WO2011089987A1 - Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif - Google Patents

Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif Download PDF

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WO2011089987A1
WO2011089987A1 PCT/JP2011/050620 JP2011050620W WO2011089987A1 WO 2011089987 A1 WO2011089987 A1 WO 2011089987A1 JP 2011050620 W JP2011050620 W JP 2011050620W WO 2011089987 A1 WO2011089987 A1 WO 2011089987A1
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group
curable
flame
moisture
flame retardant
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PCT/JP2011/050620
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English (en)
Japanese (ja)
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純 乾
慎二 占部
井上　文子
佐藤　慎一
佐藤　明寛
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コニシ株式会社
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Priority to JP2011550895A priority Critical patent/JPWO2011089987A1/ja
Publication of WO2011089987A1 publication Critical patent/WO2011089987A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • 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
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a flame retardant moisture curable resin composition, a flame retardant moisture curable adhesive containing the composition, and an adhesion method using the same, and in particular, electrical products and precision instruments that require flame retardancy. Or a flame retardant moisture curable resin composition having excellent performance as an adhesive, an adhesive, a sealing material, a pressure sensitive adhesive precursor for assembly of automobile parts, etc., and the flame retardant moisture curing TECHNICAL FIELD
  • the present invention relates to a flame-retardant moisture-curing adhesive having a mold resin composition as an active ingredient, and an adhesion method using the same.
  • a curable silicone resin whose main chain is an organic polymer and has a reactive silicon group that can be cross-linked by moisture in the atmosphere in its molecule is widely used as a base polymer for sealing materials, adhesives, paints, etc. Yes.
  • Such a curable resin becomes an elastic body after curing and can follow a strain due to a difference in thermal expansion to prevent cracking. Therefore, such a curable resin is preferably used particularly when bonding different kinds of materials.
  • a flame retardant in a flame retardant adhesive generally, a phosphorus flame retardant, a halogen flame retardant, a metal hydroxide, or the like has been used.
  • phosphorus-based flame retardants have the problem that inorganic phosphorus-based flame retardants may reduce water resistance and corrode copper.
  • Organic phosphorus-based flame retardants have a structure such as human health risk and water eutrophication. The problem is concerned.
  • halogen-based flame retardants represented by brominated flame retardants have been pointed out to have adverse effects on the environment such as human health risk, metal corrosion and air pollution. This halogen-based flame retardant greatly improves the flame retardant effect when used in combination with antimony oxide, but there is also a problem that antimony oxide is not preferable because it has toxicity.
  • Non-halogen / non-phosphorous flame retardant metal hydroxides such as aluminum hydroxide and magnesium hydroxide can be used as flame retardants as an elastic flame retardant moisture curable adhesive composition with relatively little environmental impact. It has been proposed (Patent Documents 1, 2, 3, and 4). However, in general, a hydrolyzable silicon group cannot obtain a practical curing rate unless a heavy metal catalyst such as an organic tin catalyst is used. Therefore, in the methods described in these patents, only those using organic heavy metal catalysts (especially organotin catalysts) having a substantially large environmental load can be produced.
  • the flame retardant adhesive is substantially free of organic heavy metal catalysts (especially organotin catalysts) having a large environmental load due to increasing awareness of environmental problems, or the content thereof is set to 0.
  • organic heavy metal catalysts especially organotin catalysts
  • the content thereof is set to 0.
  • it By limiting it to less than 1% (1000 ppm), it is not subject to legal regulations such as the PRTR law, and it has come to be required to design to further reduce the environmental load.
  • JP-A-11-310682 WO2005 / 088765 pamphlet JP 2007-84633 A JP 2007-332258 A
  • the present invention is an environmental load having excellent performance as an adhesive, a fixing agent, a sealing material, and a pressure sensitive adhesive precursor for members in the electric / electronic market, the automotive parts market, the construction market, the civil engineering market, etc. that require flame retardancy.
  • An object of the present invention is to provide a flame-retardant moisture-curable resin composition with reduced flame resistance, a flame-retardant moisture-curable adhesive containing the composition, and an adhesion method using the adhesive.
  • the present inventors have blended a metal hydroxide and a basic catalyst into a curable resin having a hydrolyzable silicon group having a specific structure.
