CN111094442A - Curable composition, sealing material composition, and adhesive composition - Google Patents
Curable composition, sealing material composition, and adhesive composition Download PDFInfo
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- CN111094442A CN111094442A CN201880060565.5A CN201880060565A CN111094442A CN 111094442 A CN111094442 A CN 111094442A CN 201880060565 A CN201880060565 A CN 201880060565A CN 111094442 A CN111094442 A CN 111094442A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
Abstract
The invention provides a curable composition, a sealing material composition and an adhesive composition which have excellent operability and excellent mechanical properties and weather resistance of a cured product. The curable composition comprises an oxyalkylene polymer (A) having a reactive silyl group and a (meth) acrylic polymer (B) having a double bond of 0.01meq/g or more and 1.0meq/g or less in the molecule. The (meth) acrylic polymer (B) may have 0.1 to 2.2 reactive silyl groups in the molecule.
Description
Technical Field
The present invention relates to a curable composition, and more particularly, to a curable composition which is cured at room temperature by moisture in the atmosphere or the like to form a cured product exhibiting excellent mechanical properties, a sealant composition of the curable composition, and an adhesive composition containing the curable composition.
Background
Examples of the curable composition containing a polymer having a room temperature curing type reactive group include compositions containing various polymers such as modified silicone polymers, urethane polymers, polythioether polymers, and acrylic polymers, and the curable composition is widely used as an adhesive, a sealing material, a coating material, and the like in architectural applications, electric/electronic field-related applications, automobile-related applications, and the like. For example, the modified silicone polymer is a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group, and is a material having good handling properties and a good balance of mechanical properties such as elongation at break and breaking strength, and therefore is widely used as a base polymer for adhesives and sealing materials.
However, it is known that a curable composition containing a modified silicone polymer as a base polymer has a problem that the cured product obtained therefrom has insufficient weather resistance. Therefore, a curable composition containing an acrylic polymer has been proposed.
Patent document 1 discloses a sealing material composition containing a specific vinyl polymer having an alkoxysilyl group, a polyoxyalkylene compound having an alkoxysilyl group at a terminal, and polypropylene glycol having a specific molecular weight or a specific vinyl polymer having no alkoxysilyl group. Patent document 2 discloses a sealing material composition containing an oxyalkylene polymer having a hydrolyzable silyl group and a specific vinyl polymer having a crosslinkable functional group. Patent document 3 discloses that a curable resin composition comprising a specific vinyl polymer and an oxyalkylene polymer containing a hydrolyzable silyl group can be suitably used for a sealing material and an adhesive for exterior tiles, and that the specific vinyl polymer contains a (meth) acrylate monomer having a hydrolyzable silyl group as a constituent monomer.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2004-18748
Patent document 2: international publication No. 2008/059872
Patent document 3: japanese patent laid-open No. 2014-118502
Disclosure of Invention
Problems to be solved by the invention
Cured products obtained from the compositions described in patent documents 1 to 3 exhibit good mechanical properties and improved weather resistance. However, the demand for improvement of weather resistance is high, and further improvement of weather resistance is also required for the curable composition. In addition, it is known that: generally, a polymer having a high molecular weight tends to improve weather resistance, and the composition has a high viscosity, which causes problems in coating properties and handling properties.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a curable composition, a sealant composition, and an adhesive composition which have excellent workability due to low viscosity and which provide a cured product having excellent mechanical properties and weather resistance.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: a curable composition comprising an oxyalkylene polymer having a reactive silyl group as a base resin and a (meth) acrylic polymer, wherein a specific amount of double bonds are contained in the (meth) acrylic polymer, whereby the weather resistance of a cured product, and a sealing material and an adhesive containing the cured product is improved. The present invention has been completed based on this finding. According to the present specification, the following means are provided.
[ 1] A curable composition comprising an oxyalkylene polymer (A) having a reactive silyl group and a (meth) acrylic polymer (B),
the (meth) acrylic polymer (B) has a double bond of 0.01meq/g or more and 1.0meq/g or less in the molecule.
The curable composition according to [ 1] above, wherein the (meth) acrylic polymer (B) has a weight average molecular weight of 1,000 to 50,000.
[ 3] the curable composition according to [ 1] or [ 2], wherein the viscosity of the (meth) acrylic polymer (B) at 25 ℃ is 1,000 to 300,000 mPas.
The curable composition according to any one of [ 1] to [ 3] above, wherein the (meth) acrylic polymer (B) has 0.1 to 2.2 reactive silyl groups in the molecule.
The curable composition according to [ 4] above, wherein the (meth) acrylic polymer (B) has a dialkoxysilyl group as the reactive silyl group.
The curable composition according to any one of [ 1] to [ 5], wherein the (meth) acrylic polymer (B) contains an alkyl (meth) acrylate having an alkyl group having 10 or more carbon atoms in an amount of 5% by mass or more based on the total monomer units constituting the (meth) acrylic polymer.
The curable composition according to any one of [ 1] to [ 6], wherein the oxyalkylene polymer (A) has a number average molecular weight of 22,000 or more.
The curable composition according to any one of [ 1] to [ 7], wherein the oxyalkylene polymer (A) and the (meth) acrylic polymer (B) are used in an amount of 10to 90/90 to 10 in terms of a mass ratio.
The curable composition according to any one of [ 1] to [ 8 ] above, which comprises at least one compound selected from a tin-based catalyst, a titanium-based catalyst and a tertiary amine as a curing accelerator.
A sealant composition comprising the curable composition according to any one of [ 1] to [ 9 ] above.
An adhesive composition comprising the curable composition according to any one of [ 1] to [ 9 ] above.
Effects of the invention
The curable composition of the present invention has a low viscosity and is excellent in workability. Further, a cured product having excellent strength, elongation and weather resistance is obtained from the composition. Therefore, the composition is suitably used for adhesives such as sealing materials and exterior tile adhesives which require excellent mechanical properties and high weather resistance.
Detailed Description
The present invention will be described in detail below. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth) acrylate" means acrylate and/or methacrylate. Further, "(meth) acryloyl" means acryloyl and/or methacryloyl.
The curable composition of the present invention contains, as essential components, an oxyalkylene polymer having a reactive silyl group as the component (a) and a (meth) acrylic polymer as the component (B). The details of each component will be described below.
< (A) component: oxyalkylene polymer having reactive silyl group
The oxyalkylene polymer having a reactive silyl group is not particularly limited as long as it is a compound containing a repeating unit represented by the following general formula (1).
-O-R2- (1)
(in the formula, R2Is a 2-valent hydrocarbon group. )
As R in the above general formula (1)2The following groups can be exemplified.
(CH2) n (n is an integer of 1 to 10)
CH(CH3)CH2
CH(C2H5)CH2
C(CH3)2CH2
The oxyalkylene polymer may contain one kind of the repeating unit or two or more kinds of the repeating units in combination. Among them, CH (CH) is preferable from the viewpoint of excellent workability3)CH2。
The reactive silyl group contained in the reactive silyl group-containing oxyalkylene polymer is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenosilyl group, a silanol group and the like, but an alkoxysilyl group is preferable from the viewpoint of easiness of control of reactivity. Specific examples of the alkoxysilyl group include trimethoxysilyl group, methyldimethoxysilyl group, dimethylmethoxysilyl group, triethoxysilyl group, methyldiethoxysilyl group, and dimethylethoxysilyl group.
The method for producing the oxyalkylene polymer is not particularly limited, and examples thereof include a polymerization method using a base catalyst such as KOH using a corresponding epoxy compound or diol as a raw material, a polymerization method using a transition metal compound-porphyrin complex catalyst, a polymerization method using a composite metal cyanide complex catalyst, and a polymerization method using phosphazene.
