WO2016024584A1 - Corps stratifié et procédé d'encapsulation - Google Patents

Corps stratifié et procédé d'encapsulation Download PDF

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Publication number
WO2016024584A1
WO2016024584A1 PCT/JP2015/072732 JP2015072732W WO2016024584A1 WO 2016024584 A1 WO2016024584 A1 WO 2016024584A1 JP 2015072732 W JP2015072732 W JP 2015072732W WO 2016024584 A1 WO2016024584 A1 WO 2016024584A1
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group
component
acid
compound
carbon atoms
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PCT/JP2015/072732
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English (en)
Japanese (ja)
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山下　浩平
正臣 坂部
典子 野呂
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株式会社カネカ
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Priority to JP2016542584A priority Critical patent/JP6640723B2/ja
Publication of WO2016024584A1 publication Critical patent/WO2016024584A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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

Definitions

  • the present invention relates to a laminate and a sealing method.
  • Sealing material is used between members of structures such as architecture, civil engineering, and vehicles, and joints for waterproofing and sealing.
  • the sealing material include a silicone-based sealing material, a modified silicone-based sealing material, a polysulfide-based sealing material, a urethane-based sealing material, and a polyisobutylene-based sealing material.
  • the modified silicone sealant is excellent in quality balance of various physical properties such as durability, weather resistance, low contamination, workability, and paintability. Widely used for residential use.
  • each of the above-described sealing materials is subjected to primer treatment on the surface of the base material in order to ensure adhesion with the base material forming various joint portions and to ensure sealing performance.
  • the problem to be solved by the present invention is to suppress the uncured phenomenon in the thin layer portion of the sealing material when the moisture curable sealing material having a crosslinkable silicon group is used.
  • a moisture curable sealing material having a crosslinkable silicon group and a primer composition containing an acrylic copolymer having a crosslinkable silicon group are used.
  • the present inventors have found that the uncured phenomenon can be suppressed and completed the present invention.
  • the present invention based on this finding is as follows.
  • a laminate of a primer layer and a sealing layer has the following components (A) to (C): (A) Units (a) to (c) derived from the following monomers: (A) Formula (I):
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • a unit derived from a monomer having a crosslinkable silicon group bonded to a carbon atom represented by: (B) a unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms, and (c) a unit derived from another copolymerizable monomer.
  • the sealing layer has the following components (D) and (E): (D) A group consisting of a polyoxyalkylene polymer having a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by forming a siloxane bond, and (E) a group consisting of a carboxylic acid metal salt, a carboxylic acid, and an amine compound
  • a laminate which is a layer formed from an elastic sealant composition containing at least one curing catalyst and / or curing accelerator selected from: [2] The laminate according to [1], wherein the component (C) is a reaction product of dioctyltin dilaurate
  • a sealing method comprising applying a primer composition onto an adherend to form a primer layer, and then filling an elastic sealant composition thereon,
  • the primer composition comprises the following components (A) to (C): (A) Units (a) to (c) derived from the following monomers: (A) Formula (I):
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • a unit derived from a monomer having a crosslinkable silicon group bonded to a carbon atom represented by: (B) a unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms, and (c) a unit derived from another copolymerizable monomer.
  • the elastic sealant composition has the following components (D) and (E): (D) A group consisting of a polyoxyalkylene polymer having a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by forming a siloxane bond, and (E) a group consisting of a carboxylic acid metal salt, a carboxylic acid, and an amine compound
  • the method which is a curable composition containing the at least 1 sort (s) of curing catalyst and / or hardening accelerator selected from these.
  • a moisture curable sealing material having a crosslinkable silicon group that is, an elastic sealing material composition described below
  • an uncured phenomenon in a thin layer portion can be suppressed.
  • the primer composition is used for forming a primer layer for an elastic sealant composition on an adherend.
  • the primer composition used in the present invention comprises a component (A) (crosslinkable silicon group-containing acrylic copolymer), a component (B) (a silane compound having an amino group and / or a reaction product thereof), and (C). Contains components (sulfur-free organotin curing catalyst).
  • Component (A) (crosslinkable silicon group-containing acrylic copolymer)
  • Component (A) is a unit derived from monomer (a) (monomer having a crosslinkable silicon group bonded to a carbon atom represented by formula (I)), monomer (b) (carbon number 10).
  • (B) is a crosslinkable silicon group-containing acrylic copolymer of 2 to 30% by weight of the total amount of monomers.
  • the component (A) only one type may be used, or two or more types may be used in combination.
  • the component (A) is a copolymer having a main chain obtained by substantially copolymerizing an acrylic monomer, and has a crosslinkable silicon group bonded to a carbon atom. Therefore, the primer layer formed from the primer composition containing the component (A) is excellent in adhesiveness, and has extremely excellent adhesiveness even when exposed to water, alkali and the like.
  • the average number of carbon crosslinkable silicon groups represented by the formula (I) in one molecule of component is 1 or more, preferably 1 to 15, more preferably 2 to 10.
  • the average number of crosslinkable silicon groups represented by formula (I) in one molecule of component (A) can be calculated from the monomer composition and the number average molecular weight assuming that the polymerization conversion is 100%. .
  • the average number can be calculated from 1 H-NMR measurement of the component (A).
  • the crosslinkable silicon group represented by the formula (I) may be bonded to the end of the main chain of the component (A), may be bonded to the side chain, and may be bonded to the end of the main chain and the side chain. It may be bonded.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and an i-butyl group.
  • the carbon number of the alkyl group exceeds 10, the reactivity of the crosslinkable silicon group is lowered.
  • the R 1 is a group other than an alkyl group such as a phenyl group or a benzyl group, the reactivity of the crosslinkable silicon group is lowered.
  • R 2 represents a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.
  • R 2 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms in order to improve the curability of the primer composition.
  • Examples of the alkyl group having 1 to 4 carbon atoms include those described above.
  • Examples of the aryl group having 6 to 25 carbon atoms include a phenyl group.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group.
  • a represents an integer of 0 to 2. From the viewpoint that the curability of the component (A) is improved, a is preferably 0 or 1.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • a is 0 or 1 preferable.
  • R 1 is an alkyl group having 1 to 4 carbon atoms
  • R 2 is an alkyl group having 1 to 4 carbon atoms
  • a is 0 or 1 is more preferable.
  • R 1 O When the number of (R 1 O) 3-a or (R 2 ) a present in the formula (I) is two or more, two or more R 1 or R 2 may be the same or different It may be.
  • the number average molecular weight of the component (A) is preferably from 2,000 to 50,000, more preferably 7, from the viewpoint of excellent physical properties such as adhesion strength and durability of the primer layer formed from the primer composition. 000 to 25,000. This number average molecular weight can be measured by GPC (gel permeation chromatography) as shown in Examples described later.
  • the glass transition temperature of the component (A) is preferably 20 ° C. or higher and 150 ° C. or lower in view of excellent properties such as drying properties of the primer layer formed from the primer composition and suppression of dust adhesion. It is more preferable that the temperature is from 100 ° C to 100 ° C. If it is less than 20 degreeC, the drying property at the time of low temperature will worsen, and adhesiveness will fall.