  • a metal hydroxide and a basic catalyst into a curable resin having a hydrolyzable silicon group having a specific structure.
  • the present invention has been completed by finding that a flame-retardant moisture-curable resin composition having a suitable curing rate can be obtained.
  • a hydrolyzable silicon group having a chemical structure in which a carbon atom is bonded to a silicon atom of a hydrolyzable silicon group and a hetero atom having an unshared electron pair is bonded to the carbon atom
  • It comprises a curable silicone resin (A-1) contained therein, a metal hydroxide powder (B) having an average particle size of 0.1 to 200 ⁇ m, and an aminosilane compound (C).
  • the present invention relates to a flame retardant moisture curable resin composition.
  • a cured product having flame retardancy is obtained by blending the metal hydroxide powder (B) and the aminosilane compound (C) with the curable silicone resin (A-1) having a specific structure. And a curable composition having a practical curing rate can be obtained without using an organic heavy metal catalyst having a high environmental load.
  • the metal hydroxide powder (B) is an untreated metal hydroxide powder (B-1) having an average particle diameter of 0.1 to 200 ⁇ m and / or average particles.
  • the flame-retardant moisture-curable composition according to the first invention characterized in that it is a metal hydroxide powder (B-2) treated with a silane coupling agent having a diameter of 0.1 to 200 ⁇ m. is there.
  • an untreated metal hydroxide powder (B-1) and / or a metal hydroxide powder (B-2) treated with a silane coupling agent Is used to obtain a cured product that is more stable and easy to produce, has flame retardancy, and has a practical curing rate without using an organic heavy metal catalyst with a high environmental load. be able to.
  • the third invention is characterized in that the hydrolyzable silicon group contained in the molecule of the curable silicone resin (A-1) is represented by the formula (1). It is related with the said flame-retardant moisture hardening type composition.
  • the hydrolyzable silicon group has a chemical structure represented by the following formula (1), curing is performed by introducing a heteroatom having an unshared electron pair into the carbon atom bonded to the silicon atom of the hydrolyzable silicon group relatively easily and efficiently. Can be obtained.
  • A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group, and R 1 is a carbon atom having 1 to 20 carbon atoms.
  • R 1 is a carbon atom having 1 to 20 carbon atoms.
  • a hydrogen group, R 2 is a group selected from organic groups having 1 to 20 carbon atoms, and a is 0, 1 or 2.
  • the fourth invention is a flame retardant moisture curable type according to any one of the first to third inventions, characterized in that the main chain of the curable silicone resin (A-1) is essentially polyoxyalkylene. It relates to a composition.
  • a fifth invention is characterized in that the organic group having 1 to 20 carbon atoms represented by R 2 is selected from a phenyl group, an alkyl group having 1 to 20 carbon atoms and a 2- (butoxy) ethyl group.
  • the present invention relates to a flame retardant moisture curable composition according to any one of the inventions 1 to 4.
  • a sixth invention further includes a curable silicone resin (A-2) having a hydrolyzable silicon group represented by the formula (2) in the molecule
  • the present invention relates to a flame retardant moisture curable composition according to the invention.
  • -X-SiR 3 b (OR 4 ) 3-b Formula (2) (Wherein X is a hydrocarbon group having 2 or more carbon atoms, R 3 is a hydrocarbon group having 1 to 20 carbon atoms, R 4 is a group selected from organic groups having 1 to 20 carbon atoms, and b is 0 1 or 2 is shown respectively.)
  • Adhesiveness to various adherends by using a curable silicone resin (A-2) having a hydrolyzable silicon group represented by formula (2) which is a generally known silyl group structure Therefore, it is easy to adjust various physical properties, so that it becomes easy to obtain a flame-retardant moisture-curable composition meeting various requirements.
  • a seventh invention is characterized in that the organic group having 1 to 20 carbon atoms represented by R 4 is selected from a phenyl group, an alkyl group having 1 to 20 carbon atoms and a 2- (butoxy) ethyl group.
  • the present invention relates to a flame retardant moisture curable composition according to the invention of No. 6.
  • the sixth or seventh embodiment wherein 10 parts by weight to 900 parts by weight of the curable silicone resin (A-2) is blended with 100 parts by weight of the curable silicone resin (A-1).
  • the present invention relates to a flame retardant moisture curable composition according to the invention.