The oxyalkylene polymer may be either a linear polymer or a branched polymer. Further, they may be used in combination.
The average number of reactive silyl groups contained in the 1-molecule oxyalkylene polymer is preferably in the range of 1 to 4, more preferably in the range of 1.5 to 3, from the viewpoint of the properties such as adhesiveness and tensile properties of the cured product.
The position of the reactive silyl group contained in the oxyalkylene polymer is not particularly limited, and may be a side chain and/or a terminal of the polymer.
The oxyalkylene polymer may be either a linear polymer or a branched polymer. Further, they may be used in combination.
From the viewpoint of mechanical properties, the number average molecular weight (Mn) of the oxyalkylene polymer having a reactive silyl group is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 15,000 or more. The Mn may be 18,000 or more, 22,000 or more, and 25,000 or more. From the viewpoint of workability (viscosity) at the time of coating of the curable composition, the upper limit value of Mn is preferably 60,000 or less, more preferably 50,000 or less, and further preferably 40,000 or less. The range of Mn may be set in combination with the above upper and lower limits, and may be, for example, 5,000 to 60,000, 15,000 to 60,000, 18,000 to 50,000, or 22,000 to 50,000.
As the oxyalkylene polymer having a reactive silyl group, a commercially available product can be used. Specific examples thereof include: "MS Polymer S203", "MS Polymer S303", "MS Polymer S810", "Silyl SAT 200", "Silyl SAT 350", "Silyl EST 280" and "Silyl SAT 30", manufactured by KANEKA, Inc.; and Asahi glass company "EXCESTAR S2410", "EXCESTAR S2420" and "EXCESTAR S3430" (trade names).
< (B) component: (meth) acrylic polymer
The (meth) acrylic polymer is a polymer having a structural unit derived from a (meth) acrylic monomer, and can be obtained, for example, by polymerizing a monomer mixture containing a (meth) acrylic monomer. The (meth) acrylic monomer is a monomer having a (meth) acryloyl group in the molecule, and examples thereof include (meth) acrylic acid, alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates, and the like. The amount of the (meth) acrylic monomer used is preferably in the range of 10to 100% by mass, more preferably in the range of 30 to 100% by mass, and still more preferably in the range of 50 to 100% by mass, based on the total constituent monomers of the (meth) acrylic polymer.
Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, and mixtures thereof, Pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, stearyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, heneicosyl (meth) acrylate, docosyl (meth) acrylate, ditetradecyl (meth) acrylate, hexacosyl (meth) acrylate, dioctadecyl (meth) acrylate, triacontyl (meth) acrylate, tridecyl (meth) acrylate, triacontyl (meth) acrylate, forty-alkyl (meth) acrylate, isodecyl (meth) acrylate, isoundecyl (meth) acrylate, isolauryl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth), Isotridecyl (meth) acrylate, isotetradecyl (meth) acrylate, isotentadecyl (meth) acrylate, isocetyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, isonnonadecyl (meth) acrylate, isoeicosyl (meth) acrylate, isoheneicosyl (meth) acrylate, isodocosyl (meth) acrylate, isotetradecyl (meth) acrylate, isohexacosyl (meth) acrylate, isostearyl (meth) acrylate, isotridecyl (meth) acrylate, isot, Alkyl (meth) acrylates having a linear or branched aliphatic alkyl group or an alicyclic alkyl group such as iso-forty alkyl (meth) acrylate, and one or two or more kinds of these may be used. Among them, alkyl (meth) acrylates having an alkyl group having 1 to 8 carbon atoms are preferable from the viewpoint of mechanical properties of the cured product. The amount of the alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total constituent monomers of the (meth) acrylic polymer. The upper limit value may be 100% by mass, 90% by mass, 80% by mass, or 50% by mass.
Among the above, the use of an alkyl (meth) acrylate having an alkyl group having 10 or more carbon atoms is preferable in view of ensuring good compatibility with the oxyalkylene polymer and providing good mechanical properties and weather resistance. The number of carbon atoms of the alkyl group is preferably 10to 20, more preferably 12 to 20. The amount of the alkyl (meth) acrylate having an alkyl group having 10 or more carbon atoms to be used is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, based on the total constituent monomers of the (meth) acrylic polymer. The upper limit is 100 mass% or less, may be 90 mass% or less, may be 80 mass% or less, and may be 50 mass% or less.
Specific examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, methoxyhexyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxybutyl (meth) acrylate, ethoxyhexyl (meth) acrylate, butoxymethyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxybutyl (meth) acrylate, and butoxyhexyl (meth) acrylate, and one or two or more kinds of these can be used. Among them, from the viewpoint of mechanical properties of the cured product, an alkoxyalkyl (meth) acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms is preferable, and an alkoxyalkyl (meth) acrylate having an alkoxyalkyl group having 2 to 4 carbon atoms is more preferable. The amount of the alkoxyalkyl (meth) acrylate to be used is preferably 10% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more, based on the total constituent monomers of the (meth) acrylic polymer. The upper limit is 100 mass% or less, may be 90 mass% or less, may be 80 mass% or less, and may be 50 mass% or less.
The (meth) acrylic polymer may have a reactive silyl group in the molecule. When the (meth) acrylic polymer has a reactive silyl group, the cured product tends to have good mechanical properties. The type of the reactive silyl group is not particularly limited, and examples thereof include an alkoxysilyl group, a halogenated silyl group, and a silanol group, but an alkoxysilyl group is preferable from the viewpoint of easiness of control of the reactivity. Specific examples of the alkoxysilyl group include: trialkoxysilyl groups such as trimethoxysilyl, triethoxysilyl, dimethoxyethoxysilyl and methoxydiethoxysilyl; dialkoxysilyl groups such as methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group and ethyldiethoxysilyl group; monoalkoxysilyl groups such as dimethylmethoxysilyl, dimethylethoxysilyl, diethylmethoxysilyl and diethylethoxysilyl. Among them, a dialkoxysilyl group is preferable because a cured product exhibits good elongation and excellent heat resistance stability.
When the (meth) acrylic polymer has a reactive silyl group, the average number of reactive silyl groups contained in 1-molecule polymer is preferably 0.1 or more, and more preferably 0.2 or more, from the viewpoint of the tensile strength of the cured product. The average number of reactive silyl groups may be 0.3 or more, 0.5 or more, or 1.0 or more. From the viewpoint of ensuring the elongation of the cured product, the upper limit value is preferably 5.0 pieces or less, more preferably 4.0 pieces or less, further preferably 3.0 pieces or less, further preferably 2.5 pieces or less, and further preferably 2.2 pieces or less. The range of the average value of the number of reactive silyl groups may be set by combining the above upper limit and lower limit, and is, for example, 0.1 or more and 5.0 or less, may be 0.1 or more and 3.0 or less, may be 0.1 or more and 2.2 or less, and may be 0.2 or more and 2.2 or less.
The position of the reactive silyl group contained in the (meth) acrylic polymer is not particularly limited, and may be a side chain and/or a terminal of the polymer.
The reactive silyl group can be obtained, for example, by polymerizing a monomer mixture containing a (meth) acrylic monomer and a vinyl monomer having a reactive silyl group.
Examples of the vinyl monomer having a reactive silyl group include: vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane and vinyldimethylmethoxysilane; silyl group-containing (meth) acrylates such as trimethoxysilylpropyl (meth) acrylate, triethoxysilylpropyl (meth) acrylate, dimethylmethoxysilylpropyl (meth) acrylate, and methyldimethoxysilylpropyl (meth) acrylate; silyl group-containing vinyl ethers such as trimethoxysilylpropyl vinyl ether; vinyl esters containing a silyl group such as vinyl trimethoxysilylundecanoate, and one or two or more of them may be used.
