WO2008059872A1 - Composition pour matériau d'étanchéité - Google Patents

Composition pour matériau d'étanchéité Download PDF

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Publication number
WO2008059872A1
WO2008059872A1 PCT/JP2007/072090 JP2007072090W WO2008059872A1 WO 2008059872 A1 WO2008059872 A1 WO 2008059872A1 JP 2007072090 W JP2007072090 W JP 2007072090W WO 2008059872 A1 WO2008059872 A1 WO 2008059872A1
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Prior art keywords
polymer
sealing material
meth
group
acrylate
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PCT/JP2007/072090
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English (en)
Japanese (ja)
Inventor
Koutarou Yoneda
Michihiro Kaai
Katsunobu Mochizuki
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Toagosei Co., Ltd.
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Priority to JP2008544171A priority Critical patent/JP4905459B2/ja
Publication of WO2008059872A1 publication Critical patent/WO2008059872A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a sealing material composition that can be cured at room temperature, and more particularly to a sealing material composition that has high elongation at break and excellent weather resistance.
  • a curable composition containing an organic polymer having a reactive group of room temperature curable type is used as a sealing material for a building or an adhesive.
  • a curable composition based on an oxyalkylene polymer having a hydrolyzable silyl group has good workability and a good balance of mechanical properties such as breaking elongation and breaking strength. Widely used. Since sealing materials for construction are used by filling gaps between members that expand and contract over time, such as siding materials and metal curtain walls, high elongation at break is required.
  • Patent Document 1 discloses a method in which an oxyalkylene polymer having a hydrolyzable silyl group and a bur polymer having a hydrolyzable silyl group are used in combination.
  • Patent Document 2 discloses that a bull polymer having a hydrolyzable silyl group, which is obtained by continuous bulk polymerization at high temperature and high pressure, is particularly excellent in weather resistance. Has been.
  • JP-A-2004-2604 discloses a bulle polymer having a reactive cage group, a polyoxyalkylene polymer having a reactive cage group, and a plasticizer having an acrylic component.
  • a curable composition is disclosed.
  • the sealing material containing a bulle polymer having a hydrolyzable silyl group as described above has a lower elongation at break than a sealing material composed solely of an oxyalkylene polymer, In some cases, the balance between weather resistance and weather resistance becomes insufficient.
  • Patent Document 1 Sho 59-122541
  • Patent Document 2 JP 2004-18748 A Patent Document 3: Japanese Patent Laid-Open No. 2004-2604
  • An object of the present invention is to provide a sealing material composition having a high elongation at break and excellent weather resistance.
  • the present inventor has intensively studied by paying attention to the number of crosslinkable functional groups of the bull polymer which is a constituent component of the sealing material composition.
  • the number of crosslinkable functional groups per molecule is in a specific range and the weight average molecular weight is a bulle polymer having a crosslinkable functional group and a hydrolyzable silyl group.
  • the present inventors have found that a sealing material composition containing an alkylene polymer is excellent in physical properties such as high! /, Elongation at break and weather resistance, and completed the present invention.
  • the sealing material composition of the present invention has high physical properties such as high elongation at break and weather resistance.
  • Acrylic or methacrylic is also called (meth) acryl.
  • the (A) oxyalkylene polymer having a hydrolyzable silyl group in the present invention is a polymer having an oxyalkylene unit as a repeating unit and having a hydrolyzable silyl group at the terminal. means.
  • the hydrolyzable silyl group is not particularly limited, and examples thereof include an alkoxysilyl group.
  • the alkoxysilyl group include a trimethoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, a triethoxysilyl group, and a methyljetoxysilyl group.
  • Group, and methyldimethoxyethoxysilyl group are preferable from the balance of curing speed and flexibility.
  • Examples of the oxyalkylene polymer include polymers containing the following oxyalkylene units.
  • the oxyalkylene polymer may contain one or more of the above repeating units. Among these, a polymer having an oxyalkylene unit of —CH 2 CH 2 (CH 2) —O 2 is preferred because of excellent workability!
  • the method for producing the oxyalkylene polymer is not particularly limited, but for example, using a corresponding epoxy compound or diol as a raw material, a polymerization method using an alkali catalyst such as KOH, a transition metal compound, volfilin.