  • the amount of the curable silicone resin (A-2) to 10 to 900 parts by weight it becomes easier to adjust various physical properties and cure speed. If the amount is less than 10 parts by weight, the amount of the curable silicone resin (A-2) is too small to adjust the physical properties. If the amount exceeds 900 parts by weight, the curable silicone resin (A-1) is relatively difficult to adjust. It becomes difficult to maintain the curing speed because the amount of the resin decreases.
  • a ninth invention is characterized in that the main chain of the curable silicone resin (A-2) is essentially polyoxyalkylene and / or poly (meth) acrylate.
  • the present invention relates to a flame retardant moisture curable composition according to the invention.
  • the tenth invention is the metal hydroxide powder (B), the untreated metal hydroxide powder (B-1), or the metal hydroxide powder treated with the silane coupling agent.
  • the flame retardant moisture-curable composition according to any one of the first to ninth inventions, wherein the metal hydroxide in (B-2) is aluminum hydroxide and / or magnesium hydroxide It is.
  • the eleventh aspect of the present invention is the flame retardancy according to any one of the first to tenth aspects of the present invention, characterized by containing essentially no organic tin-based catalyst or having an organic tin-based catalyst content of less than 1000 ppm.
  • the present invention relates to a moisture curable composition.
  • the twelfth invention relates to a flame retardant moisture curable adhesive comprising the flame retardant moisture curable composition of any one of the first to eleventh inventions as an active ingredient.
  • the thirteenth invention relates to a flame retardant moisture curable sealant composition
  • a flame retardant moisture curable sealant composition comprising the flame retardant moisture curable composition of any one of the first to eleventh inventions as an active ingredient.
  • the fourteenth invention relates to a flame retardant moisture curable pressure sensitive adhesive precursor composition
  • a flame retardant moisture curable pressure sensitive adhesive precursor composition comprising the flame retardant moisture curable composition of any one of the first to eleventh inventions as an active ingredient.
  • the fifteenth aspect of the present invention relates to a method for bonding an electrical product, a precision instrument, or an automobile part, characterized in that constituent members are bonded using the flame-retardant moisture-curable adhesive of the twelfth aspect of the present invention.
  • the sixteenth aspect of the invention relates to an electrical product, precision instrument or automobile part obtained by bonding constituent members using the flame retardant moisture-curing adhesive of the twelfth aspect of the invention.
  • a flame retardant moisture curable resin composition that has excellent performance and has a high environmental impact and is extremely low or substantially free of organic heavy metal catalyst, and has low human health risk and is friendly to the environment, And the effect that the adhesive agent and the adhesion
  • the curable silicone resin (A-1) in the present invention has a chemical structure in which a carbon atom is bonded to a silicon atom of a hydrolyzable silicon group, and a hetero atom having an unshared electron pair is bonded to the carbon atom. It is a curable resin having hydrolyzable silicon groups in the molecule.
  • a hydrolyzable silicon group in which a carbon atom is bonded to a silicon atom and a heteroatom having an unshared electron pair is bonded to the carbon atom exhibits a moisture reactivity much higher than that of a normal hydrolyzable silicon group.
  • the curable silicone resin (A-1) does not use an organic tin compound, or is sufficiently cured even when used in a much smaller amount than usual (less than 1000 ppm relative to the total mass part of the curable resin composition). Expresses sex.
  • a curable resin having a hydrolyzable silicon group-containing functional group represented by the following general formula (1) in the molecule is preferably used.
  • a chemical structure represented by the following general formula (1) is expressed as “ ⁇ -silane structure”.
  • A is a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in a hydrolyzable silicon group
  • R 1 is a carbon atom having 1 to 20 carbon atoms
  • R 2 is an organic group having 1 to 20 carbon atoms (this is an aryl group such as a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxyalkyl group such as a 2- (butoxy) ethyl group).
  • One or more groups selected from: a represents 0, 1 or 2, respectively
  • the heteroatom is not particularly limited as long as it has an unshared electron pair, but an atom with high nucleophilicity or an atom with high electronegativity is particularly preferable.
  • nitrogen (N) atoms, oxygen (O) atoms, sulfur (S) atoms, and halogen (I, Br, Cl, F) atoms are preferred because of the availability of raw materials and the ease of synthesis. From the balance of various performances, a nitrogen (N) atom, an oxygen (O) atom, and a sulfur (S) atom are more preferable, and a nitrogen (N) atom is particularly preferable from the viewpoint of high curability.