The (meth) acrylic polymer may be copolymerized with other monomers copolymerizable with the above monomers.
Examples of the other monomers include: functional group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and ethylene oxide adducts of (meth) acrylic acid;
aromatic (meth) acrylates such as phenyl (meth) acrylate, methylphenyl (meth) acrylate and benzyl (meth) acrylate;
fluorine-containing (meth) acrylates such as trifluoromethyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) acrylate;
fluorine-containing olefins such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride;
aromatic monomers such as styrene, vinyltoluene, α -methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof;
maleic anhydride; unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and monoalkyl esters and dialkyl esters thereof;
maleimide compounds such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, phenylmaleimide and cyclohexylmaleimide;
nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;
amide group-containing vinyl monomers such as acrylamide and methacrylamide;
vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate;
olefins such as ethylene and propylene;
conjugated dienes such as butadiene and isoprene;
vinyl chloride, vinylidene chloride, allyl alcohol, etc., but are not limited to these monomers. In addition, one or two or more of them may be used.
From the viewpoint of strength and weather resistance of the cured product, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 1,000 or more, more preferably 2,000 or more, further preferably 5,000 or more, further preferably 10,000 or more, and further preferably 15,000 or more, in terms of molecular weight in terms of polystyrene based on gel permeation chromatography (hereinafter also referred to as "GPC"). On the other hand, from the viewpoint of workability (low viscosity), the upper limit value of Mw is preferably 50,000 or less, more preferably 45,000 or less, further preferably 40,000 or less, further preferably 35,000 or less, and further preferably 30,000 or less. The Mw may be 20,000 or less, or 15,000 or less. The Mw range may be set in combination with the above upper and lower limits, and may be, for example, 1,000 to 50,000, 2,000 to 45,000, or 3,000 to 40,000.
The molecular weight distribution of the (meth) acrylic polymer is calculated as a value (Mw/Mn) obtained by dividing a weight average molecular weight (Mw) by a number average molecular weight (Mn). From the viewpoint of the balance between tensile physical properties and workability, Mw/Mn is preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, further preferably 2.5 or less, and further preferably 2.0 or less. The lower limit of Mw/Mn is usually 1.0.
The viscosity of the (meth) acrylic polymer is preferably 1,000 mPas or more, more preferably 2,000 mPas or more at 25 ℃. The viscosity may be 3,000 mPas or more, 5,000 mPas or more, or 10,000 mPas or more. The upper limit of the viscosity is preferably 300,000 mPas or less, more preferably 180,000 mPas or less, still more preferably 100,000 mPas or less, and still more preferably 60,000 mPas or less. When the viscosity is 1,000 mPas or more, sagging when applied to a vertical surface is suppressed, and therefore, it is preferable that the viscosity is 300,000 mPas or less to improve the handling properties of the curable composition. The viscosity range may be set in combination with the above upper limit and lower limit, and may be, for example, 1,000 to 300,000mPa · s, 2,000 to 180,000mPa · s, or 3,000 to 60,000mPa · s.
In the present invention, the (meth) acrylic polymer has a double bond in the molecule. When the (meth) acrylic polymer has an appropriate amount of double bonds, the double bonds react and the molecular weight increases moderately during exposure of the cured product to the outside, for example, and thus the weather resistance is improved. Therefore, in the present invention, the (meth) acrylic polymer can be inhibited from having a viscosity to ensure workability, and the cured product thereof can exhibit excellent weather resistance. The mechanism described above is assumed to be, and is not intended to limit the scope of the present invention.
From the viewpoint of the effect on weather resistance, the amount of double bonds contained in the (meth) acrylic polymer needs to be 0.01meq/g or more. The amount of double bonds may be 0.05meq/g or more, 0.10meq/g or more, 0.20meq/g or more, or 0.30meq/g or more. On the other hand, if the amount of double bonds is too large, the degree of crosslinking of the cured product becomes too high during exposure, and flexibility becomes insufficient, so that cracks tend to be easily generated. Therefore, the amount of double bonds is 1.0meq/g or less, preferably 0.50meq/g or less, and more preferably 0.30meq/g or less. The amount of the double bond may be set in combination with the above upper limit and lower limit, and may be, for example, 0.01meq/g or more and 1.0meq/g or less, 0.05meq/g or more and 1.0meq/g or less, or 0.10meq/g or more and 0.50meq/g or less.
The method for introducing the double bond is not particularly limited, and a method known to those skilled in the art can be used. Examples thereof include: a method of copolymerizing a monomer having a plurality of double bonds in a molecule; a method of producing a (meth) acrylic polymer having a functional group and then reacting the polymer with a compound having a functional group reactive with the functional group and a double bond.
Further, by producing the (meth) acrylic polymer under high temperature conditions, a double bond can be introduced. For example, if the polymerization temperature is 100 ℃ or higher, a cleavage reaction from the dehydrogenation reaction of the polymer chain occurs due to high-temperature polymerization, and thus a polymer having an ethylenically unsaturated bond represented by the following general formula (2) at the molecular terminal is obtained. The polymerization temperature is preferably 120 ℃ or higher, more preferably 150 ℃ or higher. The higher the polymerization temperature, the higher the concentration of double bonds in the polymer tends to be. According to the above method, a (meth) acrylic polymer having a double bond can be obtained easily and with good productivity. Further, the resin composition can be easily produced without containing a large amount of impurities such as an initiator and a chain transfer agent in controlling the molecular weight. Chain transfer agents such as mercaptans are preferably not used because they cause a decrease in weather resistance. On the other hand, the upper limit of the polymerization temperature is preferably 350 ℃ or lower in order to eliminate the risk of coloring of the polymerization liquid, lowering of the molecular weight, and the like due to the decomposition reaction. By carrying out the polymerization in the above temperature range, a copolymer having an appropriate molecular weight, a low viscosity, no coloration, and few inclusions can be efficiently produced. That is, according to this polymerization method, a very small amount of a polymerization initiator is used, and a high-purity copolymer can be obtained without using a chain transfer agent such as thiol or a polymerization solvent.
[ solution 1]
In the formula, M represents a monomer unit, and n is a natural number representing the degree of polymerization. R1Represents a monovalent organic group. Angle (c)
As R in the above general formula (2)1And is an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkyl group which may have other substituents, a phenyl group, a benzyl group, a polyalkylene glycol group, a dialkylaminoalkyl group, a trialkoxysilylalkyl group, an alkyldialkoxysilylalkyl group, or a hydrogen atom.
The (meth) acrylic polymer can be produced by a general radical polymerization. Any of solution polymerization, bulk polymerization and dispersion polymerization may be used, and living radical polymerization may also be used. The reaction process may be any of batch, semi-batch, and continuous polymerization. Among them, a high-temperature continuous polymerization method at 100 to 350 ℃ is preferable.
In general, when a crosslinkable functional group is uniformly introduced into a polymer, the curable composition containing the polymer has good properties such as curability and weather resistance of the resulting cured product. In this regard, when a stirred tank reactor is used as the reactor, a (meth) acrylic polymer having a narrow composition distribution (distribution of crosslinkable functional groups) and a narrow molecular weight distribution can be obtained, and therefore, such a reactor is preferable. Further, a process using a continuous stirring tank type reactor is more preferable in terms of narrowing the composition distribution and the molecular weight distribution.
