WO2010044367A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2010044367A1
WO2010044367A1 PCT/JP2009/067548 JP2009067548W WO2010044367A1 WO 2010044367 A1 WO2010044367 A1 WO 2010044367A1 JP 2009067548 W JP2009067548 W JP 2009067548W WO 2010044367 A1 WO2010044367 A1 WO 2010044367A1
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parts
meth
curable composition
group
vinyl
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PCT/JP2009/067548
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Japanese (ja)
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耕太郎 米田
道弘 河合
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東亞合成株式会社
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Priority to JP2010533881A priority Critical patent/JP5370369B2/ja
Publication of WO2010044367A1 publication Critical patent/WO2010044367A1/fr

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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
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a curable composition, and more particularly relates to a curable composition that cures at room temperature with moisture such as in the air, has high elongation at break, and exhibits excellent heat resistance and weather resistance. is there.
  • a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group has been well known, Widely used in adhesives, sealants, paints, etc. for electrical and electronic fields and automotive applications. In these applications, since a balance between good workability, high elongation at break, weather resistance, and heat resistance is required, various studies have been made so far.
  • a vinyl polymer having a hydrolyzable silyl group (particularly a (meth) acrylic polymer) has characteristics such as high weather resistance, heat resistance and transparency as compared with the oxyalkylene polymer.
  • Patent Document 1 discloses a method in which an oxyalkylene polymer having a hydrolyzable silyl group and a vinyl polymer having a hydrolyzable silyl group are used in combination.
  • Patent Document 2 discloses that as a vinyl polymer having a hydrolyzable silyl group, a polymer obtained by continuous bulk polymerization at high temperature and high pressure is particularly excellent in weather resistance.
  • Patent Document 3 discloses a curable composition containing a vinyl polymer having a reactive silicon group, a polyoxyalkylene polymer having a reactive silicon group, and a plasticizer having an acrylic component. .
  • Patent Document 4 discloses a method of producing a vinyl polymer by using a living radical polymerization method, modifying both ends thereof to hydrolyzable silyl groups, and a curable composition containing the obtained polymer. It is disclosed.
  • the living radical polymerization method is a method of growing a polymer chain by successive growth, and is a method capable of controlling the molecular weight, molecular weight distribution, terminal group, and block structure. JP 59-122541 A JP 2004-18748 A JP 2004-2604 A JP-A-11-130931
  • An object of the present invention is to provide a highly practical curable composition having good workability, high elongation at break of a cured product, and excellent heat resistance and weather resistance.
  • the present inventors have a hydrolyzable silyl group produced by a living radical polymerization method using a (meth) acrylic copolymer having a specific hydroxyl value and a weight average molecular weight. It has been found that when a specific amount is added to the vinyl polymer, a curable composition exhibiting high breaking elongation and excellent heat resistance and weather resistance can be obtained, and the present invention has been completed.
  • the curable composition according to the present invention has a vinyl copolymer (A) having a hydrolyzable silyl group, a hydroxyl value of 50 to 300 mgKOH / g, and a weight average molecular weight of 1500 to 6000.
  • the content of the (meth) acrylic copolymer (B) is 20 to 200 parts by mass with respect to 100 parts by mass of the vinyl copolymer (A).
  • the living radical polymerization is preferably polymerization using a nitrooxide radical.
  • the (meth) acrylic copolymer (B) is preferably produced by continuous polymerization at a temperature of 150 to 350 ° C.
  • the curable composition according to the present invention has a vinyl copolymer having a hydrolyzable silyl group produced by a living radical polymerization method, a specific hydroxyl value and a weight average molecular weight (meth). Contains a specific amount of an acrylic copolymer. Therefore, it has the effects of being cured at room temperature with moisture in the atmosphere, exhibiting high elongation at break, and having excellent heat resistance and weather resistance. Moreover, since the curable composition of this invention is a moderate viscosity, it is excellent in workability
  • the vinyl copolymer (A) having hydrolyzable silyl groups according to the present invention (hereinafter also referred to as “component (A)”). ] Is an organic polymer containing a silyl group in the molecule, and is a base resin of the curable composition.