  • the heteroatom is a highly nucleophilic atom or an atom with high electronegativity, it is not clear why the moisture reactivity is much higher than a normal hydrolyzable silicon group, but it is highly nucleophilic.
  • the high nucleophilic atom interacts with neighboring silicon atoms to increase the reactivity of the silicon atom.
  • the effect of the high electronegativity atom It is surmised that the reason is that the reactivity of silicon atoms is increased by electrons flowing from silicon atoms through adjacent carbon atoms.
  • the curable silicone resin (A-1) may be appropriately selected in order to obtain a desired performance, and may be used alone or in combination of two or more.
  • the curable resin (A-1) will be described in detail with a curable resin having a hydrolyzable silicon group represented by the general formula (1) in the molecule as a representative example.
  • a bonding functional group in which a hetero atom having an unshared electron pair is bonded to a silicon atom via a methylene group.
  • the bond functional group is a structure connecting the hydrolyzable silicon group and the main chain, and a heteroatom having an unshared electron pair is bonded to a methylene group bonded to a silicon atom contained in the hydrolyzable silicon group.
  • (thio) urethane groups, allophanate groups, other N-substituted urethane groups, N-substituted allophanate groups such as (thio) urethane group-derived linking groups, (thio) urea groups, biuret groups , Other N-substituted urea groups, N, N′-substituted urea groups, N-substituted biuret groups, N, N′-substituted biuret groups and the like (thio) urea-derived linking groups, amide groups, N—
  • Examples include, but are not limited to, amide group-derived linking groups such as substituted amide groups, nitrogen-containing characteristic groups typified by imino group-derived linking groups, (thio) ester groups, and (thio) ether groups.
  • a nitrogen-containing characteristic group is preferable because of high curability, and a bonding group derived from (thio) urethane group and a bonding group derived from (thio) urea are more preferable from the viewpoint of ease of synthesis.
  • the silicon atom has 1 to 3 alkoxy groups (OR 2 ) as hydrolyzable groups and 2 hydrocarbon groups (R 1 ) as the remaining bonds. ⁇ 0 are connected.
  • the alkoxy group (OR 2 ) may be an aryloxy group such as a phenoxy group, an alkoxy group having 1 to 20 carbon atoms, and an alkoxyalkoxy group such as 2- (butoxy) ethoxy group, a methoxy group, An alkoxy group having 1 to 4 carbon atoms such as an ethoxy group, a propoxy group, or a butoxy group is preferable, and a methoxy group or an ethoxy group is more preferable.
  • the hydrocarbon group (R 1 ) bonded to the remaining bond of the silicon atom may be an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a phenyl group.
  • a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.
  • the number average molecular weight of the curable silicone resin (A-1) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. preferable.
  • the number average molecular weight is less than 1,000, the resulting cured product may have brittle properties because the crosslinking density becomes too high.
  • the number average molecular weight exceeds 80,000, the viscosity is increased and workability is improved.
  • blending may be limited because a large amount of a diluent or a plasticizer is required because of deterioration.
  • Examples of the main chain skeleton of the curable silicone resin (A-1) include polyoxyalkylenes, vinyl polymers (eg, polyacrylates, polymethacrylates, etc.), saturated hydrocarbon polymers, unsaturated hydrocarbon polymers, polyesters, Examples thereof include one or more skeletons selected from main chain skeletons generally used for silicone resins such as polycarbonate and polydimethylsiloxane, and modified silicone resins. In particular, it is preferable that it is essentially polyoxyalkylene from the viewpoint of easy availability and film properties of the cured product.
  • “essentially” means that the skeleton is a main element of a repeating unit which is the main chain skeleton of the curable silicone resin (A-1), that is, 50% by weight or more.
  • the skeleton may be contained alone or two or more kinds in the curable silicone resin (A-1).
  • synthesis may be performed by a conventionally known method. For example, (1) a method in which an isocyanate methylalkoxysilane compound is reacted with a polyol compound, (2) a urethane prepolymer is synthesized by reacting a polyol compound with a polyisocyanate compound, and then a mercaptomethylalkoxysilane compound or aminomethylalkoxy is added to the urethane prepolymer.