The high-temperature continuous polymerization method may be a known method disclosed in, for example, Japanese patent application laid-open Nos. 57-502171, 59-6207, and 60-215007. Examples thereof include the following methods: after a pressurizable reactor is filled with a solvent and set to a predetermined temperature under pressure, a monomer mixture comprising each monomer and a polymerization solvent as needed is supplied to the reactor at a constant supply rate, and a polymerization liquid in an amount corresponding to the supply amount of the monomer mixture is withdrawn. Further, a polymerization initiator may be blended in the monomer mixture as necessary. The amount of the monomer mixture is preferably 0.001 to 2 parts by mass per 100 parts by mass of the monomer mixture. The pressure depends on the reaction temperature and the boiling points of the monomer mixture and the solvent used, and may be any pressure that does not affect the reaction but can maintain the reaction temperature. The residence time of the monomer mixture is preferably 1 to 60 minutes. If the residence time is less than 1 minute, there is a risk that the monomer is insufficiently reacted, and if the unreacted monomer exceeds 60 minutes, the productivity may be deteriorated. The preferable residence time is 2 to 40 minutes.
As an example of the polymerization initiator used for obtaining the (meth) acrylic polymer, any initiator may be used as long as it generates a radical at a predetermined reaction temperature. Specifically, there may be mentioned: organic peroxides such as di-t-butyl peroxide, di-t-hexyl peroxide, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, cumene hydroperoxide, t-butyl hydroperoxide, etc.; azo compounds such as 2,2 '-azobis (isobutyronitrile), 2' -azobis (2-methylbutyronitrile), azobiscyclohexanecarbonitrile, azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (2-amidinopropane) dihydrochloride, and 4, 4' -azobis (4-cyanopentanoic acid). One of them may be used alone, or two or more thereof may be used in combination. When an initiator having high dehydrogenation ability is used as a polymerization initiator, the double bond concentration of the resulting polymer tends to be high. For example, when an organic peroxide is used, a polymer having a higher double bond concentration tends to be obtained as compared with an azo compound.
The amount of the polymerization initiator to be used may be appropriately adjusted depending on the kind of the polymerization initiator and the monomer, the desired molecular weight, the polymerization conditions, and the like, and is generally 0.001 to 10 parts by mass based on 100 parts by mass of the monomer to be used. In the case of obtaining polymers of the same molecular weight, there is a tendency that: the smaller the amount of the polymerization initiator used, the higher the double bond concentration in the resulting polymer.
When an organic solvent is used for producing the (meth) acrylic polymer, the organic hydrocarbon compound is preferable, and examples thereof include: cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; one or more kinds of alcohols such as methanol, ethanol, and isopropyl alcohol can be used. In a solvent in which the (meth) acrylate copolymer is not sufficiently dissolved, scale (scale) tends to grow on the wall of the reactor, and a problem in production tends to occur in a cleaning step or the like. In addition, for example, when an organic solvent having a high chain transfer ability such as isopropyl alcohol is used, the double bond concentration in the obtained polymer tends to be low.
The amount of the solvent used is preferably 80 parts by mass or less based on 100 parts by mass of the total vinyl monomers. By setting the amount to 80 parts by mass or less, a high conversion rate can be obtained in a short time. More preferably 1 to 50 parts by mass. In addition, a dehydrating agent such as trimethyl orthoacetate or trimethyl orthoformate may be added.
A known chain transfer agent can be used for producing the (meth) acrylic polymer. When a chain transfer agent is used, the double bond concentration in the resulting polymer tends to be low. In addition, the double bond concentration is generally reduced by increasing the amount of the chain transfer agent used.
The reaction solution withdrawn from the reactor may be directly subjected to the next step, or may be subjected to distillation such as distillation to remove volatile components such as unreacted monomers, solvents, and low-molecular-weight oligomers, thereby separating the polymer. A part of volatile components such as unreacted monomers, solvents, and low-molecular-weight oligomers distilled off from the reaction solution may be returned to the raw material tank or directly returned to the reactor to be reused for the polymerization reaction.
Thus, a method of recycling the unreacted monomer and the solvent is preferable from the viewpoint of economy. In the case of recycling, it is necessary to determine the mixing ratio of the newly supplied monomer mixture in such a manner that the desired monomer ratio and the desired amount of solvent are maintained in the reactor.
The amount of double bonds introduced in the polymer can be reduced by adding a free-radical generator and carrying out a post-treatment under heating. The amount of the radical generator added is about 0.1 to 10 parts by mass per 100 parts by mass of the polymer, and the effect of reducing the double bond concentration increases as the amount of the free radical generator added increases.
The heating temperature during the heat treatment is about 50 to 130 ℃, but the effect of reducing the double bond concentration is greater as the temperature is lower. The heating temperature is preferably 50 to 110 ℃, and more preferably 50 to 100 ℃.
The heat treatment time is not particularly limited, and is preferably set so that the residual radical generating amount is less than 1% by mass relative to the polymer. If it is a person skilled in the art, the residual radicals can be calculated from the activation energy of the radical generator used, the frequency factor and the reaction temperature.
The double bond concentration can also be reduced by hydrogenating the (meth) acrylic polymer as a post-treatment. The hydrogenation may be carried out by a conventionally known method.
That is, after adding a homogeneous catalyst or an inhomogeneous catalyst to a polymer reaction solution, the system is heated under a hydrogen atmosphere at a pressure of about normal pressure to 10MPa and a temperature of about 20 to 180 ℃ to react about 2 to 20. Specific examples of the homogeneous catalyst include: rhodium complexes such as chlorotris (triphenylphosphine) rhodium; ruthenium complexes such as dichlorotris (triphenylphosphine) ruthenium and chlorohydrogenocarbonyltris (triphenylphosphine) ruthenium; platinum complexes such as dichlorobis (triphenylphosphine) platinum; iridium complexes such as carbonylbis (triphenylphosphine) iridium, and the like. On the other hand, examples of the heterogeneous catalyst include solid catalysts in which a transition metal such as nickel, rhodium, ruthenium, palladium, or platinum is supported on carbon, silica, alumina, fibers, or an organic gel. The heterogeneous catalyst is preferable in that the catalyst can be easily removed by filtration or the like, and the catalyst has stable quality and can be reused at high cost. The amount of the catalyst to be added is about 10to 1,000ppm based on the vinyl polymer in the case of a homogeneous catalyst. In the case of the heterogeneous catalyst, the amount is about 1,000 to 10,000 ppm.
< curable composition >
As described above, the curable composition of the present invention contains the components (a) and (B) as essential components. The ratio ((A)/(B)) of the component (A) to the component (B) is preferably 10to 90/90 to 10, more preferably 20 to 60/80 to 40, in terms of a mass ratio, from the viewpoint of improving the weather resistance and mechanical properties of the resulting cured product.
The curable composition of the present invention may contain components other than the component (a) and the component (B) as long as the effects exerted by the present invention are not impaired. The component includes a filler, a plasticizer, an antiaging agent, a curing accelerator, a releasing agent, an adhesion imparting agent and the like.
Examples of the filler include light calcium carbonate having an average particle size of about 0.02 to 2.0 μm, heavy calcium carbonate having an average particle size of about 1.0 to 5.0 μm, titanium oxide, carbon black, synthetic silicic acid, talc, zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass microspheres, silica microspheres, and polymethyl methacrylate microspheres. These fillers can improve the mechanical properties of the cured product and can improve the strength and elongation.
Among them, light calcium carbonate, heavy calcium carbonate and titanium oxide having a high effect of improving physical properties are preferable, and a mixture of light calcium carbonate and heavy calcium carbonate is more preferable. The amount of the filler added is preferably 20 to 300 parts by mass, more preferably 50 to 200 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). When the mixture of the light calcium carbonate and the heavy calcium carbonate is prepared as described above, the mass ratio of the light calcium carbonate/the heavy calcium carbonate is preferably in the range of 90/10 to 50/50.