  • This glass transition temperature (Tg (K)) can be calculated from the following Fox equation.
  • the amount of component (A) used is preferably 50 to 99% by weight, more preferably 80 to 95% by weight, based on the solid content of the primer composition.
  • Component (A) includes, for example, monomer (a) (monomer having a crosslinkable silicon group bonded to a carbon atom represented by formula (I)), monomer (b) (carbon number of 10 or more) (Meth) acrylic acid alkyl ester monomer having an alkyl group) and monomer (c) (other copolymerizable monomers) can be produced by polymerization.
  • monomer (a) monomer having a crosslinkable silicon group bonded to a carbon atom represented by formula (I)
  • monomer (b) carbon number of 10 or more)
  • Method acrylic acid alkyl ester monomer having an alkyl group
  • monomer (c) other copolymerizable monomers
  • Monomer (a) (monomer having a crosslinkable silicon group bonded to a carbon atom represented by formula (I))
  • Monomer (a) may use only 1 type and may use 2 or more types together. Examples of the monomer (a) include the following.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • R 5 represents a hydrogen atom or a methyl group.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • 7 represents a monovalent hydrocarbon group selected from 7 to 12 aralkyl groups
  • R 5 represents a hydrogen atom or a methyl group
  • a represents an integer of 0 to 2
  • n represents an integer of 1 to 12 Show.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • 7 represents a monovalent hydrocarbon group selected from 7 to 12 aralkyl groups
  • R 5 represents a hydrogen atom or a methyl group
  • a represents an integer of 0 to 2
  • n represents an integer of 1 to 12 .
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • 7 represents a monovalent hydrocarbon group selected from 7 to 12 aralkyl groups
  • R 5 represents a hydrogen atom or a methyl group
  • a represents an integer of 0 to 2
  • m represents an integer of 1 to 14.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and a carbon number
  • 7 represents a monovalent hydrocarbon group selected from 7 to 12 aralkyl groups
  • R 5 represents a hydrogen atom or a methyl group
  • a represents an integer of 0 to 2
  • p represents an integer of 0 to 20 Show.
  • a compound represented by The description of R 1 , R 2 and a in the above formulas (III) to (VII) is the same as the description in formula (I).
  • the monomer (a) is preferably a compound represented by the formula (IV) (hereinafter referred to as “compound (IV)”).
  • compound (IV) a compound represented by the formula (IV)
  • R 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 is a hydrogen atom.
  • Compound (IV) which is an atom or a methyl group, a is 0 or 1, and n is an integer of 1 to 10.
  • R 1 is an alkyl group having 1 to 4 carbon atoms
  • R 2 is an alkyl group having 1 to 4 carbon atoms
  • R 5 is a hydrogen atom or a methyl group.
  • A is 0 or 1
  • n is an integer of 1 to 5.
  • the amount of the monomer (a) used is preferably 1 to 30% by weight of the total amount of the monomer, more preferably from the viewpoint that the durability of the primer layer formed from the primer composition is excellent and the strength is increased. It is 2 to 20% by weight, more preferably 2 to 15% by weight. When the amount used is less than 1% by weight, the curability of the primer composition tends to be insufficient, and when it exceeds 30% by weight, the storage stability of the primer composition tends to decrease. .
  • Monomer (b) ((meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms)
  • the monomer (b) is a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 or more carbon atoms.
  • Monomer (b) may use only 1 type and may use 2 or more types together.
  • the upper limit of the carbon number of the alkyl group is not particularly limited, but the carbon number is preferably 30 or less, more preferably 20 or less.
  • Examples of the monomer (b) include lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, docosanyl (meth) acrylate, behenyl (meth) acrylate, and 12 carbon atoms. And (meth) acrylic acid ester having 13 to 13 alkyl groups.
  • the monomer (b) is preferably a (meth) acrylic acid alkyl ester monomer having an alkyl group having 10 to 30 carbon atoms, more preferably an alkyl group having 10 to 20 carbon atoms (meta ) Acrylic acid alkyl ester monomer, more preferably at least one selected from the group consisting of stearyl (meth) acrylate and (meth) acrylic acid ester having an alkyl group having 12 to 13 carbon atoms.
  • the amount of monomer (b) used is 2 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 20% by weight, based on the total amount of monomers.
  • the amount used is less than 2% by weight, adhesion to the adherend is difficult to obtain, and when it exceeds 30% by weight, the compatibility with the component (D) decreases.
  • Monomer (c) (Other copolymerizable monomer)
  • the monomer (c) is different from other copolymerizable monomers, that is, monomers (a) and (b), and is a monomer copolymerizable therewith.
  • Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, Fluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, ( (Meth) acrylamide, ⁇ -ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl (meth
  • Unsaturated carboxylic acid esters such as vinyl acetate, vinyl propionate, diallyl phthalate or allyl compounds; amino group-containing vinyl compounds such as vinyl pyridine, aminoethyl vinyl ether; itaconic acid diamide, crotonic acid amide, maleic acid Diamide, fumaric acid diamide, N Amido group-containing vinyl compounds such as vinylpyrrolidone; 2-hydroxyethyl vinyl ether, methyl vinyl ether, cyclohexyl vinyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, fluoroolefin maleimide, N-vinylimidazole, vinyl sulfonic acid, etc. And other vinyl compounds.
  • a monomer (c) may be used independently and may be used together 2 or more types.
  • the monomer (c) is preferably at least one selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylamide, ethyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. More preferably at least one selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylamide.
  • the amount of monomer (c) used is preferably 5 to 95% by weight, more preferably 30 to 90% by weight, and still more preferably 40 to 85% by weight of the total amount of monomers.
  • a segment formed by a urethane bond or a siloxane bond in the main chain is not more than 50% by weight when the component (A) is produced. It may be introduced.
  • the component (A) is produced by, for example, a hydrosilylation method or a solution polymerization method using a monomer having a crosslinkable silicon group described in JP-A Nos. 54-36395 and 57-55954. be able to. From the standpoint of ease of synthesis, it is particularly preferable to use a monomer having a crosslinkable silicon group and a solution polymerization method using an azo radical polymerization initiator such as azobisisobutyronitrile.
  • the solvent used in the solution polymerization method is not particularly limited as long as it is a non-aqueous solvent.
  • hydrocarbons such as toluene, xylene, n-hexane, and cyclohexane
  • acetates such as ethyl acetate and butyl acetate
  • Cellosolves such as cellosolve and butylcellosolve
  • ether esters such as cellosolve acetate
  • ketones such as methyl ethyl ketone, ethyl acetoacetate, acetylacetone, methylisobutylketone, and acetone
  • methanol isopropyl alcohol, n-butanol, isobutanol, hexanol, octanol, etc. Alcohols.
  • mercaptopropyltriethoxysilane (CH 3 O) 3 Si—S—S—Si (OCH 3 ) 3 , (CH 3 O) 3 Si—S 8 —Si (OCH 3 ) 3
  • the chain transfer agent may be used.