  • a silane compound having a chemical structure with bonded atoms , And the like [process is described, for example, WO2010 / 004948, etc.] which method of addition reaction by silylation reactions.
  • trialkoxysilane, alkyldialkoxysilane, and dialkylalkoxysilane are collectively referred to as “alkoxysilane”.
  • the amino group of the aminomethylalkoxysilane compound may be a primary amino group or a secondary amino group.
  • the secondary amino group is more preferably a curable silicone resin (A-1). ) Is preferable because it can be adjusted to a relatively low viscosity.
  • the aminomethylalkoxysilane compound having a secondary amino group can be derived from an aminomethylalkoxysilane compound having a primary amino group.
  • the curable silicone resin (A-1) can be easily synthesized by the method described in JP-T-2004-518801, JP-T-2004-536957, JP-T-2005-501146, and the like.
  • a commercially available product of the curable silicone resin (A-1) is GENIOSIL STP-E10 (number average molecular weight about 10,000 converted from methoxy group equivalent, viscosity about 10,000 mPa ⁇ s / 25 ° C. manufactured by Wacker Chemie AG. (Catalog value)), GENIOSIL STP-E30 (number average molecular weight about 16,000 converted from methoxy group equivalent, viscosity about 30,000 mPa ⁇ s / 25 ° C. (catalog value)), and the like.
  • a in the above formula (1) is —O—CO—NH—
  • R 1 is CH 3
  • R 2 is CH 3
  • the curable silicone resin (A-2) in the present invention is a curable silicone resin having a hydrolyzable silicon group represented by the following general formula (2) in the molecule.
  • the curable silicone resin (A-2) used in the present invention is preferably liquid at room temperature from the viewpoint of workability. Further, the curable silicone resin (A-2) may be used alone or in combination of two or more according to the desired performance.
  • Formula (2) (Where X is a hydrocarbon group having 2 or more carbon atoms, R 3 is a hydrocarbon group having 1 to 20 carbon atoms, R 4 is an organic group having 1 to 20 carbon atoms (this is an aryl group such as a phenyl group) A group selected from a group represented by an alkyl group having 1 to 20 carbon atoms and an alkoxyalkyl group of 2- (butoxy) ethyl group), b represents 0, 1 or 2, respectively.
  • hydrolyzable silicon group As represented by the general formula (2), 2 to 0 hydrocarbon groups (R 3 ) are bonded, and 1 hydrolyzable group (OR 4 ) is bonded to the silicon atom. ⁇ 3 are connected. The main chain is bonded to the silicon atom via the hydrocarbon group X.
  • the hydrocarbon group (R 3 ) is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, or an aryl group such as a phenyl group. , A propyl group and a butyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.
  • Examples of the hydrolyzable group (OR 4 ) include a methoxy group, an ethoxy group, a propoxy group, an alkoxy group having 1 to 4 carbon atoms such as butoxy, an aryloxy group such as a phenoxy group, and an alkoxy of 2- (butoxy) ethyl group.
  • Alkyl groups can be used. Among these, an alkoxy group is preferable from the viewpoint of ease of handling, availability, and the like.
  • the alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group, and more preferably a methoxy group or an ethoxy group.
  • main chain skeleton of the curable silicone resin (A-2) examples include polyoxyalkylene, vinyl polymers (eg, polyacrylate, polymethacrylate, etc.), saturated hydrocarbon polymers, unsaturated hydrocarbon polymers, polyesters, One or more skeletons selected from main chain skeletons generally used for silicone resins such as polycarbonate and polydimethylsiloxane and modified silicone resins are employed. In particular, it is preferably polyoxyalkylene and / or poly (meth) acrylate from the viewpoints of easy availability and film properties of the cured product.
  • skeleton is a main element of a repeating unit which is the main chain skeleton of the curable silicone resin (A-2), that is, 50% by weight or more, particularly 90% by weight or more. Means. Further, the skeleton may be contained alone or two or more kinds may be contained in the curable silicone resin (A-2).
  • the number average molecular weight of the curable silicone resin (A-2) is not particularly limited, but is preferably 1,000 to 80,000, more preferably 1,500 to 60,000, and particularly preferably 2,000 to 40,000. preferable.