Examples of the plasticizer include a liquid urethane resin, a polyester plasticizer obtained from a dicarboxylic acid and a diol, an etherified substance or an esterified substance of a polyalkylene glycol such as polyethylene glycol or polypropylene glycol, a polyether plasticizer such as a saccharide polyether obtained by addition polymerization of an alkylene oxide such as ethylene oxide or propylene oxide to a saccharide polyol such as sucrose and the like and then etherification or esterification of the resulting product, a polystyrene plasticizer such as poly- α -methylstyrene, and a poly (meth) acrylate having no crosslinkable functional group, among which a poly (meth) acrylate having no crosslinkable functional group is preferable from the viewpoint of durability such as weather resistance of a cured product, and among them, a poly (meth) acrylate having an Mw in the range of 1,000 to 7,000 and a glass transition temperature of-30 ℃ or lower and having no crosslinkable functional group is more preferable.
When the total amount of the components (a) and (B) is 100 parts by mass, the amount of the plasticizer used in the curable composition is preferably in the range of 0to 100 parts by mass, may be in the range of 0to 80 parts by mass, and may be in the range of 0to 50 parts by mass.
As the age resister, there can be used: ultraviolet absorbers such as benzophenone-based compounds, benzotriazole-based compounds and oxanilide-based compounds; light stabilizers such as hindered amine compounds; antioxidants such as hindered phenol type antioxidants; a heat stabilizer; or an anti-aging agent as a mixture thereof.
Examples of the ultraviolet absorber include those sold under the trade names "Tinuvin 571", "Tinuvin 1130" and "Tinuvin 327" manufactured by BASF corporation. Examples of the light stabilizer include: trade names "Tinuvin 292", "Tinuvin 144", "Tinuvin 123" manufactured by BASF corporation; trade name "Sanol 770" manufactured by Sanko Co. Examples of the heat stabilizer include those sold under the trade names "Irganox 1135", "Irganox 1520", and "Irganox 1330" manufactured by BASF corporation. The product "Tinuvin B75" manufactured by BASF corporation, which is a mixture of an ultraviolet absorber, a light stabilizer and a heat stabilizer, may also be used.
As the curing accelerator, known compounds such as tin-based catalysts, titanium-based catalysts, tertiary amines, and the like can be used.
Examples of the tin-based catalyst include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dipropionate, and dioctyltin dilaurate. Specifically, the trade names "NEOSTANN U-28", "NEOSTANN U-100", "NEOSTANN U-200", "NEOSTANN U-220H", "NEOSTANN U-303", and "SCAT-24" manufactured by Nissanghua corporation may be exemplified.
Examples of the titanium-based catalyst include tetraisopropyl titanate, tetra-n-butyl titanate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetylacetonate, titanium dibutoxybisacetoacetonate, titanium diisopropoxybisacetoacetonate, titanium octyleneglycolate (titanium octylene glycol), and titanium lactate.
Examples of the tertiary amines include triethylamine, tributylamine, triethylenediamine, hexamethylenetetramine, 1, 8-diazabicyclo [ 5,4,0 ] undec-7 (DBU), Diazabicyclononene (DBN), N-methylmorpholine and N-ethylmorpholine.
The amount of the curing accelerator used is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 2 parts by mass, based on 100 parts by mass of the total of the components (A) and (B).
Examples of the release agent include: the acrylic oligomer is available under the trade names "ARONIXM 8030", "M8100", "M309", manufactured by east asia synthesis company, or a mixture thereof with a photopolymerization initiator; saturated fatty acid oils such as tung oil and linseed oil; trade name "R15 HT" manufactured by gloss oil corporation; trade name "PBB 3000" manufactured by Nippon Caoda corporation; a trade name "Gohselac 500B" manufactured by Nippon synthetic chemical Co., Ltd.
Examples of the adhesion-imparting agent include aminosilanes such as "KBM 602", "KBM 603", "KBE 602", "KBE 603", "KBM 902" and "KBM 903" manufactured by shinning silicone corporation.
In addition, a dehydrating agent such as methyl orthoformate, methyl orthoacetate, or vinyl silane, an organic solvent, or the like may be added.
The curable composition of the present invention may be prepared as a one-pack type composition in which all the components are mixed in advance, and the composition is stored in a sealed state and cured by absorbing moisture in the air after application. In addition, a two-component type in which a curing catalyst, a filler, a plasticizer, water and other components separately added as a curing agent are blended in advance and the blended materials and the polymerization composition are mixed before use may be adjusted. More preferably, the one-pack type is easy to handle and has less mixing errors during coating.
The curable composition of the present invention is cured at room temperature to obtain a cured product having excellent weather resistance and mechanical properties. Therefore, it can be suitably used as a sealing material composition requiring high durability. The sealant composition of the present invention contains the curable composition, and if necessary, other components are blended according to a conventional method.
The curable composition can be suitably used for adhesives. In the field of adhesives for building materials, it is required to ensure high weather resistance and high durability for 10 years or longer, and the adhesive composition of the present invention can satisfy this requirement. In particular, in tile bonding of an outer wall, it is required to maintain appearance and adhesiveness for a long period of time, and the requirements can be met. The adhesive composition of the present invention contains the above curable composition, and if necessary, other components are blended according to a conventional method.
The adhesive composition of the present invention may be an adhesive composition to which an epoxy resin is added. Examples of the epoxy resin include epichlorohydrin-bisphenol a type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, phenol novolac type epoxy resins, hydrogenated bisphenol a type epoxy resins, glycidyl ether type epoxy resins of bisphenol a propylene oxide adducts, glycidyl ether p-hydroxybenzoate type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane modified epoxy resins, various alicyclic epoxy resins, N-diglycidylaniline, N-diglycidylolotylamine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, hydantoin type epoxy resins, and the like. Further, flame-retardant epoxy resins such as glycidyl ether of tetrabrominated bisphenol a, glycidyl ethers of polyhydric alcohols such as glycerin, and epoxides of unsaturated polymers such as petroleum resin can be exemplified, but the epoxy resins are not limited to these epoxy resins, and commonly used epoxy resins can be used. Among these epoxy resins, epoxy resins having at least two epoxy groups in the molecule are preferred, in particular, because they have high reactivity during curing and the cured product is likely to form a three-dimensional network. Among them, bisphenol a type epoxy resins, phenol novolac type epoxy resins, and the like are more preferable.
The epoxy resin is preferably used in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total polymer (total mass of the oxyalkylene polymer (a) having a reactive silyl group and the (meth) acrylic polymer (B)) of the present invention. When the amount of the epoxy resin exceeds 100 parts by mass, the weather resistance may be lowered.
When an epoxy resin is used, a curing agent for the epoxy resin is preferably used in combination. Examples of the curing agent for epoxy resin include: primary amines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, diaminodicyclohexylmethane, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; (CH)3)2N(CH2)nN(CH3)2(wherein n is an integer of 1 to 10) or a linear diamine (CH)3)2-N(CH2)n-CH3A linear tertiary amine represented by the formula (wherein N is an integer of 0to 10), tetramethylguanidine, and N { (CH)2)nCH3}3(in the formula, n1-10 integer), triethanolamine, piperidine, N' -dimethylpiperazine, triethylenediamine, pyridine, picoline, diazabicycloundecene, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol, Lamiron C-260 manufactured by BASF, Araldit HY-964 manufactured by CIBA, and Rohm&Secondary or tertiary amines such as menthane diamine (menthane diamine) manufactured by Haas corporation; ketimines such as 1, 2-ethylenebis (isoamylene amine), 1, 2-hexylenebis (isoamylene amine), 1, 2-propylenebis (isoamylene amine), p' -biphenylylenebis (isoamylene amine), 1, 2-ethylenebis (isopropylene amine), 1, 3-propylenebis (isopropylene amine), and p-phenylenebis (isoamylene amine); anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride; various polyamide resins; dicyandiamide and derivatives thereof; and various imidazoles and the like. The amount of the curing agent to be used is preferably 5 to 100 parts by mass per 100 parts by mass of the epoxy resin.