  • a crosslinkable silicon group can be introduced at the end of the component (A).
  • the amount of the chain transfer agent used is 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, based on the total amount of the polymerization components used.
  • Component (B) (aminosilane compound and / or reaction product thereof)
  • the component (B) is a silane compound having an amino group and / or a reaction product thereof.
  • a component may be used independently and may be combined 2 or more types. Examples of the component (B) include aminoethylaminopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyldimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyldiethoxysilane, bis ( Aminosilane compounds such as 3-trimethoxysilylpropyl) amine; these aminosilane compounds and epoxy compounds such as Epicoat 828 and Epicoat 1001 (above, manufactured by Yuka Shell Epoxy Co., Ltd.) and ⁇ -glycidoxypropyltrimethoxysilane (E.g., aminosilane (A1100) having one amino
  • reaction product of bis (3-trimethoxysilylpropyl) amine, ⁇ -aminopropyltrimethoxysilane, aminoethylaminopropyltrimethoxysilane and ⁇ -glycidoxypropyltrimethoxysilane, or a combination thereof It is preferable from the viewpoint of adhesion.
  • the amount of component (B) used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 30 parts by weight, and still more preferably 0.5 to 20 parts by weight per 100 parts by weight of component (A). Part. When this amount is less than 0.1 part, the adhesion with the adherend is not sufficiently improved, and when this amount exceeds 50 parts by weight, the compatibility with the component (A) may be lowered.
  • Component (C) (Sulfur-free organotin curing catalyst) Component (C) is an organic tin curing catalyst that does not contain sulfur. (C) A component may use only 1 type and may use 2 or more types together.
  • (C) As a component, the following are mentioned, for example.
  • Organotin compound containing no sulfur (1-i) Carboxylic acid type organotin compound containing no sulfur (1-ia) Dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin Bis (2-ethylhexanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate), dibutyltin bis (butylmaleate), dibutyltin bis (octylmaleate), dibutyltin bis ( Carboxylic acid-type dibutyltin compounds containing no sulfur such as tridecyl maleate), dibutyltin bis (benzyl maleate), dibutyltin diacetate and the like.
  • Component (C) is preferably an organic tin compound not containing sulfur, or a reaction product of an organic tin compound not containing sulfur and a silicate compound (for example, ethyl silicate) from the viewpoint of adhesion and curability of the primer composition. And at least one selected from the group consisting of carboxylic acid-type organic tin compounds not containing sulfur, chelate-type organic tin compounds not containing sulfur, and reaction products of organotin compounds not containing sulfur and silicate compounds. And at least one selected from the group consisting of carboxylic acid-type organic tin compounds containing no sulfur, organotin compounds containing no sulfur, and silicate compounds, particularly preferably sulfur-free carboxylic acids.
  • a silicate compound for example, ethyl silicate
  • Reaction of acid-type dioctyltin compounds, organotin compounds containing no sulfur and tetraethoxysilane is those, particularly more preferably a reaction product of dioctyltin dilaurate and / or dioctyl tin and tetraethoxysilane, and most preferably dioctyl tin dilaurate.
  • the amount of component (C) used is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of component (A).
  • the amount used is less than 0.05 parts by weight, the curability of the primer composition tends to decrease.
  • the amount used exceeds 20 parts by weight, the water resistance of the primer layer obtained from the primer composition is low. It tends to decrease.
  • the primer composition used in the present invention may contain a solvent.
  • the solvent include esters such as ethyl acetate, alcohols such as isopropanol, and ketones such as methyl ethyl ketone.
  • the amount is preferably 30 to 90% by weight, more preferably 50 to 80% by weight in the primer composition.
  • the primer composition used in the present invention may contain a dehydrating agent.
  • the dehydrating agent include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, trimethyl orthobutyrate, ortho Ortho esters such as triethyl butyrate, trimethyl orthoisobutyrate, triethyl orthoisobutyrate and the like can be mentioned.
  • methyl orthoacetate is preferable from the viewpoint of dehydration effect. These may be used alone or in combination of two or more.
  • the dehydrating agent may be added to the component before the polymerization of the component (A), may be added during the polymerization of the component (A), or the obtained component (A) and other components may be added. It may be added at the time of mixing, and there is no particular limitation on the addition timing.
  • a dehydrating agent By adding a dehydrating agent, the storage stability of the primer composition is improved.
  • the amount of the dehydrating agent used is not particularly limited, but the amount is preferably 0.5 to 20 parts, more preferably 2 to 10 parts by weight per 100 parts by weight of component (A).
  • primer composition used in the present invention examples include titanium oxide, ultramarine blue, bitumen, zinc white, bengara, yellow lead, white lead, carbon black, transparent iron oxide, aluminum powder, and other inorganic pigments, azo pigments, Organic pigments such as phenylmethane pigments, quinoline pigments, anthraquinone pigments, phthalocyanine pigments; additives such as diluents, UV absorbers, light stabilizers, sagging inhibitors, leveling agents; nitrocellulose, cellulose acetate butyrate A resin such as epoxy resin, melamine resin, vinyl chloride resin, fluororesin, chlorinated polypropylene, chlorinated rubber, polyvinyl butyral, polysiloxane, and the like may be added as appropriate.
  • azo pigments Organic pigments such as phenylmethane pigments, quinoline pigments, anthraquinone pigments, phthalocyanine pigments
  • additives such as diluents
  • the elastic sealant composition used in the present invention comprises a component (D) (a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by forming a siloxane bond (hereinafter referred to as a crosslinkable silicon group).
  • a polyoxyalkylene polymer) and component (E) at least one curing catalyst selected from the group consisting of carboxylic acid metal salts, carboxylic acids, and amine compounds, and / or curing acceleration).
  • a curable composition containing an agent a curable composition containing an agent.
  • Component (D) (polyoxyalkylene polymer having a hydroxyl group that can be crosslinked by forming a siloxane bond or a silicon group having a hydrolyzable group)
  • the component (D) is a polyoxyalkylene polymer having a silicon group having a hydroxyl group or a hydrolyzable group that can be crosslinked by forming a siloxane bond.
  • a component may use only 1 type and may use 2 or more types together.
  • the crosslinkable silicon group in component (D) 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.
  • a typical example of the crosslinkable silicon group in the component (D) 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.
  • R 6 and R 7 are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an ⁇ -carbon having 1 to 10 carbon atoms).
  • a haloalkyl group, or R ′ 3 SiO— R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different).
  • the hydrolyzable group represented by X is not particularly limited as long as it is a conventionally known hydrolyzable group.
  • the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
  • an alkoxy group, an acyloxy group, an amino group, an amide group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, and an alkoxy group is particularly preferable from the viewpoint of mild hydrolysis and easy handling.
  • the hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and (sum of b) + c is preferably in the range of 1 to 5.
  • two or more hydrolyzable groups or hydroxyl groups are bonded to a silicon atom, they may be the same or different.
  • the number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
  • the number of silicon atoms forming the crosslinkable silicon group may be one or two or more, but in the case of silicon atoms linked by a siloxane bond or the like, there may be about 20 silicon atoms.