  • alkali catalyst such as KOH
  • transition metal compound such as a transition metal compound
  • volfilin examples thereof include a polymerization method using a complex catalyst, a polymerization method using a complex metal cyanide complex catalyst, and a polymerization method using phosphazene.
  • the polymerization method using a composite metal cyanide complex catalyst using an epoxy compound as a raw material is suitable for obtaining a polymer having a high molecular weight and a narrow molecular weight distribution, and has an excellent balance between the viscosity of the sealing material composition and the elongation at break of the cured product. Therefore, it is preferable.
  • the average number of hydrolyzable silyl groups per molecule of the oxyalkylene polymer having hydrolyzable silyl groups is preferably 1 to 4. If the number exceeds 4, the resulting composition may become hard, and if it is less than 1, the resulting composition may be insufficiently cured.
  • the weight average molecular weight of the oxyalkylene polymer having a hydrolyzable silyl group is preferably 2,000 to 500,000 in terms of polystyrene by gel permeation chromatography (GPC). If the weight average molecular weight is less than 2,000, the cured sealant may have insufficient flexibility. If the weight average molecular weight exceeds 50,000, the composition will have high viscosity. Workability may be reduced during construction.
  • oxyalkylene polymer having a hydrolyzable silyl group examples include “MS Polymer S203” (trade name), “MS Polymer S303” (trade name), “Syryl SA T200J ( "Product name)” and “Cyrill SAT30" (product name), “Etasester ESS2410” (product name), “Etasester ESS2420” (product name), “Etasester ESS3430” (product name), etc. manufactured by Asahi Glass Co., Ltd. These can be used in the invention.
  • the BUL polymer having a crosslinkable functional group (B) in the present invention has an average number of crosslinkable functional groups per molecule of 0.5;! To 0.5, and a weight average molecular weight of gel permeation. It is 12,000-25,000 in terms of polystyrene by Aeon Chromatography (GPC). From the viewpoint of weather resistance and elongation at break, the average number of crosslinkable functional groups per molecule is preferably 0.;! To 0.4. 0;;! To 0.3. More preferably. From the viewpoint of the balance between weather resistance and workability, the weight average molecular weight is preferably 15,000-22,000, and more preferably 17,000-21,000.
  • the sealing material composition may have insufficient curability, and the resulting cured product may have insufficient weather resistance.
  • the number exceeds 0.5, the curability of the sealing material composition is too strong, and the flexibility (elongation) of the resulting cured product may not be satisfactory.
  • the average number of crosslinkable functional groups per molecule is determined as the product of polystyrene-reduced number average molecular weight (g / mol) and crosslinkable functional group concentration (mol / g) by GPC. It is done.
  • the sealing material composition may be insufficiently curable, and the resulting cured product may have insufficient weather resistance. It may become a thing.
  • the higher the weight average molecular weight the more easily the cured product has excellent weather resistance, but when it exceeds 25,000, the viscosity increases, and the sealant composition manufacturing process and the sealant composition coating process Workability may be reduced.
  • crosslinkable functional group examples include a hydrolyzable silyl group, a hydroxyl group, an epoxy group, an alkenyl group, an amino group, and a polymerizable carbon-carbon double bond.
  • hydrolyzable silyl groups are preferred because they are easily cross-linked with an oxyalkylene polymer having a hydrolyzable silyl group.
  • hydrolyzable silyl group examples include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, and a diisopropoxymethylsilyl group.
  • a method for introducing a crosslinkable functional group a method in which a monomer having these functional groups is copolymerized with another raw vinyl monomer and a method in which a functional group is introduced into a bulle polymer by a polymer reaction. Is mentioned.
  • a monomer having a hydrolyzable silyl group is used as a method for introducing a hydrolyzable silyl group.
  • a method of copolymerizing with other raw material bull monomers, a method of adding a hydrosilane compound having a hydrolyzable silyl group to a bulle polymer having an alkenyl group using a hydrosilylation catalyst, and a butyl polymer having a hydroxyl group A method of reacting a hydrolyzable silyl group with a compound having a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule, a chain transfer agent having a hydrolyzable silyl group in the synthesis of a vinyl polymer, And a method using an initiator.