  • a vinyl-type monomer used for manufacture of a component (A) It is a (meth) acrylic-acid type copolymer from the point of the mechanical physical property and weather resistance when it is set as a curable composition. It is preferable to use an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms in the ester chain, a vinyl monomer having an alkoxysilyl group, and other vinyl monomers.
  • a preferred ratio of each monomer is an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the ester chain: 40 to 99.5 parts by mass, a vinyl monomer having an alkoxysilyl group as a crosslinkable functional group: 0.5 to 20 parts by mass, other vinyl monomers: 0 to 59.5 parts by mass are preferably used.
  • the more preferable ratio of each monomer is 60 to 99 parts by weight, 0.5 to 7 parts by weight, and 0 to 39 parts by weight (based on 100 parts by weight of all monomers used for producing the vinyl polymer). Ratio).
  • the glass transition temperature may be high and the rubber elasticity may be lowered. If it exceeds 99.5 parts by mass, the glass becomes soft. The strength of the cured product may decrease. If the vinyl monomer having an alkoxysilyl group is less than 0.5 parts by mass, the crosslink density may be low and the strength may be reduced. .
  • alkyl acrylate ester having an alkyl group having 1 to 8 carbon atoms in the ester chain include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, and acrylic acid.
  • vinyl monomers having an alkoxysilyl group examples include vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, trimethoxysilylpropyl acrylate, triethoxysilyl acrylate.
  • vinyl silanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, trimethoxysilylpropyl acrylate, triethoxysilyl acrylate.
  • Silyl group-containing acrylic esters such as propyl and methyldimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate, methyldimethoxysilylpropyl methacrylate, and silyl groups such as dimethylmethoxysilylpropyl methacrylate
  • Silyl group-containing vinyl ethers such as methacrylic acid esters, trimethoxysilylpropyl vinyl ether, silicic acid such as vinyl trimethoxysilylundecanoate Group-containing vinyl esters, and the like.
  • a preferable monomer is an acrylic acid ester or a methacrylic acid ester having a methoxysilyl group or an ethoxysilyl group, more preferably methyl methacrylate because of copolymerization with an acrylic acid ester and flexibility of the copolymer. Dimethoxysilylpropyl, trimethoxysilylpropyl methacrylate, methyldiethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate.
  • vinyl monomers can be used as long as the physical properties of the component (A) and its blend are not impaired.
  • examples of such monomers include alkyl acrylates having an alkyl group having 12 or more carbon atoms, such as lauryl acrylate, tridecyl acrylate, and stearyl acrylate.
  • methacrylic acid esters specifically, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, tricyclodecynyl methacrylate, lauryl methacrylate, methacrylic acid, Examples include acid stearyl. Among these, methacrylic acid esters are preferable. Those having 4 or more carbon atoms in the alcohol residue of the ester are preferable because the viscosity of the polymer is low and the water resistance and weather resistance of the curable composition are excellent.
  • a monomer having ultraviolet absorbing ability examples include 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, methacryloxyhydroxypropyl-3- [3- (2H-benzotriazole-2 -Yl) -5-tertiarybutyl-4-hydroxyphenyl] propionate and 2-hydroxy-4- (methacryloxyethoxy) benzophenone.
  • the light-stable monomer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and 2,2,6,6-tetramethyl-4-piperidyl methacrylate.
  • Examples of the functional group-containing monomer include epoxy group-containing monomers such as glycidyl (meth) acrylate and vinyl glycidyl ether, acrylic acid and methacrylic acids, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, methacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide and the like can be mentioned.
  • epoxy group-containing monomers such as glycidyl (meth) acrylate and vinyl glycidyl ether, acrylic acid and methacrylic acids, acrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, methacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide and the like can be mentioned.
  • ⁇ -olefins such as ethylene, propylene, 1-butene and isobutylene, chloroethylenes such as vinyl chloride and vinylidene chloride, and fluoroethylenes such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene and vinylidene fluoride , Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, Veova 9, Veova 10 (manufactured by Shell Chemical, carbon number 9 and 10 fatty acid vinyl) and vinyl esters such as vinyl laurate, and allyl ethers such as ethyl allyl ether and butyl allyl ether.