  • R 1 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an ⁇ -haloalkyl group having 1 to 10 carbon atoms, or R ′ 3
  • a triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different); When two or more R 1 are present, they may be the same or different, X represents a hydroxyl group or a hydrolyzable group, and when two or more X are present, they are the same. A may represent 1, 2 or 3).
  • the crosslinkable silicon group represented by is preferable from the viewpoint of easy availability.
  • R 1 in the above chemical formula is, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, or an ⁇ -chloro group such as an ⁇ -chloromethyl group.
  • Examples thereof include a chloroalkyl group and a triorganosiloxy group represented by R ′ 3 SiO— in which R ′ is a methyl group, a phenyl group or the like.
  • a methyl group is preferable because the balance between curability and stability of the polymer is good, and an ⁇ -chloromethyl group is preferable because the curing rate of the cured product is particularly high.
  • a methyl group is particularly preferable because of availability.
  • the crosslinkable silicon group of component (D) is preferably a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, ⁇ -chloro At least one selected from the group consisting of a methyldimethoxysilyl group and an ⁇ -chloromethyldiethoxysilyl group, more preferably at least one selected from the group consisting of a dimethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group. And more preferably a dimethoxymethylsilyl group.
  • a trimethoxysilyl group is more reactive than a dimethoxymethylsilyl group
  • a polymer having a trimethoxysilyl group is more reactive than a polymer having a dimethoxymethylsilyl group and has a higher curing speed, but the cured product is broken. Elongation tends to be smaller.
  • a curable composition having a high curing rate can be obtained by using a polymer having a trimethoxysilyl group or by using a polymer having a trimethoxysilyl group and a polymer having a dimethoxymethylsilyl group in combination.
  • a curable composition having a high curing rate can also be obtained by introducing both groups into the same polymer.
  • the amount of a highly reactive polymer such as a polymer having a trimethoxysilyl group and the ratio of both groups in the same polymer are appropriately determined so that the desired elongation at break and curing rate can be obtained. It is done.
  • the introduction of the crosslinkable silicon group can be performed by a known method. That is, a compound having a functional group and a crosslinkable silicon group reactive to this functional group in a polymer having an unsaturated group such as a hydroxyl group or vinyl group in the molecule, or a functional group such as an epoxy group or an isocyanate group. React. For example, the following methods are mentioned.
  • a polymer having an unsaturated group is obtained by reacting a polymer having a functional group such as a hydroxyl group in the molecule with an organic compound having an active group and an unsaturated group that are reactive with the functional group. .
  • an unsaturated group-containing polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound.
  • hydrosilylation is performed by allowing hydrosilane having a crosslinkable silicon group to act on the obtained reaction product.
  • a hydroxyl group-terminated polyoxyalkylene polymer obtained using a double metal cyanide complex catalyst such as zinc hexacyanocobaltate is alkoxideized and then reacted with allyl chloride to form allyloxy (CH 2 ⁇ CHCH 2 O—).
  • a double metal cyanide complex catalyst such as zinc hexacyanocobaltate
  • allyl chloride to form allyloxy (CH 2 ⁇ CHCH 2 O—).
  • Examples thereof include a method in which a base-terminal polyoxyalkylene polymer is produced and hydrosilylated by the action of a silane compound such as dimethoxymethylsilane.
  • hydroxylating the hydroxyl group-terminated polyoxyalkylene polymer it can be reacted with methallyl chloride to produce a methallyloxy group-terminated polyoxyalkylene polymer, and hydrosilylated with a silane compound such as dimethoxymethylsilane.
  • a methallyloxy (CH 2 ⁇ C (CH 3 ) CH 2 O—) group-terminated polyoxyalkylene polymer is used, a polymer having a higher silylation rate than an allyloxy group-terminated polyoxyalkylene polymer can be obtained.
  • the curable composition using a polymer can give a cured product having a large mechanical strength.
  • the polymer having a crosslinkable silicon group derived from a methallyloxy group-terminated polyoxyalkylene polymer can be used by mixing with a polymer having a crosslinkable silicon group derived from an allyloxy group-terminated polyoxyalkylene polymer.
  • a polymer having a functional group such as a hydroxyl group, an epoxy group or an isocyanate group in a molecule and a compound having a functional group showing reactivity to the functional group and a crosslinkable silicon group are reacted.
  • a method of reacting a polymer having a hydroxyl group at a terminal with a compound having an isocyanate group and a crosslinkable silicon group is high in a relatively short reaction time. It is preferable because a conversion rate can be obtained. Furthermore, the composition containing a polymer having a crosslinkable silicon group obtained by the method ( ⁇ ) has a lower viscosity and better workability than the composition containing a polymer obtained by the method ( ⁇ ).
  • the method ( ⁇ ) is particularly preferred because the polymer obtained by the method ( ⁇ ) has a strong odor based on the compound having a mercapto group and a crosslinkable silicon group.
  • the main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit or may contain other repeating units.
  • the repeating unit include repeating units derived from ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide and the like.
  • a polymer mainly composed of polypropylene oxide containing propylene oxide units of 80% by weight or more, preferably 90% by weight or more is preferable from the viewpoint of being amorphous or having a relatively low viscosity.
  • a method for synthesizing a polyoxyalkylene polymer for example, a polymerization method using an alkali catalyst such as KOH, or a transition such as a complex obtained by reacting an organoaluminum compound and a porphyrin disclosed in JP-A-61-215623.
  • Polymerization method using metal compound-porphyrin complex catalyst JP-B-46-27250, JP-B-59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No.
  • the ones proposed in Japanese Patent Laid-Open Nos. 61-197631, 61-215622, 61-215623, 61-218632, and 3-72527 are also disclosed.
  • Proposed number average molecular weight 6,000 or more, Mw / Mn is 1.6 or less high molecular weight polyoxypropylene system with narrow molecular weight distribution
  • a crosslinkable silicon group such as dimethoxymethylsilyl group by a hydrosilylation or the like coalescence
  • the component may be linear or branched. If the molecular weight is the same, the use of a linear polymer increases the elongation at break of the cured product compared to the branched polymer, but the viscosity of the composition before curing increases and is difficult to handle. Tend to be.
  • the lower limit of the number average molecular weight of component (D) is preferably 10,000.
  • the upper limit is preferably 50,000, more preferably 30,000, and even more preferably 25,000. If the number average molecular weight is less than 10,000, the elongation property at break of the cured product obtained from the elastic sealing material composition is lowered.
  • the concentration of the crosslinkable functional group (concentration of the crosslinkable silicon group) ) Becomes too low, the curing rate of the composition decreases, and the viscosity of the composition becomes too high, making it difficult to handle.
  • the number average molecular weight of the component (D) is based on the principle of the method for measuring the hydroxyl value of JIS K 1557 and the method for measuring the elementary value as defined in JIS K 0070. Based on the titration analysis based on the molecular weight (terminal group molecular weight) corresponding to the number average molecular weight obtained by directly measuring the end group concentration and considering the polymer structure (branching degree determined by the polymerization initiator used) Defined.