  • the monomer constituting the bulle polymer is not particularly limited, but it preferably contains a (meth) acrylic acid ester from the viewpoint of mechanical properties and weather resistance as a sealing material composition. In particular, it is preferable to contain 1 to 40 parts by weight of methacrylic acid ester.
  • 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 bule monomer having a crosslinkable functional group: 0.5 to 10 parts by mass, other bull monomers: 0 to 59.5 parts by mass are exemplified.
  • the more preferable ratio of each monomer is 60 to 99 parts by mass, 0.5 to 7 parts by mass, and 0 to 39 parts by mass (based on 100 parts by mass of all monomers used for the production of the bull polymer). Ratio).
  • a monomer having an alkoxysilyl group is preferred as a monomer having a crosslinkable functional group! /.
  • the glass transition temperature may increase and the rubber elasticity may decrease, exceeding 99.5 parts by mass.
  • the strength of the cured product may decrease. If the amount of the butyl monomer having a crosslinkable functional group is less than 0.5 parts by mass, the crosslink density may be low and the strength may be reduced. If the content exceeds 10 parts by mass, the crosslink density increases and the cured product has insufficient elongation. It may be a thing.
  • 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, and isobutyl acrylate.
  • butyl monomer having an alkoxysilyl group examples include butylsilanes such as butyltrimethoxysilane, butyltriethoxysilane, butylmethyldimethoxysilane, butyldimethylmethoxysilane, trimethoxysilylpropyl acrylate, and triacrylate acrylate.
  • Silyl group-containing acrylates such as ethoxysilyl pills and methyldimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl methacrylate and methyldimethoxysilylpropyl methacrylate, dimethylmethoxysilyl methacrylate
  • Silyl group-containing methacrylates such as rupropyl, silyl group-containing butyl ethers such as trimethoxysilylpropyl vinyl ether, and trimethoxysilyl undecanoic acid vinyl Silyl group-containing Bulle esters etc., and the like.
  • (meth) acrylic acid ester having a methoxysilyl group or ethoxysilyl group is more preferable than methacrylic acid ester because of copolymerizability with (meth) acrylate and flexibility of the copolymer.
  • These are methyldimethoxysilylpropyl acid, trimethoxysilylpropyl methacrylate, methyljetylsilylpropyl methacrylate, and triethoxysilylpropyl methacrylate.
  • a functional group-containing monomer other than a butyl monomer having an alkoxysilyl group hydroxymethyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) ⁇ -strength prolatatone addition reaction product of hydroxyethyl acrylate, hydroxyalkyl (meth) acrylates such as methacrylic acid, epoxy group-containing monomers such as glycidyl (meth) acrylate and vinyl glycidyl ether, acrylic acid and methacrylic acid, Atalinoleamide, ⁇ -methyl acrylamide, ⁇ , ⁇ -dimethyl acrylamide, ⁇ , ⁇ -jetyl clinoleamide, methacrylamide, ⁇ -methyl methacrylamide and ⁇ , ⁇ -dimethyl methacrylamide and the like.
  • Other monomers can be used in a range that does not impair the physical properties of the bull polymer.
  • examples of such monomers include methacrylic acid esters having an alkyl group having 1 to 20 carbon atoms, alkyl acrylate esters having an alkyl group having 9 or more carbon atoms, and functional group-containing monomers. Acid esters are preferred.
  • Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, neopentyl methacrylate, methacrylic acid.
  • Aliphatic alkyl methacrylates such as 2-ethylhexyl acid and cyclohexyl methacrylate, 2-methoxyethyl methacrylate, dimethylaminoethyl methacrylate, chloroethyl methacrylate, trifluoroethyl methacrylate and tetrahydrofurfuryl methacrylate
  • the power that includes the heteroatom-containing methacrylates is not limited to these.
  • An ester having an alcohol residue having 4 or more carbon atoms is preferable because the sealing material having a low polymer viscosity is excellent in water resistance and weather resistance.
  • An ester having an alcohol residue having 10 or more carbon atoms also has an effect of improving compatibility with an oxyalkylene polymer having a hydrolyzable silyl group.
  • alkyl acrylate ester having an alkyl group having 9 or more carbon atoms examples include Noel (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, and stearyl (meth) acrylate. Is exemplified.