  • Preferred monomers are methacrylic acid esters, and particularly preferred are methyl methacrylate, butyl me
  • Component (A) can be produced by a living radical polymerization method.
  • a living radical polymerization method a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced into any position of the polymer.
  • Examples of the living radical polymerization method include an ATRP method using copper bromide as a catalyst disclosed in JP-A-11-130931, and a vinyl monomer in the presence of a thiocarbonylthio compound disclosed in JP 2000-515181 A.
  • Examples include an addition-cleavage chain transfer method (RAFT method) for polymerizing a living radical polymerization method using a nitrooxide radical disclosed in JP-T-2003-500378.
  • RAFT method addition-cleavage chain transfer method
  • the living radical polymerization method using a nitrooxide radical is preferable because there is no need to use a highly toxic copper compound unlike the ATRP method.
  • the living radical polymerization can be carried out in the range of 0 to 200 ° C., preferably 50 to 150 ° C.
  • the weight average molecular weight of component (A) is a polystyrene equivalent molecular weight determined by gel permeation chromatography (hereinafter also referred to as “GPC”), and the number average molecular weight (Mn) is preferably 5000 to 50000. More preferred is 8000 to 25000. When Mn is lower than 5000, the crosslink density of the cured product becomes too high, and the elongation of the cured product becomes extremely small. When Mn is higher than 50000, the viscosity becomes very high and workability is remarkably deteriorated.
  • the glass transition temperature of component (A) is preferably ⁇ 70 to 30 ° C., more preferably ⁇ 70 to 10 ° C. If it exceeds 30 ° C., there is a risk that the rubber will not have sufficient rubber elasticity in winter, and the workability will also deteriorate.
  • the hydrolyzable silyl group contained in the component (A) is a group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond by a reaction with a curing catalyst. Although it does not specifically limit as a hydrolysable silyl group, The thing of the following general formula (1) is preferable at the point which is easy to bridge
  • R represents a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.
  • X is a halogen atom, hydrogen A reactive group selected from an atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. (It may be the same group or different groups.
  • X is preferably an alkoxy group.
  • N is an integer of 0, 1 or 2.
  • alkoxysilyl group of component (A) those having a trimethoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, a methyldiethoxysilyl group, or a methyldimethoxyethoxysilyl group are preferable.
  • a trimethoxysilyl group or a methyldimethoxysilyl group is particularly preferred from the viewpoint of the balance between curing speed and flexibility.
  • the number of alkoxysilyl groups in one molecule of component (A) is preferably 0.1 to 4, more preferably 0.3 to 3. If it is less than 0.1, curing is insufficient, and if it exceeds 4, the cured product becomes hard.
  • the radical polymerization initiator used for the production of the component (A) may be any initiator that generates radicals at a predetermined reaction temperature.
  • peroxides such as diisopropyl peroxydicarbonate, di-2-ethoxyethyloxydicarbonate, tertiary butyl peroxypivalate, ditertiary butyl peroxide, benzoyl peroxide and lauroyl peroxide, or 2, Azo compounds such as 2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis (2,4-dimethylvaleronitrile), ammonium persulfate and persulfate Examples thereof include inorganic peroxides such as potassium and metal complexes used for living polymerization.
  • a thermally initiated radical generated from styrene or the like may be used.
  • ditertiary butyl peroxide, ditertiary hexyl peroxide, ditertiary amyl peroxide, and azo initiator are inexpensive and the initiator radicals are less likely to cause hydrogen abstraction.
  • the hydrogen abstraction reaction occurs frequently, the molecular weight distribution becomes wide, and a low molecular weight component into which no crosslinkable functional group is introduced is likely to be formed, and the weather resistance may be deteriorated.
  • (Meth) acrylic copolymer (B) according to the present invention [hereinafter also referred to as “component (B)”. ] Is an organic polymer having a hydroxyl value of 50 to 300 mgKOH / g and a weight average molecular weight of 1500 to 6000.
  • the component (B) functions as a plasticizer in the curable composition, and has an effect of adjusting workability and improving workability before the composition is cured. Moreover, after hardening of a composition, it has the effect
  • “(meth) acryl” means “acryl or methacryl”.