  • a calibration curve of polystyrene-converted number average molecular weight (GPC molecular weight) obtained by general GPC measurement of the polymer precursor and the above-mentioned end group molecular weight is prepared, and the GPC of the polymer is obtained. It is possible to obtain the molecular weight by converting it into a terminal group molecular weight.
  • the molecular weight distribution (Mw / Mn) of the component (D) is preferably narrow from the viewpoint of reducing the viscosity of the elastic sealing material composition.
  • the molecular weight distribution (Mw / Mn) is more preferably 1.6 or less, and still more preferably 1.5 or less.
  • the molecular weight distribution (Mw / Mn) is measured using GPC (polystyrene conversion).
  • the average number of crosslinkable silicon groups in one molecule of the component is preferably 1.2 or more, more preferably 1.3 or more.
  • the upper limit of the average number is not particularly limited, but the average number is preferably 3.0 or less, more preferably 2.4 or less, and even more preferably 2.1 or less.
  • the average number of crosslinkable silicon groups contained in one molecule of component is less than 1.2, the curability of the elastic sealant composition will be insufficient, and if too large, the network structure of the cured product will be insufficient. Too dense, the cured elastic sealant composition will not exhibit good mechanical properties.
  • the average number of crosslinkable silicon groups in one molecule of the component is defined as the average number obtained by a method of quantifying protons on carbon to which the crosslinkable silicon groups are directly bonded by high resolution 1 H-NMR measurement. ing.
  • the crosslinkable silicon group of component (D) may be present as a side chain inside the molecular chain or may be present at the end, but is finally formed when the crosslinkable silicon group exists as a side chain.
  • the amount of the effective network chain contained in the cured product becomes small, so that it becomes easy to obtain a rubber-like cured product having a high elastic modulus and low elongation at break.
  • the crosslinkable silicon group is present near the end of the molecular chain, the amount of effective network chain contained in the finally formed cured product increases, so that the rubber exhibits high strength, high elongation at break and low elastic modulus. It becomes easier to obtain a cured product.
  • the elastic sealant composition containing the component (D) having a crosslinkable silicon group at the end of the molecular chain is preferably used as a sealant for a building in which it is desirable to have large elongation at break and rubber elasticity rich in flexibility as tensile properties. Is preferred.
  • the component (D) is preferably a trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, ⁇ -chloromethyldimethoxysilyl group
  • the component (D) more preferably has one crosslinkable silicon group selected from the group consisting of a dimethoxymethylsilyl group, a trimethoxysilyl group, and a triethoxysilyl group, and is an average of the crosslinkable silicon groups in one molecule.
  • a polyoxyalkylene polymer having a number of 1.3 to 2.4, a number average molecular weight of 10,000 to 30,000, and a molecular weight distribution (Mw / Mn) of 1.5 or less.
  • the component (D) more preferably has a dimethoxymethylsilyl group, the average number of dimethoxymethylsilyl groups in one molecule is 1.3 to 2.4, and the number average molecular weight is 10,000 to 25, It is a polyoxypropylene polymer having a molecular weight distribution (Mw / Mn) of 1.5 or less.
  • the amount of component (D) used is preferably 10 to 90% by weight, more preferably 20 to 50% by weight, based on the solid content of the elastic sealant composition.
  • Component (E) (at least one curing catalyst and / or curing accelerator selected from the group consisting of carboxylic acid metal salts, carboxylic acids, and amine compounds)
  • the component (E) is at least one curing catalyst and / or curing accelerator selected from the group consisting of carboxylic acid metal salts, carboxylic acids, and amine compounds.
  • the component (E) is a curing catalyst and / or a curing accelerator for the component (D).
  • carboxylic acid examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, Linear saturated fatty acids such as heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and laccellic acid; undecylenic acid, lindelic acid, tuzuic acid, fizeteric acid, Myristoleic acid, 2-hexadecenoic acid, 6-hexadecenoic acid, 7-hexadecenoic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclepic acid,
  • carboxylic acid metal salt examples include calcium salts, vanadium salts, iron salts, titanium salts, potassium salts, barium salts, manganese salts, nickel salts, cobalt salts, zirconium salts, tin salts, and lead salts of the carboxylic acids exemplified above.
  • tin salts, bismuth salts, and zirconium salts are preferable from the viewpoint of availability and catalytic activity, and tin carboxylate is more preferable from the viewpoint of balance between mechanical properties of the cured product and no coloring.
  • tin carboxylates tin versatate, tin 2-ethylhexanoate, tin neodecanoate, tin vivalate and the like are more preferable because of their high curing speed and low coloration of the cured product.
  • Examples of the amine compound include butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) Undecene-7 (DBU) is exemplified. Of these, laurylamine and diethylaminopropylamine are preferred in view of availability and catalytic activity.
  • Component (E) is preferably at least one selected from the group consisting of carboxylic acid metal salts and amine compounds, more preferably at least one selected from the group consisting of tin carboxylates and amine compounds, and more preferably Is at least one selected from the group consisting of tin versatate, tin 2-ethylhexanoate, tin neodecanoate, tin vivalate, laurylamine and diethylaminopropylamine, particularly preferably tin 2-ethylhexanoate and laurylamine At least one selected from the group consisting of
  • the amount of the component (E) used is preferably about 0.1 to 20 parts by weight, more preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the component (D).
  • the amount used is less than 0.1 parts by weight, the curing rate of the component (D) tends to be slow, and the curing reaction tends not to proceed sufficiently.
  • the amount used exceeds 20 parts by weight, local heat generation and foaming occur at the time of curing, and it becomes difficult to obtain a good cured product.
  • the elastic sealant composition used in the present invention preferably contains at least one curable compound selected from the group consisting of a photocurable compound, an oxygen curable compound, and an epoxy compound, more preferably light. It contains at least one curable compound selected from the group consisting of a curable compound and an epoxy compound.
  • a photocurable substance is a substance that undergoes a chemical change in its molecular structure in a very short time due to the action of light, resulting in a change in physical properties such as curing.
  • Many compounds such as organic monomers, oligomers, resins or compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, and the like.
  • Unsaturated acrylic compounds include monomers, oligomers or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, including propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl Examples thereof include monomers such as glycol di (meth) dimethacrylate and oligoesters having a molecular weight of 10,000 or less.
  • Aronix M-210 special acrylate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; (Trifunctional) Aronix M -305, Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and (multifunctional) Aronix M-400.
  • a compound having an acrylic functional group is particularly preferable, and a compound having an average of 3 or more functional groups per molecule is preferable (all Aronix is a product of Toagosei Co., Ltd.).
  • polyvinyl cinnamate examples include photosensitive resins having a cinnamoyl group as a photosensitive group, and many polyvinyl cinnamate derivatives are exemplified in addition to those obtained by esterifying polyvinyl alcohol with cinnamic acid.
  • the azide resin is known as a photosensitive resin having an azide group as a photosensitive group.
  • a photosensitive resin in addition to a rubber photosensitive solution in which a diazide compound is added as a photosensitive agent, a “photosensitive resin” (March 17, 1972).