  • the number average molecular weight is less than 1,000, the resulting cured product may have brittle properties because the crosslinking density becomes too high.
  • the number average molecular weight exceeds 80,000, the viscosity is increased and workability is improved.
  • blending may be limited, for example, a large amount of a solvent or a diluent is required due to deterioration.
  • the hydrolyzable silicon group and the main chain skeleton of the curable silicone resin (A-2) are bonded via a hydrolyzable silicon group-derived hydrocarbon group X having 2 or more carbon atoms and a main chain-derived linking group.
  • the linking group is generated from the main chain by a chemical reaction when a hydrolyzable silicon group is introduced into the main chain skeleton.
  • an alkylene group having 2 to 8 carbon atoms such as ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, dimethylbutylene group, hexylene group, phenylene group, (thio) urethane bond, (thio ) Urea bonds, substituted (thio) urea bonds, (thio) ether bonds, carbonate groups, and the like, and divalent chemical bonds including a plurality of these and other chemical structures.
  • an alkylene group having 2 to 8 carbon atoms such as ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, dimethylbutylene group, hexylene group, phenylene group, (thio) urethane bond, (thio ) Urea bonds, substituted (thio) urea bonds, (thio) ether bonds, carbonate groups, and the like, and divalent chemical bonds including a plurality of these and other chemical structures.
  • the curable silicone resin (A-2) has a hydrolyzable silicon group in the molecule and a specific polar group in the molecule (particularly preferably in the bonding group).
  • a curable resin can be suitably used.
  • the specific polar group is a urethane bond group, a thiourethane bond group, a urea bond group, a thiourea bond group, a substituted urea bond group, a substituted thiourea bond group, an amide bond group, a sulfide bond group, a hydroxy group,
  • urethane bonding group thiourethane bonding group, urea bonding group, thiourea bonding group, substituted urea bonding group, substituted thiourea bonding group, amide bonding group, primary amino group
  • a nitrogen-containing polar group such as a secondary amino group and a tertiary amino group
  • a urethane bond group (—NHCOO—), a urea bond group (—NHCONH—), a substituted urea bond group (—NHCONR—;
  • R an organic group, for example, an alkyl group, an aryl group, a reaction residue of an ⁇ , ⁇ -unsaturated compound, etc.) is most preferable.
  • curability of the curable resin itself is increased is that the specific polar groups present in the molecule of the curable resin form domains, and as a result, the coupling reaction between hydrolyzable silicon groups of the curable resin occurs. This is considered to be further promoted.
  • a large number of commercially available curable silicone resins are sold as silicone resins or modified silicone resins.
  • Kaneka's Silyl series Kaneka MS polymer series, MA series, EP series, SA series, OR series, Exastar series made by Asahi Glass, GENIOSIL STP-E15, GENIOSIL STP-E35 made by Wacker Chemie AG
  • Examples include silane-modified polyalphaolefins manufactured by Degussa Japan, KC series, KR series, X-40 series, XPR series manufactured by Toagosei Co., Ltd. However, it is not limited to these.
  • the curable resin having a hydrolyzable silicon group in the molecule and the above-mentioned specific polar group in the molecule can be synthesized by a conventionally known method.
  • a conventionally known method for example, the method described in Japanese Patent No. 3030020, Japanese Patent Application Laid-Open No. 2005-54174, Japanese Patent Application Laid-Open No. 2005-139452, Japanese Patent Application Publication No. 2004-518801, Japanese Patent Application Publication No. 2004-536957, Japanese Patent Application Publication No. 2005-501146. The method described in the publication etc. is mentioned.
  • the blending amount of the curable silicone resin (A-2) is 1000 parts by weight or less, preferably 10 to 900 parts by weight, and preferably 20 to 200 parts by weight with respect to 100 parts by weight of the curable silicone resin (A-1). 800 parts by weight are more preferable, and 30 to 700 parts by weight are particularly preferable. If the amount of the curable silicone resin (A-2) is too large, the curing time may be delayed. On the other hand, if the amount of the curable silicone resin (A-2) is too small, it is difficult to obtain the effect on the physical properties to which the curable silicone resin (A-2) is added.
  • the main chain skeletons of the curable silicone resins (A-1) and (A-2) may be the same or different. However, it is preferable that the curable silicone resins (A-1) and (A-2) are compatible since the effects of the present invention are more easily obtained.