  • Component (B) is a copolymer of a hydroxyl group-containing (meth) acrylic monomer and another (meth) acrylic monomer, which is one or two (meth) acrylic monomers When polymerizing more than seeds, a small amount of a hydroxyl group-containing (meth) acrylic monomer is used as a copolymer component. The ratio of the hydroxyl group-containing (meth) acrylic monomer to the total monomers used in the production of component (B) is adjusted so that the hydroxyl value of component (B) falls within the range of 50 to 300 mgKOH / g.
  • Hydroxyl group-containing (meth) acrylic monomers include ⁇ -caprolactone addition reaction of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and hydroxyethyl (meth) acrylate And (meth) acrylic acid hydroxyalkyl compounds.
  • hydroxyethyl acrylate is preferable from the viewpoint of elongation at break and workability of the curable composition.
  • the other (meth) acrylic monomers are not particularly limited, but (meth) acrylic acid alkyl esters having an alkyl group having 1 to 8 carbon atoms in the ester chain are preferable from the viewpoint of mechanical properties of the cured product. .
  • (meth) acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms in the ester chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth ) Isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, (meth) acrylic acid 2 -Aliphatic alkyl (meth) acrylates such as ethylhexyl, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, (meth) acrylic Such as
  • Component (B) can be produced by ordinary radical polymerization, and any of solution polymerization, bulk polymerization, and dispersion polymerization may be used, and a living radical polymerization method developed in recent years may be used.
  • the reaction process may be any of batch, semi-batch and continuous polymerization. However, it is most preferable that it is obtained by a high temperature continuous polymerization method at 150 to 350 ° C. Moreover, it is preferable not to use chain transfer agents such as mercaptans because they lead to a decrease in weather resistance.
  • the component (B) is obtained by ordinary radical polymerization
  • a high temperature continuous polymerization method at 150 to 350 ° C. is preferred.
  • the polymerization temperature is less than 150 ° C.
  • branching reaction occurs and the molecular weight distribution is widened, and a large amount of initiator and chain transfer agent are required to lower the molecular weight, thus adversely affecting durability such as weather resistance and heat resistance. give.
  • production problems such as heat removal may occur.
  • it is higher than 350 ° C., a decomposition reaction occurs and the polymerization solution is colored or the molecular weight is lowered.
  • stirred tank reactor it is preferable to use a stirred tank reactor as the reactor because a (meth) acrylic acid ester copolymer having a relatively narrow composition distribution (distribution of crosslinkable functional groups) and molecular weight distribution can be obtained. Also, a process using a continuous stirred tank reactor is more preferable than a tubular reactor because the composition distribution and molecular weight distribution are narrowed.
  • a known method disclosed in JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, or the like may be used. For example, after filling a pressurizable reactor with a solvent and setting it to a predetermined temperature under pressure, the reactor is charged with a monomer mixture composed of each monomer and, if necessary, a polymerization solvent at a constant supply rate. And a method of extracting a polymerization solution in an amount commensurate with the supply amount of the monomer mixture. Moreover, a polymerization initiator can also be mix
  • the blending amount when blended is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass of the monomer mixture.
  • the pressure depends on the reaction temperature, the monomer mixture used and the boiling point of the solvent, and does not affect the reaction, but may be any pressure that 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, the monomer may not sufficiently react, and if the unreacted monomer exceeds 60 minutes, the productivity may deteriorate.
  • the preferred residence time is 2 to 40 minutes.
  • the hydroxyl value of component (B) is 50 to 300 mgKOH / g, preferably 70 to 130 mgKOH / g, more preferably 90 to 120 mgKOH / g. If the hydroxyl value is less than 50 mgKOH / g, the elongation at break is insufficient, and if it exceeds 300 mgKOH / g, the viscosity becomes high, so that the effect as a plasticizer is lowered and the workability of the curable composition is lowered. In addition, the weather resistance also decreases.
  • the hydroxyl value in the present invention is a value determined according to JIS K 0070.
  • the weight average molecular weight of the component (B) is 1500 to 6000, preferably 1500 to 5000, more preferably 1500 to 3000, in terms of polystyrene by GPC.
  • the weight average molecular weight is less than 1500, the weather resistance may be insufficient.