  • ⁇ -olefins such as ethylene, propylene, 1-butene and isobutylene, chloroethylenes such as butyl chloride and vinylidene chloride, tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, fluoride Fluoroethylenes such as vinylidene, methinolevinoleateodia, ethinolevinoleateoleno, butinolevininoleethenole, butyl ethers such as isobutyl butyl ether and cyclohexyl butyl ether, butyl acetate, butyl propionate, Butyl esters such as butyrate, caproate, force prillate, Beva 9, Beova 10 (manufactured by Shell Chemical Co., Ltd., fatty acid vinyl having 9 and 10 carbon atoms) and laurate such as laurate Tyraryl ether and butyral ether
  • the viscosity of the bull polymer having a crosslinkable functional group in the present invention is preferably 10000 to 150,000 mPa's as measured with an E-type viscometer under the conditions of 25 ° C and 5 rpm. . More preferably (between 20000 and 70000 mPa's. If the force is less than SOOOOmPa's, or if it exceeds 150,000 mPa's, workability as a sealing material may be reduced. Further, the glass transition temperature of the bull polymer (B) is preferably from 70 to 10 ° C, more preferably from -65 to -20 ° C. If it exceeds 10 ° C, it may become hard in winter and may not be used. If it is below 70 ° C, contamination resistance may be poor.
  • the BUL polymer having a crosslinkable functional group (B) in the present invention can be obtained by ordinary radical polymerization, and may be any of solution polymerization, bulk polymerization, and dispersion polymerization, and has been developed in recent years. Living radical polymerization may be used.
  • the reaction process may be any of batch, semi-batch, and continuous polymerization. Among these, a high-temperature continuous polymerization method of 150 to 350 ° C is preferable.
  • the molecular weight can be easily produced without containing a large amount of impurities such as an initiator and a chain transfer agent.
  • the ratio of the crosslinkable functional group introduced into the bulle polymer is small, the uniform introduction of the crosslinkable functional group into the polymer indicates that the resulting sealing material composition has excellent curing properties. It is important to develop performance such as durability and weather resistance.
  • a stirred tank reactor as the reactor because a bull polymer having a relatively narrow composition distribution (distribution of crosslinkable functional groups) and molecular weight distribution can be obtained. Further, 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.
  • the liquid level of the reaction liquid in the reactor may be controlled so that a head space (gas phase part) force S is generated at the upper part of the reaction liquid, or the reaction liquid is seen in the reactor (the gas phase part is It may be controlled so that it becomes full.
  • a radical polymerization initiator can be blended with the monomer mixture as necessary. The blending amount is preferably 0.00;! To 2 parts by mass with respect to 100 parts by mass of the monomer mixture.
  • the reaction liquid extracted from the reactor can be isolated by distilling off volatile components such as unreacted monomers, solvents, and low molecular weight oligomers by distillation or the like.
  • the A part of the volatile components such as unreacted monomer, solvent, and low molecular weight oligomer distilled off from the reaction solution can be returned to the raw material tank or directly returned to the reactor and used again for the polymerization reaction.
  • a method of recycling unreacted monomers and solvents is a preferable method from the viewpoint of economy.
  • the proportion of the distillate returned to the raw material tank or the reactor is preferably 30 to 98%, more preferably 50 to 95%. If it exceeds 98%, gel may form in the reactor during polymerization, and scale may adhere. If it is less than 30%, the economic effect is low.
  • the polymerization pressure depends on the reaction temperature and the boiling point of the monomer mixture and solvent to be used, and does not affect the reaction, but may be any pressure that can maintain the reaction temperature.
  • the residence time of the monomer mixture in the polymerization reaction is preferably !!-60 minutes. If the residence time is less than 1 minute, the monomer may not react sufficiently, and if the residence time exceeds 60 minutes, productivity may deteriorate. More preferably the residence time is 2 to 40 minutes, most preferably 5 to 20 minutes.
  • the polymerization temperature is more preferably 160 ° C to 220 ° C, and more preferably 160 ° C to 200 ° C. By polymerizing in this temperature range, it is possible to efficiently produce a non-colored, low-viscosity copolymer having an appropriate molecular weight and low viscosity.
