伸張時のモジュラス(M50)、破断時強度(TB)、破断時伸び率(EB)を測定した。その結果を下記表に示す。
表4および5に示す量で重合体(A-3)、重合体(B-3)、高分子量可塑剤(C-1)、充填剤、紫外線吸収剤、ヒンダードアミン系光安定剤(HALS)、脱水剤、接着性付与剤、触媒(錫化合物、アミン、カルボン酸)を混合して硬化性組成物を調製し、実施例13と同様にして評価を行った。その結果を下記表に示す。
また、上記表5および6中において商品名で示す各成分の物質名およびメーカーは以下の通りである。
白艶華CCR:脂肪酸処理膠質炭酸カルシウム(白石工業(株)、平均一次粒子径0.08μm)
ナノコートS25:脂肪酸処理重質炭酸カルシウム(丸尾カルシウム(株)、平均一次粒子径1.0μm)
ナノックス#30:重質炭酸カルシウム(丸尾カルシウム(株)、平均一次粒子径0.7μm)
タイペークR-820:酸化チタン(石原産業(株))
ハイジライトH42M:水酸化アルミニウム(昭和電工(株))
PANSIL Ultraspheres2000:中空アルミナシリカ微粒子(TOLSA)
スミソーブ400:2,4-ジ-tert-ブチルフェニル-3,5-ジ-tert-ブチル-4-ヒドロキシベンゾエート(住友化学(株))
アデカスタブLA-63P:1,2,2,6,6-ペンタメチル-4-ピペリジノールとβ,β,β′,β′-テトラメチル-2,4,8,10-テトラオキサスピロ(5.5)ウンデカン-3,9-ジエタノールとの縮合物((株)ADEKA)
A-171:ビニルトリメトキシシラン(Momentive(株))
KBM-603:N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン(信越化学工業(株))
ネオスタンU-810:ジオクチル錫ジラウレート(日東化成(株))
ネオスタンU-50:ビスネオデカン酸錫(日東化成(株))
バーサティック10:ネオデカン酸(ジャパンエポキシレジン(株))
Claims (23)
- 一般式(1):
-SiR1 aX3-a (1)
(式中、R1は、炭素数1~20の置換または非置換の炭化水素基を表す。Xは、それぞれ独立に水酸基または加水分解性基を表す。aは、0または1を示す。)
で表される反応性ケイ素基を1分子中に平均して1個より多く有するオキシアルキレン系重合体(A)、
一般式(2):
-SiX3 (2)
(式中、Xは、それぞれ独立に水酸基または加水分解性基を表す。)
で表される反応性ケイ素基を有し、反応性ケイ素基当量が0.30mmol/g以上である(メタ)アクリル酸エステル系重合体(B)、および
反応性ケイ素基を1分子中に平均して0~1個有する高分子量可塑剤(C)
を含有する硬化性組成物。 - 重合体(A)が、反応性ケイ素基を1分子中に平均して1.2個以上有する請求項1に記載の硬化性組成物。
- 重合体(A)の反応性ケイ素基が、ジメトキシメチルシリル基である請求項1または2に記載の硬化性組成物。
- 高分子量可塑剤(C)が、反応性ケイ素基を1分子中に平均して0個より多く、且つ1個以下有する高分子量可塑剤(C1)である請求項1~3のいずれか1項に記載に硬化性組成物。
- 高分子量可塑剤(C)が、反応性ケイ素基を有さない高分子量可塑剤(C2)である請求項1~3のいずれか1項に記載の硬化性組成物。
- 高分子量可塑剤(C)が、反応性ケイ素基を1分子中に平均して0個より多く、且つ1個以下有する高分子量可塑剤(C1)および反応性ケイ素基を有さない高分子量可塑剤(C2)である請求項1~3のいずれか1項に記載の硬化性組成物。
- 重合体(A)が有する反応性ケイ素基と高分子量可塑剤(C)が有する反応性ケイ素基とが同一である請求項4または6に記載の硬化性組成物。
- 高分子量可塑剤(C)が、オキシアルキレン系重合体である請求項1~7のいずれか1項に記載の硬化性組成物。
- 高分子量可塑剤(C)が、(メタ)アクリル酸エステル系重合体である請求項1~7のいずれか1項に記載の硬化性組成物。
- 高分子量可塑剤(C)の数平均分子量が、1,000~15,000である請求項1~9のいずれか1項に記載の硬化性組成物。
- 高分子量可塑剤(C)の含有量が、重合体(A)および重合体(B)の合計含有量100重量部に対して20~100重量部である請求項1~10のいずれか1項に記載の硬化性組成物。
- 重合体(A)と重合体(B)の重量比(重合体(A):重合体(B))が90:10~30:70である請求項1~11のいずれか1項に記載の硬化性組成物。
- 重合体(A)が、1つの末端部位に平均して1個より多い反応性ケイ素基を有する請求項1~12のいずれか1項に記載の硬化性組成物。
- 重合体(B)を構成する単量体が、アルキルの炭素数が1~6である(メタ)アクリル酸アルキル、およびアルキルの炭素数が7~30である(メタ)アクリル酸アルキルを含有する請求項1~13のいずれか1項に記載の硬化性組成物。
- 重合体(B)を構成する単量体が、ホモポリマーのガラス転移温度が80℃以下であり、反応性ケイ素基を有さない単量体(b1)を全単量体中40重量%以上で含有する請求項1~14のいずれか1項に記載の硬化性組成物。
- 重合体(B)の数平均分子量が、4,000以上である請求項1~15のいずれか1項に記載の硬化性組成物。
- 重合体(B)の数平均分子量が、1,000以上4,000未満である請求項1~15のいずれか1項に記載の硬化性組成物。
- 重合体(B)を構成する単量体が、ホモポリマーのガラス転移温度が-25℃以上であり、反応性ケイ素基を有さない単量体(b2)を全単量体中40重量%以上で含有する請求項1~17のいずれか1項に記載の硬化性組成物。
- 充填剤として、さらに平均一次粒子径が1μmより小さい重質炭酸カルシウムを含有する請求項1~18のいずれか1項に記載の硬化性組成物。
- 充填剤として、さらに酸化チタンを含有する請求項1~19のいずれか1項に記載の硬化性組成物。
- 充填剤として、さらに水酸化アルミニウムを含有する請求項1~20のいずれか1項に記載の硬化性組成物。
- 請求項1~21のいずれか1項に記載の硬化性組成物を含む塗膜防水剤。
- 請求項1~21のいずれか1項に記載の硬化性組成物から得られる硬化物。
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Also Published As
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JPWO2014192914A1 (ja) | 2017-02-23 |
CN105324436B (zh) | 2018-08-28 |
JP6475615B2 (ja) | 2019-02-27 |
EP3006504B1 (en) | 2019-04-03 |
US20160108235A1 (en) | 2016-04-21 |
CN105324436A (zh) | 2016-02-10 |
EP3006504A1 (en) | 2016-04-13 |
EP3006504A4 (en) | 2016-11-16 |
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