  • the weight average molecular weight exceeds 6000, the viscosity becomes high, so that the effect as a plasticizer is lowered and the workability of the curable composition is lowered.
  • the viscosity of component (B) at 25 ° C. is preferably 500 to 15000 mPa ⁇ s, more preferably 800 to 12000 mPa ⁇ s. If the viscosity is less than 500 mPa ⁇ s, sagging may occur during construction, and if it exceeds 15000 mPa ⁇ s, the workability of the curable composition is deteriorated.
  • the glass transition temperature of component (B) is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
  • the glass transition temperature is ⁇ 10 ° C. or higher, the rubber elasticity of the curable composition tends to be insufficient in winter, and the workability also deteriorates.
  • the content of the component (B) in the curable composition according to the present invention is 20 to 200 parts by weight, preferably 30 to 150 parts by weight, more preferably 40 to 40 parts by weight with respect to 100 parts by weight of the component (A). 130 parts by mass.
  • the content of the component (B) is less than 20 parts by mass, the workability of the curable composition is deteriorated, and when it exceeds 200 parts by mass, the crosslinking density of the curable composition is lowered and the durability may be lowered.
  • the curable composition according to the present invention may contain components other than the components (A) and (B).
  • Such components include fillers, thixotropic agents, anti-aging agents, curing accelerators, adhesion enhancing agents, dehydrating agents and the like.
  • Fillers include light calcium carbonate with an average particle size of about 0.02 to 2.0 ⁇ m, heavy calcium carbonate with an average particle size of about 1.0 to 5.0 ⁇ m, titanium oxide, carbon black, synthetic silicic acid, talc, Examples include zeolite, mica, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass balloon, silica balloon, and polymethyl methacrylate balloon. With these fillers, the mechanical properties of the cured product are improved, and the strength and elongation can be improved.
  • an ultraviolet absorber such as a benzophenone compound, a benzotriazole compound and an oxalic acid anilide compound, a light stabilizer such as a hindered amine compound, an antioxidant such as a hindered phenol, or an antioxidant that is a mixture thereof
  • Tin curing accelerators such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin diacetacetonate, amide wax, silica-based thixotropy imparting agent, adhesion imparting agents such as aminosilane, epoxysilane, vinylsilane, methylsilanes Or a dehydrating agent such as methyl orthoformate and methyl orthoacetate, or an organic solvent.
  • Examples of the ultraviolet absorber include trade names “Tinubin 571”, “Tinubin 1130”, and “Tinubin 327” manufactured by Ciba Specialty Chemicals.
  • Examples of the light stabilizer include trade names “Tinuvin 292”, “Tinuvin 144”, “Tinuvin 123” manufactured by the same company, and a trade name “Sanol 770” manufactured by Sankyo.
  • Examples of the heat stabilizer include trade names “Irganox 1135”, “Irganox 1520”, and “Irganox 1330” manufactured by Ciba Specialty Chemicals. Mixture of ultraviolet absorber / light stabilizer / heat stabilizer; trade name “Tinubin B75” manufactured by Ciba Specialty Chemicals may be used.
  • tin-based catalyst trade names “U28”, “U100”, “U200”, “U220”, “U303”, “SCAT-7”, “SCAT-46A” manufactured by Nitto Kasei Co., Ltd.
  • the product name “No. 918” is exemplified.
  • examples of the thixotropic agent include trade names “Dispalon 3600N”, “Dispalon 3800”, “Dispalon 305”, and “Dispalon 6500” manufactured by Enomoto Kasei Co., Ltd.
  • Anti-tacking agents include trade names “Aronix M8030”, “M8060”, “M8100”, “M309” manufactured by Toagosei Co., Ltd., which are acrylic oligomers, or mixtures with photopolymerization initiators, tung oil, linseed oil Examples include unsaturated fatty acid oils, trade name “R15HT” manufactured by Idemitsu Petrochemical Co., Ltd., trade name “PBB3000” manufactured by Nippon Soda Co., Ltd., and trade name “GOSELAC 500B” manufactured by Nippon Synthetic Chemical.
  • aminosilanes examples include “KBM602”, “KBM603”, “KBE602”, “KBE603”, “KBM903”, and “KBE903” manufactured by Shin-Etsu Silicone.