  • the radical polymerization initiator used for the polymerization reaction may be a radical polymerization at a predetermined reaction temperature. As long as it is an initiator that generates water, it is not particularly limited! /.
  • diisopropyl peroxide dicarbonate, di-2-ethoxy ethynole oxydicarbonate, tertiary butinole peroxybivalate, ditertiary butino liver oxide, ditertiary hexyl peroxide, ditertiary mil peroxide benzoy Peroxides such as ruperoxide and lauroyl peroxide, or 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and 2,2'-azobis ( 2, 4-dimethino valeronitryl), inorganic peroxides such as ammonium persulfate and potassium persulfate, and metal complexes used in living polymerization.
  • a thermally initiated radical generated from styrene or the like may be used.
  • these particularly preferred are ditertiary butyl peroxide, ditertiary hexyl oxide, ditertiary milperoxide, and azo initiators, which 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 without a bridging functional group can be produced or a sealing material that can be obtained immediately.
  • the composition may have poor weather resistance. .
  • organic hydrocarbon compounds are suitable, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethyl acetate. And esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and alcohols such as methanol, ethanol, and isopropanol are exemplified, and one or more of these should be used. Power S can be.
  • the amount of the solvent used is preferably 80 parts or less with respect to 100 parts by mass of the total amount of monomers.
  • the sealing material composition of the present invention is one to which a component functioning as a plasticizer is added in addition to the above (A) and (B).
  • (C) A (meth) acrylic polymer is used.
  • the one with added plasticizer as a component is preferred.
  • the (meth) acrylic polymer that functions as a plasticizer is obtained by continuously polymerizing (meth) acrylic monomers and other bulle monomers as necessary at a temperature of 150 to 350 ° C. And a weight average molecular weight of 1,200 to 25,000, a glass transition temperature of ⁇ 70 to ⁇ 10 ° C., and no alkoxysilyl group.
  • an attalinoleic acid ester polymer described in JP-A No. 2001-207157 is preferably used.
  • Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( (Meth) isobutyl acrylate, (meth) acrylic acid s-butyl, (meth) acrylic acid t-butyl, (meth) acrylic acid neopentyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isodecyl, (meta ) Alkyl (meth) acrylates such as lauryl acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tri (meth) acrylate (Meth) atalinoleic acid alicycl
  • Heteroatom-containing (meth) acryl such as 2-methoxyethyl, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate Powers including acid esters are not limited to these. One or more of these may be polymerized.
  • copolymerize a copolymerizable monomer other than (meth) acrylic acid ester examples thereof include bulle monomers such as ⁇ -olefins, buresters and burethers.
  • Plasticizers containing the (meth) acrylic polymer as a component include A RUFON (registered trademark) "UP1000”, “UP1010”, “UP1020”, “UP1060”, “UP10” manufactured by Toagosei Co., Ltd. Examples include “80”, “UP1110”, “UH2000”, “UH2130” (all are trade names), and these can be used in the present invention.
  • plasticizers can also be used.
  • phthalates such as bis (2-ethylhexyl) phthalate, polypropylene glycol having a weight average molecular weight of 1,000 to 50,000.
  • a certain commercial item can be used as it is.
  • the preferred weight average molecular weight of polypropylene glycol is 3,000-20,000. If it is less than 1,000, the weather resistance is insufficient, and if it exceeds 50,000, the workability is increased due to the high viscosity.
  • Preminol 4010 (trade name), “Preminol 5005” (trade name), “Preminol 3010” (trade name), Nippon Oil & Fats Co., Ltd. “Uniol D4000” (trade name), “UNIOL TG4000” (trade name) can be used.
  • the amount of the plasticizer comprising (C) the (meth) acrylic polymer as a component is 20 to 100 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the mass part is preferred. If it is less than 20 parts by mass, the plasticizing effect is insufficient, and if it exceeds 100 parts by mass, the cured product becomes too soft.
  • the sealing material composition of the present invention includes a filler, a curing accelerator, an adhesion-imparting agent, a dehydrating agent, a light stabilizer, an ultraviolet absorber, and a thixotropic property. Agents etc. may be included.