  • sensitizers such as ketones and nitro compounds and accelerators such as amines may enhance the effect of the photocurable compound.
  • the amount of the photocurable compound to be used is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (D). If the amount used is less than 0.01 parts by weight, the effect of enhancing the weather resistance of the cured product obtained from the elastic sealant composition is small, and if the amount used exceeds 20 parts by weight, the cured product becomes too hard, Since it cracks, it is not preferable.
  • oxygen curable compound examples include unsaturated compounds that can react with oxygen in the air.
  • the oxygen curable compound reacts with oxygen in the air to form a cured film near the surface of the cured product, and acts to prevent stickiness of the surface and adhesion of dust and dust to the surface of the cured product.
  • oxygen curable substance examples include drying oils typified by paulownia oil and linseed oil, and various alkyd resins obtained by modifying the compounds; acrylic polymers modified with drying oils, epoxy resins, silicones Resin; Liquid weight such as 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymer obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene And a liquid copolymer such as NBR and SBR obtained by copolymerizing a monomer such as acrylonitrile or styrene having copolymerizability with these diene compounds so that the diene compound is a main component, And various modified products thereof (maleinized modified products, boiled oil modified products, etc.).
  • drying oils typified by paulownia oil and linseed oil, and various alkyd resins obtained by modifying
  • tung oil and liquid diene polymers are particularly preferable.
  • the oxygen curable compound when used in combination with a catalyst or a metal dryer that promotes the oxidative curing reaction, the effect of the oxygen curable compound may be enhanced.
  • these catalysts or metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, zirconium octylate, and amine compounds.
  • the amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of component (D).
  • the amount used is less than 0.1 parts by weight, the improvement of the contamination of the cured product obtained from the elastic sealing material composition is not sufficient, and when the amount used exceeds 20 parts by weight, the tensile properties of the cured product, etc. Tend to be damaged.
  • the oxygen curable substance is preferably used in combination with a photocurable substance.
  • the epoxy compound is not particularly limited as long as it is a compound having an epoxy group.
  • a compound having an epoxy group When a compound having an epoxy group is used, the restorability of the cured product can be improved.
  • the compound having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, compounds shown in epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxy octyl stearate, epoxy butyl Examples include stearate.
  • E-PS is particularly preferred.
  • a compound having one epoxy group in the molecule is preferably 0.5 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of component (D).
  • the silane coupling agent and a reaction product of the silane coupling agent can be added as an adhesiveness imparting agent to the elastic sealant composition used in the present invention. Moreover, adhesiveness imparting agents other than a silane coupling agent can also be used.
  • silane coupling agent examples include ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, ⁇ -isocyanatopropylmethyldimethoxysilane, ⁇ -isocyanatemethyltrimethoxysilane, Isocyanate group-containing silanes such as ⁇ -isocyanatomethyldimethoxymethylsilane; ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy
  • amino-modified silyl polymers silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters, etc., which are derivatives obtained by modifying these, are also used as silane coupling agents. be able to.
  • the amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of component (D).
  • Fillers include reinforcing silica such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; heavy calcium carbonate, colloidal calcium carbonate, carbonic acid Magnesium, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, resin powder (for example, PVC powder, PMMA powder) And fibrous fillers (for example, asbestos, glass fibers and filaments).
  • the amount used is preferably 1 to 300 parts by weight, more preferably 10 to 200 parts by weight, per 100 parts by weight of component (D).
  • a filler selected from fine calcium carbonate, calcined clay, clay, activated zinc white and the like is used in an amount of 1 to 200 parts by weight based on 100 parts by weight of component (D), preferable results are obtained.
  • the component (D) When the component (D) is used in an amount of 5 to 200 parts by weight with respect to 100 parts by weight, preferable results can be obtained.
  • calcium carbonate has a greater effect of improving the strength at break, elongation at break, and adhesion of the cured product as the value of the specific surface area increases.
  • These fillers may be used alone or in combination of two or more.
  • Fatty acid surface-treated colloidal calcium carbonate can be used in combination with calcium carbonate having a particle size of 1 ⁇ m or more, such as heavy calcium carbonate that has not been surface-treated.
  • the elastic sealant composition used in the present invention may contain a physical property modifier that adjusts the tensile properties of the cured product to be produced, if necessary.
  • the physical property modifier is not particularly limited, but examples thereof include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkylisopropenoxysilanes such as ⁇ -glycidoxypropylmethyldiisopropenoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxy Silane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoeth
  • the hardness of the cured product obtained from the elastic sealing material composition can be increased, or conversely, the hardness can be decreased and elongation at break can be produced.
  • the said physical property modifier may be used independently and may be used together 2 or more types.
  • a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis has an action of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
  • Particularly preferred are compounds that produce trimethylsilanol.
  • Examples of the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis include compounds described in JP-A-5-117521.
  • derivatives of alkyl alcohols such as hexanol, octanol and decanol, which are silicone compounds that generate R 3 SiOH such as trimethylsilanol by hydrolysis, trimethylolpropane, glycerin described in JP-A No.
  • a silicone compound that is a derivative of a polyhydric alcohol having 3 or more hydroxyl groups, such as pentaerythritol or sorbitol, and generates R 3 SiOH such as trimethylsilanol by hydrolysis.
  • the amount of the physical property modifier used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of component (D).
  • a thixotropic agent (anti-sagging agent) may be added to prevent sagging and improve workability.
  • the thixotropy imparting agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents may be used alone or in combination of two or more.
  • the amount of the thixotropic agent used is preferably 0.1 to 20 parts by weight per 100 parts by weight of component (D).
  • an antioxidant antioxidant
  • an antioxidant antioxidant
  • cured material obtained from an elastic sealing material composition can be improved.
  • the antioxidant include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants.
  • a hindered phenol antioxidant is preferable.
  • the antioxidant include those described in JP-A-4-283259 and JP-A-9-194731.
  • the amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of component (D).
  • a light stabilizer can be used as necessary.
  • a light stabilizer is used, photooxidative deterioration of the cured product obtained from the elastic sealant composition can be prevented.
  • light stabilizers include benzotriazole light stabilizers, hindered amine light stabilizers, and benzoate light stabilizers, with hindered amine light stabilizers being particularly preferred.
  • Examples of the light stabilizer include Tinuvin 622LD, Tinuvin 144; CHIMASSORB 944LD, CHIMASSORB 119FL (all of which are manufactured by BASF); All are manufactured by ADEKA Corporation); Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all of which are manufactured by Sankyo Lifetech Co., Ltd.) ) And the like.
  • the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of component (D). Specific examples of the light stabilizer are also described in JP-A-9-194731.
  • a tertiary amino group-containing hindered amine light is used as described in JP-A-5-70531.
  • the use of a stabilizer is preferred for improving the storage stability of the elastic sealant composition.
  • the tertiary amino group-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144; CHIMASSORB119FL (all manufactured by BASF); Adekastab LA-57, LA-62, LA-67, LA-63 (all of these are strains) ) Manufactured by ADEKA); Sanol LS-765, LS-292, LS-2626, LS-1114, LS-744 (all of which are Sankyo Lifetech Co., Ltd.).