The adhesive composition provided in the present invention has a reactive silyl group, and therefore, when the above epoxy resin is used, the strength of the cured adhesive composition can be improved by adding a compound having a group capable of reacting with both the reactive silyl group and the epoxy group, and specific examples of the compound having a group capable of reacting with both the reactive silyl group and the epoxy group include N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, and γ -aminopropyltriethoxysilane.
The adhesive composition provided by the invention contains the curable composition. Therefore, the effect of the curable composition can be exhibited in the application of the adhesive, and the adhesion to the top-coat paint can be improved. In particular, the effect of the curable composition can be exhibited to a high degree in an exterior tile adhesive.
Examples
The present invention will be specifically described below based on examples. The present invention is not limited to these examples. In the following, unless otherwise specified, "parts" and "%" mean parts by mass and% by mass.
The methods for analyzing the polymers obtained in the production examples, examples and comparative examples and the method for evaluating the cured product obtained from the curable composition are described below.
< method for quantifying double bond amount >
By passing1The H-NMR measurement is based on the ratio of the integrated value of the signal from hydrogen bonded to a double bond in the vicinity of 5.5ppm to the integrated value of the signal from hydrogen bonded to a carbon adjacent to an ester group in the range of 3.0 to 4.5ppm, the composition of the polymer, and the double bond concentration per unit mass of the polymer.
< determination of molecular weight >
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were obtained in terms of polystyrene using a gel permeation chromatography apparatus (type name "HLC-8320", manufactured by Tosoh corporation) under the following conditions. From the obtained values, the molecular weight distribution (Mw/Mn) was calculated.
○ measurement conditions
A chromatographic column: TSKgel SuperMultiporeHZ-Mx 4 root, made by Tosoh
Column temperature: 40 deg.C
Eluent: tetrahydrofuran (THF)
A detector: RI (Ri)
<theaverage number of reactive silyl groups contained in a (meth) acrylic polymer
The number (average number) f (si) of alkoxysilyl groups as reactive silyl groups was calculated from the mass parts of the monomer having reactive silyl groups, assuming that all the constituent monomers were 100 mass parts, using the following formula.
(si) ((silyl monomer mass part/(silyl monomer molecular weight × 100/Mn) }
Viscosity of (meth) acrylic polymer
The E-type viscosity was measured under the following conditions using a TVE-20H-type viscometer (salt water/plate system, manufactured by Toyobo industries Co., Ltd.).
○ measurement conditions
The shape of the cone is as follows: angle 1 degree 34', radius 24mm (less than 10000 mPa. s)
Angle 3 °, radius 7.7mm (10000mPa s or more)
Temperature: 25 ℃ plus or minus 0.5 DEG C
< weather resistance test (1) >
Each of the curable compositions was applied to a Teflon (registered trademark) sheet in a thickness of 2mm, and cured at 23 ℃ and 50% RH for 1 week to prepare a cured sheet. The resulting cured product was put into a metal tube weather resisting machine (DAIPLA METAL WEATHER KU-R5NCI-A, manufactured by DAIPLA WINTES Co.) to carry out a weather resistance acceleration test. The conditions were 63 ℃ irradiation, 70% RH irradiation and 80mW/cm illuminance2The test was carried out with 2 hour 1-time and 2 minute shower (shower) each. The time at which the appearance started to develop abnormalities such as cracking, bleeding, etc. was recorded.
< weather resistance test (2) >
Each of the curable compositions was applied to a Teflon (registered trademark) sheet in a thickness of 2mm, and cured at 23 ℃ and 50% RH for 1 week to prepare a cured sheet. The resulting cured product was put into a weather resistant metal lamp (product of DAIPLA WINTES, DAIPLA METAL WEATHER KU-R5 NCI-A) and subjected to accelerated weather resistance test. The conditions were 63 ℃ irradiation, 70% RH irradiation and 80mW/cm illuminance2The test was carried out 2 hours and 1 time for 1000 hours and the test was carried out by showering for 2 minutes each time, the surface state was visually confirmed (presence or absence of cracks) after 1000 hours, the color difference (△ E) was obtained by a colorimeter (Spectroscopy colorimeter SE-2000 manufactured by Nippon Denshoku Co., Ltd.), and the weather resistance was evaluated from the degree of color fading, and the color difference (△ E) was determined from the luminance (L) measured by the spectrocolorimeter＊) Chromaticity in the red-green direction (a)＊) And chromaticity in the yellow-blue direction (b)＊) The value of (b) is obtained by substituting the following equation.
[ number 1]
< tensile test >
Each of the curable compositions was applied to a Teflon (registered trademark) sheet in a thickness of 2mm, and cured at 23 ℃ and 50% RH for 1 week to prepare a cured sheet. A tensile test dumbbell (JIS K62513 type) was prepared from the resulting cured product, and the elongation at break and the strength at break were measured at a tensile rate of 200 mm/min using a tensile tester (automatic plotter AGS-J, Shimadzu corporation).
< adhesion Strength test >
The test was carried out using a mortar board and an exterior mosaic tile according to JIS a5557(2006) method for testing the adhesion strength of an organic adhesive for exterior tile adhesion.
An adhesive was applied to a mortar board (TP technical standard, 10X 50mm) to a thickness of about 5mm, and after the adhesive was combed with a comb trowel, a commercially available exterior mosaic tile (45X 45mm) suitable for the specification of JIS A5209 was bonded. After curing the plate at 23 ℃ and 50% RH for 4 weeks, a special jig was attached to the tile side and the mortar side, and a tensile test was performed at 23 ℃ and a tensile rate of 3 mm/min using a tensile tester (AGS-J, Shimadzu corporation), thereby measuring the adhesive strength.
Component (A): production of oxyalkylene Polymer
Synthesis example 1 (production of oxyalkylene Polymer A-1)
A1000 mL-capacity pressure-type stirred tank reactor equipped with an oil jacket (oil jack) was charged with zinc hexacyanocobaltate glyme complex (0.05g), polypropylene glycol (Mn: 2000, 50g), and propylene glycol (520g), and the mixture was heated to 120 ℃ to react until the pressure change disappeared. Subsequently, the mixture was heated at 120 ℃ for 1 hour under vacuum to distill off volatile components. Thereafter, 28% methanol solution (15.2g) of sodium methoxide was added thereto, and the mixture was decompressed at 100 ℃ for 1 hour, and methanol was distilled off. Subsequently, allyl chloride (6.3g) was added thereto, and the mixture was heated at 100 ℃ for 2 hours. Thereafter, the reaction solution was washed with water (300ml) 2 times to remove salts. After dehydration by heating at 100 ℃ for 2 hours under vacuum, chloroplatinic acid hexahydrate (0.02g) and methyldimethoxysilane (8.3g) were added and reacted for 4 hours to obtain both terminal silylated products of polypropylene glycol. The results of GPC measurement were Mn: 19000. mw: 20700.