  • filler As the filler, light calcium carbonate having an average particle size of about 0.02-2.0 m, heavy calcium carbonate having an average particle size of about 1.0 to 5.0 m, titanium oxide, carbon black, synthesis Examples include caytic acid, talc, zeolite, my strength, silica, calcined clay, kaolin, bentonite, aluminum hydroxide and barium sulfate, glass balloon, silica balloon, and polymethyl methacrylate balloon. These fillers can improve mechanical properties and improve strength and elongation. Among these, light calcium carbonate, heavy calcium carbonate, and titanium oxide, which are highly effective in improving physical properties, are preferable.
  • the added amount of the filler is preferably 50 to 300 parts by mass based on 100 parts by mass of the total amount of (A) and (B). More preferably, it is 100-250 mass parts. If the amount of filler is too small or too large, the mechanical properties of the sealing material may be impaired.
  • dibutyltin dilaurate, dibutyltin diacetate, and dibutyl as curing accelerators Dibutyltin dicetyl maltonate, dibutyltin diethylhexanolate, dibutyltin diiotate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin diisooctylmalate, dibutyltin ditridecylmalate, Tetravalent tin compounds such as dibutyltin dibenzyl maleate, dibutyltin maleate, dioctyltin diacetate, dioctyltin distearate, dioctyltin dilaurate, dioctyltin diethyl malate, dioctyltin diisooctylmalate, t
  • silanol condensation catalysts such as silane coupling agents having amino groups such as ( ⁇ -aminoethyl) aminopropylmethyldimethoxysilane, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These curing accelerators may be used alone or in combination of two or more.
  • Amino silane, epoxy silane, bur silane, methyl silanes, etc. as adhesion-imparting agents, methyl orthoformate and methyl orthoacetate as dehydrators, hindered amine compounds as light stabilizers, benzophenone compounds, benzotriazole as UV absorbers, etc. Aging such as amide waxes and silicas as thixotropic agents, hindered phenols as antioxidants, etc. It can be mixed with an inhibitor and an organic solvent.
  • Examples of commercially available additives include Tinuvin 571, Tinuvin 1130, and Tinuvin 327 (V, manufactured by Ciba Specialty).
  • Examples of light stabilizers include Tinuvin 292, Tinuvin 144 and Tinuvin 123 (all manufactured by Ciba Specialty) and Sanol 770 (manufactured by Sankyo).
  • Ilganox 1135, Irganox 1520, Irganox 1330 (all manufactured by Ciba Specialty) are exemplified as the heat stabilizer.
  • a mixture of UV absorber / light stabilizer / heat stabilizer Tinuvin B75 (manufactured by Ciba Specialty) may be used.
  • curing accelerators examples include U28, U100, U200, U220 and U303 (all manufactured by Nitto Kasei Co., Ltd.), SCAT-7, SCAT-46A Shobi No918 (manufactured by Sansha Co., Ltd.) Is done.
  • thixotropic agent examples include DISRONON 3600N, DISRONON 3800, DISPARON 305, and DISPARON 6500 (all manufactured by Enomoto Kasei Co., Ltd.).
  • a part means a mass part.
  • the number average molecular weight of polymer 1 in terms of polystyrene (hereinafter referred to as Mn) measured by gel permeation chromatography (hereinafter referred to as GPC) using tetrahydrofuran as a solvent was 6,300, and the weight average molecular weight. (Hereinafter referred to as Mw) was 21,300.
  • Mn polystyrene
  • Mw weight average molecular weight
  • a copolymer was synthesized by polymerizing and treating in the same manner as in Synthesis Example 1 except that the conditions shown in Table 1 were changed.
  • the obtained polymers are referred to as polymers 2, 3, 5, 7, 8, 9 respectively.
  • Table 1 shows the results of these analyses.
  • MMA methyl methacrylate
  • HA 21 ⁇
  • MSi 8 parts of MOA
  • 0.2 part of ditertiary hexyloxide as a polymerization initiator 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.
  • reaction temperature was maintained at 164 to 166 ° C.
  • reaction collection start point The time when the temperature became stable from the start of monomer mixture supply was taken as the reaction collection start point, and as a result of continuing the reaction for 25 minutes, 1.2 kg of monomer mixture was supplied and 1.2 kg of monomer mixture was supplied.