  • an ultraviolet absorber can be used as necessary.
  • an ultraviolet absorber When an ultraviolet absorber is used, the surface weather resistance of the hardened
  • UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylate UV absorbers, substituted tolyl UV absorbers, and metal chelate UV absorbers. Particularly, benzotriazole UV absorbers Agents are preferred.
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of component (D). It is preferable to use a phenolic antioxidant or a hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.
  • additives may be added as necessary for the purpose of adjusting the physical properties or the physical properties of the cured product obtained therefrom.
  • additives include flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, solvents, Examples include fungicides.
  • flame retardants include flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents, solvents, Examples include fungicides.
  • additives may be used alone or in combination of two or more. Additives are described in, for example, JP-B-4-69659, JP-B-7-108928, JP-A-63-254149, JP-A-64-22904, JP-A-2001-72854, and the like. .
  • the elastic sealant composition used in the present invention can be prepared as a one-component composition that is pre-mixed and then sealed and stored and cured by moisture in the air after construction. Also, an elastic sealant composition is prepared as a two-component composition in which a main component composition containing component (D) and a curing agent composition containing component (E) are separately prepared and mixed before use. You can also
  • the elastic sealant composition used in the present invention is a one-component composition
  • the components containing moisture are used after being dehydrated and dried in advance or during mixing.
  • the elastic sealant composition used in the present invention is a two-component composition
  • the composition is preferably prepared by dehydration and drying.
  • the dehydration drying method when the elastic sealing material composition used in the present invention is a solid such as a powder, a heat drying method is preferable.
  • the elastic sealant composition is liquid, a vacuum dehydration method or a dehydration method using synthetic zeolite, activated alumina, silica gel or the like is preferable. Further, a small amount of an isocyanate compound may be blended in the elastic sealant composition, and the isocyanate group and water may be reacted to dehydrate.
  • the elastic sealing material composition may include lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane.
  • lower alcohols such as methanol and ethanol
  • n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, ⁇ -mercaptopropylmethyldimethoxysilane By adding an alkoxysilane compound such as ⁇ -mercaptopropylmethyldiethoxysilane or ⁇ -glycidoxypropyltrimethoxysilane, the storage stability is further improved.
  • the amount of the dehydrating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of component (D). Part.
  • the specific gravity of the elastic sealing material composition used in the present invention is preferably 0.9 or more and 1.3 or less.
  • the lower limit of the specific gravity is more preferably 1.0, and the upper limit of the specific gravity is more preferably 1.28. If this specific gravity is less than 0.9, a large amount of filler such as calcium carbonate cannot be filled, and the strength of the resulting cured product may be low. Moreover, when this specific gravity exceeds 1.3, when it constructs on a vertical joint, there exists a possibility that a sealing material composition may sag.
  • the elastic sealant composition described above can be used as a sealant for buildings, ships, automobiles, roads and the like. Furthermore, the above-mentioned elastic sealant composition adheres to various adherends such as glass, porcelain, wood, metal, and resin moldings with the help of the primer layer formed from the above-described primer composition. Can do. Therefore, the above-mentioned elastic sealant composition can be used as a sealant and an adhesive for various applications. Moreover, the above-mentioned elastic sealant composition can be used as a contact adhesive in addition to a normal adhesive. Furthermore, the above-mentioned elastic sealant composition is useful as a food packaging material, a cast rubber material, a molding material, and a paint.
  • the present invention is a primer layer (specifically, a layer obtained by curing the primer composition) which is a layer formed from the above primer composition, and a layer formed from the above elastic sealant composition.
  • a laminate with a certain sealing layer (specifically, a layer obtained by curing an elastic sealing material composition) is provided.
  • the present invention also provides a sealing method comprising applying a primer composition onto an adherend to form a primer layer and then filling the elastic sealant composition thereon.
  • the method for applying the primer composition and the method for filling the elastic sealing material composition are not particularly limited, and conventionally known application means such as application by brush, application by roll, application by spray, etc. can be widely employed.
  • the application amount (dry weight) of the primer composition is preferably 3 to 50 g, more preferably 5 to 20 g per 1 m 2 of the adherend area.
  • it may be dried at room temperature or heated at a temperature of about 50 to 120 ° C.
  • a sealing material formed from an elastic sealing material composition can be satisfactorily adhered to various adherends such as metal, glass, porcelain, stone, wood, and resin molding.
  • the thickness of the elastic sealing material composition layer obtained by filling the elastic sealing material composition is usually preferably 0.1 to 5 cm, more preferably 0.5 to 3 cm, and still more preferably 1 to 2 cm.
  • the thickness of the thin layer portion of the elastic sealant composition layer is preferably 0.5 to 40 ⁇ m, more preferably 0.5 to 20 ⁇ m. The same applies to the thickness of the sealing layer obtained by curing this and the thickness of the thin layer portion.
  • a paint for example, a water-based acrylic paint
  • the sealing layer obtained in the present invention does not cause the plasticizer to flow out to the surface of the sealing layer, and the resulting contamination around the sealing joints and contamination of the paint.
  • Conventional urethane-based sealing materials cannot be used in areas where weather resistance is a problem, but in the sealing materials obtained in the present invention, areas where weather resistance is a problem, and areas where paint is applied Any of these can be used.
  • crosslinkable silicon group-containing acrylic copolymer (component (A)) 50 parts by weight of butyl acetate was charged into a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel, The temperature was raised to 110 ° C. while introducing gas.
  • the number average molecular weight of the obtained crosslinkable silicon group-containing acrylic copolymer was 16,000.
  • the number average molecular weight was measured by GPC (Tosoh HLC-8120GPC was used as the liquid feeding system, Tosoh TSK-GEL H type was used as the column, and THF was used as the solvent).
  • the glass transition temperature of the obtained crosslinkable silicon group-containing acrylic copolymer was 52 ° C. when calculated based on the Fox equation.
  • the average number of crosslinkable silicon groups in one molecule of the crosslinkable silicon group-containing acrylic copolymer was 4.3. This average number was calculated from the monomer composition and the number average molecular weight on the assumption that the polymerization conversion was 100%.
  • Primer Composition As shown in Table 1, in 100 parts by weight of the solution (solid content 40% by weight) of the crosslinkable silicon group-containing acrylic copolymer (component (A)) obtained as described above, 2 parts by weight of bis (3-trimethoxysilylpropyl) amine (component (B)), 3 parts by weight of trimethyl orthoacetate as a dehydrating agent, and 28 parts by weight of ethyl acetate as a solvent were added and stirred to obtain a composition. 0.5 parts by weight of a curing catalyst (an organic tin curing catalyst (component (C)) containing no sulfur or an organic tin curing catalyst containing sulfur) is added to each of the obtained compositions, and primer compositions AD Got.
  • a curing catalyst an organic tin curing catalyst (component (C)) containing no sulfur or an organic tin curing catalyst containing sulfur
  • dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd., trade name “Neostan U-810”
  • dibutyltin diacetylacetonate Nitto Kasei Co., Ltd.