  • the curable composition according to the present invention contains the above components, but the production method is not particularly limited. Specifically, it can be produced by mixing using a stirrer, a planetary stirrer, or the like.
  • the curable composition of the present invention can also be prepared as a one-component type that cures by preliminarily blending and storing all the blended components and absorbing moisture in the air after coating, and is separately prepared as a curing agent.
  • Components such as a curing catalyst, a filler, a plasticizer, and water may be blended, and the blended material and the polymer composition may be adjusted as a two-component type that is mixed before use.
  • a one-component type that is easy to handle and has few errors during coating is more preferable.
  • the present invention will be described more specifically based on synthesis examples and examples, but the present invention is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the scope of the present invention.
  • the polymer and the curable composition were evaluated as follows. In the following, “parts” means parts by mass.
  • the viscosity in the present invention was measured with an E-type viscometer under the conditions of 25 ° C. and 5 rpm.
  • the jacket temperature was adjusted so that the reaction solution temperature was maintained at 120 ° C.
  • the polymerization rate of BA was 90%.
  • MTMS 3-methacryloxypropyltrimethoxysilane
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 490 parts by mass of a polymer.
  • the properties of the polymer were Mw32400, Mn23100, Mw / Mn1.4, E-type viscosity (25 ° C.) 152000 mPa ⁇ s.
  • the acid value was 0.2 mgKOH / g, and the reaction rate of the carboxyl group of the living polymerization initiator [Formula (2)] was 88%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.7.
  • Polymer B A pressurized stirring tank reactor having a capacity of 1 liter equipped with a soot oil jacket was charged with 360 parts by weight of BA, 9.0 parts by weight of a living polymerization initiator [Formula (2)], and butyl acetate (hereinafter referred to as “BAc”). This was mixed with 108 parts by mass, 6.1 parts by mass of 3-glycidoxypropyltrimethoxysilane, and 1.8 parts by mass of TBAB, and the mixture was sufficiently deaerated by nitrogen bubbling. The jacket temperature was raised to 120 ° C. to initiate the polymerization reaction, and the jacket temperature was adjusted so that the reaction solution temperature was maintained at 120 ° C. After 6 hours, the polymerization rate of BA was 88%.
  • MTMS 6.5 mass part was added there, and it was made to react with it at 120 degreeC for 4 hours.
  • the polymerization rate of BA was 95%
  • the polymerization rate of MTMS was 98%.
  • the reaction solution was taken out and dried under reduced pressure with an evaporator at a reduced pressure of 0.3 kPa and 90 ° C. for 5 hours to obtain about 320 parts by mass of a polymer.
  • the properties of the polymer were Mw 39900, Mn 14800, Mw / Mn 2.7, E-type viscosity (25 ° C.) 354000 mPa ⁇ s.
  • the reaction rate of the carboxyl group of the living polymerization initiator [Formula (2)] was 97%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.9.
  • the acid value was 0.3 mgKOH / g, and the reaction rate of the carboxyl group of the living polymerization initiator [Formula (2)] was 78%.
  • the number of alkoxysilyl groups f (Si) per one polymer chain of the polymer was 1.6.
  • IPA isopropyl alcohol
  • a monomer mixture comprising 1.5 parts of ditertiary butyl peroxide as a polymerization initiator, at a constant feed rate (48 g / Min., Residence time: 12 minutes), continuous supply from the raw material tank to the reactor was started, and a reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet.
  • a reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 246 to 248 ° C. by controlling the oil jacket temperature.
  • the component (B) obtained by the reaction is referred to as “polymer 1”.
  • polymer 8 The copolymer obtained by the reaction is referred to as “polymer 8”.
  • Synthetic Example 13 Synthetic Example 1 except that the monomer mixture is changed to 80 parts HA, 20 parts HEA, 50 parts IPA, 3 parts ditertiary butyl peroxide as the polymerization initiator, and the reaction temperature is changed to 249-251 ° C. Polymerization and treatment were performed in the same manner to synthesize a copolymer. Mw was 1000. The copolymer obtained by the reaction is referred to as “polymer 13”.