  • the reaction solution was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a concentrated solution (referred to as polymer 4). Tetrahydrofuran was used as the solvent, and Mn of polystyrene-converted polymer 4 measured by GPC was 5300 and Mw was 17500. Also polymerization The number of hydrolyzable silyl groups per molecule in the body 4 was 0.30.
  • a copolymer was synthesized by polymerizing and treating in the same manner as in Synthesis Example 4 except that the conditions shown in Table 1 were changed.
  • the obtained polymers are referred to as polymers 6, 10, and 11, respectively.
  • Table 1 shows the results of these analyses.
  • Table 2 shows the composition of Examples and Comparative Examples.
  • ES-S2420 (Asahi Glass Co., Ltd.) was used as the polyoxyalkylene polymer having a hydrolyzable silyl group.
  • the above blend was applied at a thickness of 2 mm and cured for 1 week under conditions of 23 ° C and 50% RH to prepare a cured sheet.
  • a dumbbell for tensile test (JIS K 6251 No. 3 type) was prepared from the obtained cured product, and the elongation at break was measured with a tensile tester (manufactured by Toyo Seiki, Tensilon 200) (tensile speed: 50 mm / min).
  • the above blend was applied at a thickness of 2 mm and cured for 1 week under conditions of 23 ° C and 50% RH to prepare a cured sheet.
  • An accelerated weathering test was performed with a metering weather meter (DAIPLA METAL WEATHER U-R5NCI-A, manufactured by Dybla Winthes Co., Ltd.), and the time when abnormalities such as cracks and bleeds started to appear was recorded.
  • the sealing material composition of the present invention is excellent in elongation at break and weather resistance, and is useful as a sealing material and an adhesive for buildings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un matériau d'étanchéité qui présente d'excellentes propriétés d'allongement à la rupture, de résistance à la rupture et de résistance aux intempéries. La présente invention concerne plus spécifiquement une composition pour matériau d'étanchéité contenant un polymère oxyalkylène (A) ayant un groupe silyle hydrolysable, et un polymère vinylique (B) contenant de 0,1 à 0,5 groupes fonctionnels réticulables par molécule et ayant un poids moléculaire moyen en poids de 12 000 à 25 000 en terme de polystyrène tel que déterminé par chromatographie d'exclusion diffusion (GPC).
PCT/JP2007/072090 2006-11-16 2007-11-14 Composition pour matériau d'étanchéité WO2008059872A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011153192A (ja) * 2010-01-26 2011-08-11 Toagosei Co Ltd 硬化性組成物
JP2014118502A (ja) * 2012-12-18 2014-06-30 Toagosei Co Ltd シリル基含有ビニル重合体、及びこれを含む硬化性樹脂組成物
JP2017206610A (ja) * 2016-05-18 2017-11-24 東亞合成株式会社 硬化性組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS649268A (en) * 1986-09-30 1989-01-12 Kanegafuchi Chemical Ind Curable composition
WO2004092270A1 (fr) * 2003-04-11 2004-10-28 Kaneka Corporation Composition durcissable
JP2005320519A (ja) * 2004-04-05 2005-11-17 Kaneka Corp 硬化性組成物
JP2006131650A (ja) * 2003-01-22 2006-05-25 Kaneka Corp 物性や硬化性が改善された硬化性組成物及び重合体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS649268A (en) * 1986-09-30 1989-01-12 Kanegafuchi Chemical Ind Curable composition
JP2006131650A (ja) * 2003-01-22 2006-05-25 Kaneka Corp 物性や硬化性が改善された硬化性組成物及び重合体
WO2004092270A1 (fr) * 2003-04-11 2004-10-28 Kaneka Corporation Composition durcissable
JP2005320519A (ja) * 2004-04-05 2005-11-17 Kaneka Corp 硬化性組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011153192A (ja) * 2010-01-26 2011-08-11 Toagosei Co Ltd 硬化性組成物
JP2014118502A (ja) * 2012-12-18 2014-06-30 Toagosei Co Ltd シリル基含有ビニル重合体、及びこれを含む硬化性樹脂組成物
JP2017206610A (ja) * 2016-05-18 2017-11-24 東亞合成株式会社 硬化性組成物

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JPWO2008059872A1 (ja) 2010-03-04

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