  • organotin curing catalyst component (C)
  • component (C) organotin curing catalyst containing no sulfur
  • Dibutyltin bis (lauryl mercapto) manufactured by Nitto Kasei Co., Ltd., trade name “SCAT-1” was used as a curing catalyst.
  • polyoxyalkylene polymer having crosslinkable silicon group component (D)
  • polypropylene triol as an initiator, polymerization of propylene oxide with zinc hexacyanocobaltate glyme complex catalyst, and number average molecular weight (terminal group molecular weight) )
  • a hydroxy-terminated polyoxypropylene polymer having a branched structure of 18,000 was obtained.
  • methanol was distilled off, and allyl chloride was further added to form a terminal hydroxyl group. Converted to an allyl group.
  • a branched polyoxypropylene polymer having a methylsilyl group (component (D)) was obtained.
  • the average number of dimethoxymethylsilyl groups in one molecule of the polymer was 2.1.
  • the elastic sealant compositions used in Examples and Comparative Examples are two-component compositions (a main component composition containing (D) component and a curing agent composition containing component (E)). Manufactured as.
  • component (D) Production of main component composition containing component To 100 parts by weight of the polyoxyalkylene polymer having a crosslinkable silicon group obtained as described above (component (D)), colloidal calcium carbonate (Shiraishi Kogyo ( Co., Ltd., trade name “Tenka CCR”) 120 parts by weight, heavy calcium carbonate (Shiraishi Calcium Industry Co., Ltd., trade name “Whiteon SB”) 20 parts by weight, plasticizer (Shin Nippon Rika Co., Ltd.) 44 parts by weight, product name “DINP”, epoxy compound (manufactured by Shin Nippon Rika Co., Ltd., product name “E-PS”), anti-sagging agent (manufactured by Enomoto Kasei Co., Ltd., product name “Dispalon”) # 308 ") 3 parts by weight, UV absorber (BASF, trade name” Tinubin 326 ”) 1 part, antioxidant (BASF, trade name” Irganox 1010 ”) 1 part, photocurable compound (
  • Curability test Primer compositions A to D obtained as described above, or commercially available primer E (main component: urethane resin / synthetic rubber), or commercially available primer F (main component: urethane resin) Using the thus obtained elastic sealant composition (main agent composition and hardener composition), the curability of the elastic sealant composition layer was evaluated.
  • primer composition A, primer composition B or primer composition C is used, and in Comparative Examples 1 to 3, primer composition D, commercially available primer E or commercially available primer F is used. did.
  • An anodized aluminum plate (150 ⁇ 70 ⁇ 0.8 mm) was used as the adherend.
  • Masking tape (thickness: about 50 ⁇ m) was pasted to both ends of the surface of the aluminum plate with a width of about 10 mm from the end.
  • Primer compositions A to D or a commercially available primer E or F (hereinafter abbreviated as “primer”) were applied once to this adherend (application amount per 1 m 2 of adherend area (dry weight)): 8 g ).
  • the primer was dried and cured at 23 ° C. and 50% RH for 30 minutes to form a primer layer, and then the main component composition and the curing agent composition obtained as described above were mixed at a weight ratio of 317: 29.9. This was applied to the test specimen with a glass rod so as to have the same thickness as the masking tape to form an elastic sealing material composition layer having a thickness of 50 ⁇ m.
  • an elastic sealing material composition layer having a thickness of 1 to 2 ⁇ m was formed in the same manner as described above except that no masking tape was applied to the adherend.
  • Examples 1 to 3 using the primer compositions A to C containing the components (A) to (C) are organotin curing catalysts containing sulfur instead of the component (C) ( Comparative Example 1 using primer composition D containing dibutyltin bis (lauryl mercapto)) and commercially available primer E (main component: urethane resin / synthetic rubber) or commercially available primer F (main component: urethane resin) Compared with Comparative Examples 2 and 3 to be used, the curability of the elastic sealing material composition layer (particularly the curability of the elastic sealing material composition layer having a thickness of 1 to 2 ⁇ m) is good.
  • the laminate and sealing method of the present invention can be used for various applications (for example, sealing of buildings, ships, automobiles, roads, etc.).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Sealing Material Composition (AREA)

Abstract

　La présente invention concerne un corps stratifié comprenant une couche primaire et une couche d'étanchéité, dans lequel la couche primaire est formée à partir d'une composition primaire qui contient (A) un copolymère acrylique contenant un groupe silicium réticulable, (B) un composé de silane comprenant des groupes amino et/ou un produit de réaction de celui-ci, et (C) un catalyseur de durcissement organostannique qui ne contient pas de soufre. Ladite couche d'étanchéité est formée à partir d'une composition de matériau d'étanchéité élastique qui contient (D) un copolymère de polyoxyalkylène comprenant des groupes silicium qui comprennent des groupes hydrolysables aptes à la réticulation par formation de liaisons siloxane, et (E) au moins un catalyseur de durcissement et/ou un accélérateur de durcissement choisi dans le groupe constitué par des sels métalliques d'acide carboxylique, des acides carboxyliques, et des composés amines.
PCT/JP2015/072732 2014-08-11 2015-08-11 Corps stratifié et procédé d'encapsulation WO2016024584A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11209684A (ja) * 1998-01-23 1999-08-03 Kanegafuchi Chem Ind Co Ltd 窯業系サイディング用プライマー
WO2012036109A1 (fr) * 2010-09-14 2012-03-22 株式会社カネカ Composition durcissable
JP2012229398A (ja) * 2011-04-13 2012-11-22 Kaneka Corp 反応性可塑剤およびこれを含む硬化性組成物
JP2013091754A (ja) * 2011-10-27 2013-05-16 Yokohama Rubber Co Ltd:The 湿気硬化型樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3687320B2 (ja) * 1998-01-23 2005-08-24 株式会社カネカ プライマー組成物
JP2003071376A (ja) * 2001-08-31 2003-03-11 Sunstar Eng Inc 薄層塗布部の硬化方法
JP2003073617A (ja) * 2001-09-05 2003-03-12 Konishi Co Ltd プライマー組成物
JP4246458B2 (ja) * 2002-08-28 2009-04-02 コニシ株式会社 プライマー組成物
JP2007023224A (ja) * 2005-07-20 2007-02-01 Kaneka Corp 変成シリコーン用１液プライマー組成物
JP5667854B2 (ja) * 2010-12-01 2015-02-12 株式会社カネカ １液組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11209684A (ja) * 1998-01-23 1999-08-03 Kanegafuchi Chem Ind Co Ltd 窯業系サイディング用プライマー
WO2012036109A1 (fr) * 2010-09-14 2012-03-22 株式会社カネカ Composition durcissable
JP2012229398A (ja) * 2011-04-13 2012-11-22 Kaneka Corp 反応性可塑剤およびこれを含む硬化性組成物
JP2013091754A (ja) * 2011-10-27 2013-05-16 Yokohama Rubber Co Ltd:The 湿気硬化型樹脂組成物

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