synthesis example 2 (production of oxyalkylene Polymer A-2)
A1000 mL-capacity pressurized stirred tank reactor equipped with an oil jacket was charged with zinc hexacyanocobaltate glyme complex (0.05g), polypropylene glycol (Mn: 2000, 50g), and propylene glycol (500g), and heated to 120 ℃ to react until the pressure change disappeared. Subsequently, the mixture was heated at 120 ℃ for 1 hour under vacuum to distill off volatile components. Thereafter, 28% methanol solution (10.1g) of sodium methoxide was added thereto, and the mixture was decompressed at 100 ℃ for 1 hour, and methanol was distilled off. Subsequently, allyl chloride (4.2g) was added thereto, and the mixture was heated at 100 ℃ for 2 hours. Thereafter, the reaction solution was washed with water (300ml) 2 times to remove salts. After dehydration by heating at 100 ℃ for 2 hours under vacuum, chloroplatinic acid hexahydrate (0.02g) and methyldimethoxysilane (5.6g) were added and reacted for 4 hours to obtain both terminal silylated products of polypropylene glycol. The results of GPC measurement were Mn: 25800. mw: 29000.
component (B): production of (meth) acrylic acid-based Polymer
Synthesis example 3 (production of (meth) acrylic Polymer B-1)
○ polymerization step
The temperature of a pressurized stirred tank reactor having a capacity of 1000mL and equipped with an oil jacket (oil jack) was maintained at 265 ℃. Then, while the pressure in the reactor was kept constant, a mixture of 3.3 parts of 3-methacryloxypropylmethyldimethoxysilane (trade name "Z6033", hereinafter referred to as "DMS", manufactured by Toray Dow Corning Co., Ltd.), 10 parts of tetradecyl acrylate (hereinafter referred to as "TDA") and 66.7 parts of 2-ethylhexyl acrylate (hereinafter referred to as "HA") as monomers, a monomer mixture comprising 20 parts of methyl methacrylate (hereinafter referred to as "MMA"), 20 parts of methyl ethyl ketone (hereinafter referred to as "MEK") and 0.2 parts of di-t-butyl peroxide (Japanese oil preparation, trade name "perbutylD", hereinafter referred to as "DTBP") as a polymerization initiator was continuously supplied from a stock tank to a reactor at a constant supply rate (48 g/min, residence time: 12 min), and a reaction liquid in an amount corresponding to the supply amount of the monomer mixture was continuously withdrawn from an outlet. Immediately after the start of the reaction, the reaction temperature was temporarily lowered, and then a temperature rise due to the heat of polymerization was observed, and the reaction temperature was maintained at 264 to 266 ℃ by controlling the temperature of the oil jacket.
The reaction was continued for 25 minutes after the start of the supply of the monomer mixture and the temperature was stabilized, and as a result, 1.2kg of the monomer mixture was supplied and 1.2kg of the reaction mixture was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator, and volatile components such as unreacted monomers were separated to obtain a concentrated solution.
○ post-treatment procedure
Then, 100 parts of the concentrated solution obtained in the polymerization step was added to the flask after the replacement with nitrogen, and the mixture was heated and stirred until the liquid temperature reached 90 ℃ while nitrogen gas was passed therethrough. When the temperature reached 90 ℃, 0.5 part of tert-butyl 2-ethylhexanoate peroxide (product name "PERHEXYL O" available from Nichiku corporation) as a radical generator was added thereto and stirred for 16 hours while maintaining the temperature at 90 ℃ to obtain (meth) acrylic polymer B-1. The properties of the polymer are shown in Table 1.
Synthesis examples 4 to 8 (production of (meth) acrylic polymers B-2 to B-6)
(meth) acrylic polymers B-2 to B-6 were obtained in the same manner as in Synthesis example 3, except that the amount of the radical generator (PERHEXYL O) added and the treatment conditions in the post-treatment step were changed as shown in Table 1 using the concentrated solution obtained after the polymerization step in Synthesis example 3. The properties of each polymer are shown in table 1.
Synthesis examples 9 to 19 (production of (meth) acrylic polymers B-7 to B-17)
(meth) acrylic polymers B-7 to B-17 were obtained in the same manner as in Synthesis example 3, except that the raw materials and reactor internal temperature used in the polymerization step, and the amount of the radical generator (PERHEXYL O) added and the treatment conditions used in the post-treatment step were changed as shown in tables 1 to 3. In addition, in Synthesis example 16 ((meth) acrylic polymer B-14), post-treatment of the concentrated solution obtained after the polymerization step was not performed. The properties of each polymer are shown in tables 1 to 3.
Synthesis example 20 (production of (meth) acrylic Polymer B-18)
Butyl acetate (100 parts) was added to a flask equipped with a reflux condenser, and the internal temperature was maintained at 122 ℃ in an oil bath, followed by stirring. A mixture of DMS (3 parts), BA (57 parts), HA (20 parts), TDA (10 parts), MMA (10 parts) and ABN-E (4 parts) was added dropwise over 4 hours from a dropping funnel. The mixture was further stirred for 2 hours while maintaining the temperature at 122 ℃. Thereafter, the reaction mixture was desolventized at 90 ℃ and 10mmHg by an evaporator to separate volatile components, thereby obtaining a (meth) acrylic polymer B-18. The properties of the polymer are shown in Table 3.
[ Table 1]
[ Table 2]
[ Table 3]
The details of the compounds shown in tables 1 to 3 are as follows.
BA: acrylic acid butyl ester
HA: 2-ethylhexyl acrylate
TDA: acrylic acid tridecyl ester
MMA: methacrylic acid methyl ester
DMS: 3-methacryloxypropylmethyldimethoxysilane
TMS: 3-methacryloxypropyltrimethoxysilane
IPA: isopropanol (I-propanol)
MOA: acetic acid methyl ester
MEK: methyl ethyl ketone
BAC: acetic acid butyl ester
DTBP: di-tert-butyl peroxide
DTHP: di-tert-hexyl peroxide
ABN-E: 2, 2' -azobis (2-methylbutyronitrile)
PHO: tert-butyl peroxy-2-ethylhexanoate (product name "PERHEXYL O" manufactured by Nichiku Co., Ltd.)
AIBN: 2, 2' -azobis (isobutyronitrile)
Preparation and evaluation of curable composition
Examples 1 to 26 and comparative examples 1 to 3
The oxyalkylene polymer (component A) and the (meth) acrylic polymer (component B) obtained in the above synthesis examples and commercially available raw materials were mixed at the ratios shown in tables 4 to 6, and mixed for 1 hour at a temperature of 60 ℃ and a pressure of 10Torr by using a planetary mixer, thereby obtaining a curable composition. The weather resistance test and the tensile test were performed on the cured products obtained from each composition, and the results are shown in tables 4 to 6.
[ Table 4]
[ Table 5]
[ Table 6]
The details of the compounds shown in tables 4 to 6 are as follows.
PPG: exenol 2020 (manufactured by Asahi glass Co., Ltd.)
CCR: light calcium carbonate (trade name "Bai Yan Hua CCR" manufactured by Bai Shi Ca Co., Ltd.)
Super SS: ground calcium carbonate (Super SS, product name of pill tail calcium Co.)
R820: titanium oxide (manufactured by stone original product Co., Ltd.)
Tinuvin B75: anti-aging agent (manufactured by BASFJAPAN Co., Ltd.)
U220H: dibutyltin bisacetoacetonate (manufactured by Ridong Kasei Co., Ltd.)
Nacem Titan: titanium dibutoxybisacetonate (trade name "NacemTian" manufactured by Nippon chemical industries Co., Ltd.)
DBU: 1, 8-diazabicyclo [ 5,4,0 ] undec-7-ene
SH 6020: 3- (2-aminoethyl) aminopropyltrimethoxysilane (manufactured by Dongli-Dow Corning Co., Ltd.)
SZ 6030: vinyl trimethoxy silane (Dongli-manufactured by Dow Corning Co., Ltd.)
Examples 1 to 26 are evaluations of the curable composition of the present invention, and show good weather resistance and good mechanical properties.