  • Examples 1 to 12 Comparative Examples 1 to 8> The compositions of Examples and Comparative Examples and the evaluation results of the compositions are shown in Tables 2 and 3. In Tables 2 and 3, the following components were used other than the polymer. Synthetic calcium carbonate: Shiraishi Calcium Co., Ltd. Heavy calcium carbonate: Maruo Calcium Co., Ltd. Trade name “Super SS” Titanium oxide: Product name “R-820” manufactured by Ishihara Sangyo Co., Ltd.
  • Anti-aging agent Product name “Tinubin B75” manufactured by Ciba Specialty Chemicals Dehydrating agent: Vinylsilane Adhesion imparting agent: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane Curing accelerator: Dibutyltin diacetylacetonate
  • the composition of the comparative example 3 had too high a viscosity, and could not produce the test piece for evaluation.
  • the curable composition of the present invention includes a vinyl copolymer having a hydrolyzable silyl group produced by a living radical polymerization method, and a (meth) acrylic compound having a specific hydroxyl value and a weight average molecular weight. Since it contains a copolymer, it is cured at room temperature with moisture in the atmosphere and the resulting cured product exhibits high elongation at break and has excellent heat resistance and weather resistance. Therefore, the curable composition of the present invention can be used as a sealing material, an adhesive, a paint, and the like, and can be widely applied in the architectural field, the electric / electronic field, the automobile field, and the like.

Abstract

L'invention porte sur une composition durcissable ayant une utilité pratique élevée qui présente une aptitude au façonnage avantageuse, qui est durcie par l'humidité atmosphérique ou similaire, qui donne une matière durcie avec un allongement à la rupture élevé et qui a une résistance à la chaleur et une résistance aux intempéries remarquables. La composition durcissable contient un copolymère vinylique (A) ayant un groupe silyle hydrolysable et un copolymère (méth)acrylique (B) ayant un indice d'hydroxyle de 50-300 mg de KOH/g et une masse moléculaire moyenne en poids de 1 500-6 000, le copolymère vinylique (A) ayant un groupe silyle hydrolysable étant produit par polymérisation radicalaire vivante et la teneur du copolymère (méth)acrylique (B) susmentionné étant de 20-200 parties en masse pour 100 parties en masse du copolymère vinylique (A) susmentionné.
PCT/JP2009/067548 2008-10-16 2009-10-08 Composition durcissable WO2010044367A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011079994A (ja) * 2009-10-08 2011-04-21 Toagosei Co Ltd 塗料用湿気硬化性組成物
JP2011157409A (ja) * 2010-01-29 2011-08-18 Toagosei Co Ltd 塗料用熱硬化性組成物

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178456A (ja) * 1998-10-08 2000-06-27 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2002129097A (ja) * 2000-10-20 2002-05-09 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物
WO2004069923A1 (fr) * 2003-01-22 2004-08-19 Kaneka Corporation Polymere et compositions durcissables a stabilite de stockage amelioree
JP2008239859A (ja) * 2007-03-28 2008-10-09 Toagosei Co Ltd 湿気硬化性組成物、それを含有する接着剤組成物及びシーリング剤組成物
WO2009145245A1 (fr) * 2008-05-30 2009-12-03 東亞合成株式会社 Composition durcissable

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000178456A (ja) * 1998-10-08 2000-06-27 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2002129097A (ja) * 2000-10-20 2002-05-09 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物
WO2004069923A1 (fr) * 2003-01-22 2004-08-19 Kaneka Corporation Polymere et compositions durcissables a stabilite de stockage amelioree
JP2008239859A (ja) * 2007-03-28 2008-10-09 Toagosei Co Ltd 湿気硬化性組成物、それを含有する接着剤組成物及びシーリング剤組成物
WO2009145245A1 (fr) * 2008-05-30 2009-12-03 東亞合成株式会社 Composition durcissable

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011079994A (ja) * 2009-10-08 2011-04-21 Toagosei Co Ltd 塗料用湿気硬化性組成物
JP2011157409A (ja) * 2010-01-29 2011-08-18 Toagosei Co Ltd 塗料用熱硬化性組成物

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JPWO2010044367A1 (ja) 2012-03-15

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