In the weather resistance test and the tensile test, the workability (ease of application) was good when each curable composition was applied to a teflon (registered trademark) sheet in a thickness of 2 mm. Therefore, the curable composition provided by the present invention is excellent in weather resistance, mechanical properties, and workability, and can be suitably used as a sealing material composition.
On the other hand, comparative examples 1 to 3 are experimental examples of the curable composition in which the double bond concentration of the (meth) acrylic polymer is outside the range specified in the present invention. The (meth) acrylic polymer having a high double bond concentration (comparative example 1) and the (meth) acrylic polymer having a low double bond concentration (comparative examples 2 and 3) were not sufficient in weather resistance of the resulting cured product.
Preparation and evaluation of adhesive composition
Examples 27 to 30 and comparative examples 4 to 5
Excestar S-3430 (manufactured by Asahi glass Co., Ltd.) used as the oxyalkylene polymer (component A), the (meth) acrylic polymer (component B) obtained in the above synthesis example, and a commercially available raw material were mixed at a ratio shown in Table 7, and mixed for 1 hour at a temperature of 60 ℃ and a pressure of 10Torr using a planetary mixer to obtain an adhesive composition. The weather resistance test (2) and the adhesive strength test were performed on each composition, and the results are shown in table 7.
[ Table 7]
Details of the compounds shown in table 7 are shown below.
PPG: exenol 2020 (manufactured by Asahi glass Co., Ltd.)
jER 828: epoxy resin (manufactured by Mitsubishi chemical Co., Ltd.)
jER curing H30: epoxy hardener (manufactured by Mitsubishi chemical corporation)
CCR: light calcium carbonate (trade name "Bai Yan Hua CCR" manufactured by Bai Shi Ca Co., Ltd.)
Super SS: ground calcium carbonate (Super SS, product name of pill tail calcium Co.)
# 45: carbon black (manufactured by Mitsubishi chemical Co., Ltd.)
R820: titanium oxide (manufactured by stone original product Co., Ltd.)
Tinuvin B75: anti-aging agent (manufactured by BASFJAPAN Co., Ltd.)
U220H: dibutyltin bisacetoacetonate (manufactured by Ridong Kasei Co., Ltd.)
S340: ketimine silane coupling agent Sila-Ace (JNC Co., Ltd.)
SZ 6030: vinyl trimethoxy silane (Dongli-manufactured by Dow Corning Co., Ltd.)
The results of the adhesion strength test show that: in examples 27 to 30 and comparative examples 4 to 5, both the strength and the broken state were not problematic, and the level was such that the adhesive could be used as an adhesive. In the weather resistance test (2), the workability (ease of application) was good when each curable composition was applied to a teflon (registered trademark) sheet in a thickness of 2mm in each of examples and comparative examples. In the adhesion strength test, workability in each step was good in a series of bonding operations such as applying an adhesive to a mortar board to a thickness of about 5mm, scraping with a comb trowel, and bonding exterior mosaic tiles.
On the other hand, as a result of the weather resistance test (2), it was found that in examples 27 to 30 in which the (meth) acrylic polymer (B component) had an appropriate amount of double bonds in the molecule, there was no change in the surface state, and the color difference (△ E) was small, whereas in comparative example 4 in which the (meth) acrylic polymer (B component) containing an excessive amount of double bonds was used, cracks were generated on the surface, and the weather resistance was insufficient.
From the results of the adhesive strength test and the weather resistance test (2), it is understood that the adhesive composition provided in the present invention is excellent in adhesive strength, weather resistance and workability.
Industrial applicability
The curable composition of the present invention is cured at room temperature by moisture in the atmosphere or the like, and a cured product having excellent weather resistance and mechanical properties is obtained. Further, since the resin composition has an appropriate viscosity, the workability is also excellent. Therefore, the curable composition is suitable for adhesives such as sealing materials and exterior tile adhesives.
Claims (11)
1. A curable composition comprising an oxyalkylene polymer (A) having a reactive silyl group and a (meth) acrylic polymer (B), wherein,
the (meth) acrylic polymer (B) has a double bond of 0.01meq/g or more and 1.0meq/g or less in the molecule.
2. The curable composition according to claim 1,
the weight average molecular weight of the (meth) acrylic polymer (B) is 1,000 to 50,000.
3. The curable composition according to claim 1 or 2,
the (meth) acrylic polymer (B) has a viscosity of 1,000 mPas or more and 300,000 mPas or less at 25 ℃.
4. The curable composition according to any one of claims 1 to 3,
the (meth) acrylic polymer (B) has 0.1 to 2.2 reactive silyl groups in the molecule.
5. The curable composition according to claim 4,
the (meth) acrylic polymer (B) has a dialkoxysilyl group as a reactive silyl group.
6. The curable composition according to any one of claims 1 to 5,
the (meth) acrylic polymer (B) contains an alkyl (meth) acrylate having an alkyl group having 10 or more carbon atoms in an amount of 5% by mass or more based on the total monomer units constituting the (meth) acrylic polymer.
7. The curable composition according to any one of claims 1 to 6,
the oxyalkylene polymer (A) has a number average molecular weight of 22,000 or more.
8. The curable composition according to any one of claims 1 to 7,
the amount of the oxyalkylene polymer (A) and the (meth) acrylic polymer (B) used is 10to 90/90 to 10 in terms of mass ratio.
9. The curable composition according to any one of claims 1 to 8,
contains at least one compound selected from tin catalysts, titanium catalysts and tertiary amines as a curing accelerator.
10. A sealant composition characterized in that,
a curable composition comprising the curable composition according to any one of claims 1 to 9.
11. An adhesive composition characterized by comprising, in a specific ratio,
a curable composition comprising the curable composition according to any one of claims 1 to 9.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017179762 | 2017-09-20 | ||
| JP2017-179762 | 2017-09-20 | ||
| JP2018-026848 | 2018-02-19 | ||
| JP2018026848A JP6376300B1 (en) | 2018-02-19 | 2018-02-19 | Curable composition and adhesive composition |
| JP2018-027476 | 2018-02-20 | ||
| JP2018027476A JP6376302B1 (en) | 2017-09-20 | 2018-02-20 | Curable composition and sealing material composition |
| PCT/JP2018/029551 WO2019058794A1 (en) | 2017-09-20 | 2018-08-07 | Curable composition, sealing material composition, and adhesive composition |
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| Publication Number | Publication Date |
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| CN111094442A true CN111094442A (en) | 2020-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201880060565.5A Pending CN111094442A (en) | 2017-09-20 | 2018-08-07 | Curable composition, sealing material composition, and adhesive composition |
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| Country | Link |
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| CN (1) | CN111094442A (en) |
| PH (1) | PH12020550086A1 (en) |
| WO (1) | WO2019058794A1 (en) |
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| JP2007023293A (en) * | 2006-09-07 | 2007-02-01 | Auto Kagaku Kogyo Kk | Curable composition and sealant composition |
| JP6376301B1 (en) * | 2018-02-19 | 2018-08-22 | 東亞合成株式会社 | Curable composition and adhesive composition |
| JP6376303B1 (en) * | 2017-09-20 | 2018-08-22 | 東亞合成株式会社 | Curable composition and sealing material composition |
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- 2018-08-07 CN CN201880060565.5A patent/CN111094442A/en active Pending
- 2018-08-07 WO PCT/JP2018/029551 patent/WO2019058794A1/en active Application Filing
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| TW593592B (en) * | 2001-07-26 | 2004-06-21 | Ucb Sa | Polymeric compositions |
| CN1668698A (en) * | 2002-07-25 | 2005-09-14 | 株式会社钟化 | Curable composition and sealing method for siding boards |
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| WO2019058794A1 (en) | 2019-03-28 |
| PH12020550086A1 (en) | 2020-10-12 |
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