  • a conventionally known technique can be used. For example, a compound generally known as a compatibilizing agent can be added.
  • the main chain skeletons of the curable silicone resins (A-1) and (A-2) can be improved by selecting a combination having good compatibility. Specifically, the compatibility can be improved by using the main chain skeleton having a relatively close polarity.
  • the compatibility is very good. Even if they are not the same, it is also preferable to select skeletons having relatively similar structures such as polyolefin skeletons or polyether skeletons. Furthermore, it is known that a polyoxyalkylene skeleton and a poly (meth) acrylate skeleton having a specific structure also have good compatibility. Examples of combinations having good compatibility as described above are exemplified, but the present invention is not limited to these.
  • the metal hydroxide powder refers to a metal hydroxide formed into a powder form.
  • the metal hydroxide constituting the metal hydroxide powder (B) aluminum hydroxide, magnesium hydroxide, calcium hydroxide, composite metal hydroxide or the like is used, and aluminum hydroxide and / or magnesium hydroxide is used. Are preferably used.
  • a metal hydroxide powder (B) may be used individually by 1 type, and may be used together 2 or more types. Examples of the metal hydroxide powder (B) include an untreated metal hydroxide powder and a metal hydroxide powder treated with a treating agent. An untreated metal hydroxide powder (B- Metal hydroxide powder (B-2) treated with 1) or a silane coupling agent is preferred.
  • the untreated metal hydroxide powder (B-1) in the present invention is used without special treatment of the powder surface after obtaining a metal hydroxide powder.
  • the metal hydroxide powder (B-2) treated with the silane coupling agent in (1) is one in which the metal hydroxide powder is surface-treated with the silane coupling agent.
  • the surface of the metal hydroxide powder is not treated at all (B-1), it can be used without any problem.
  • surface treatment fillers obtained by treating the surface of the powder, which is a filler, with a treatment agent have been well known, and are often used to improve various physical properties, improve dispersibility, improve separation properties, etc. It has been.
  • the flame retardant that is more stable and easier to produce by using the specific surface-treated metal hydroxide powder. It is easy to obtain a moisture-curable composition.
  • the desired flame-retardant moisture-curable composition can be obtained by devising the blending amount and production method. Obtainable.
  • the curable silicone resin (A-1) having an ⁇ -silane structure, which has a very fast reactivity with moisture is used as the curable resin, and the metal hydroxide powder has a conventional structure because of its structure. Because it is easier to contain moisture than powder fillers, when using metal oxide powders that have been surface-treated with commonly used processing agents such as fatty acids, linseed oil, and titanium coupling agents, manufacture of curable compositions There is a possibility that the treating agent acts as a curing catalyst, and the curable resin reacts with moisture in the system to be cured or significantly thickened.
  • the metal hydroxide powder is dehydrated in advance in the absence of the curable resin, and the curable resin is added later to this, or an additive for maintaining stability is added, Or the device, such as utilizing as a two-component type, is necessary.
  • the average particle diameter of the metal hydroxide powder (B) is 0.1 to 200 ⁇ m.
  • the average particle size is preferably 0.3 to 100 ⁇ m, particularly preferably 0.5 to 50 ⁇ m.
  • the average particle size is less than 0.1 ⁇ m, the final composition viscosity is remarkably increased due to the thickening effect of the powder and workability tends to deteriorate.
  • the average particle size exceeds 200 ⁇ m, long-term storage In addition, sedimentation and separation of the powder component in the composition is likely to occur, and storage stability is likely to deteriorate.
  • the thing of a coating device etc. tends to be clogged when a thing with a large particle diameter is used, it becomes easy to attach restrictions with respect to a coating device and a coating condition.
  • the “average particle diameter” in the present application refers to an arithmetic average diameter calculated from a particle size distribution (volume distribution) detected by a laser diffraction / scattering method (microtrack method).
  • the compounding amount of the metal hydroxide powder (B) is 100 to 400 parts by weight, preferably 150 to 350 parts per 100 parts by weight of the total of the curable silicone resins (A-1) and (A-2). Part by weight, particularly preferably 180 to 300 parts by weight.
  • the blending amount with respect to 100 parts by weight of the polymer (A) is less than 100 parts by weight, a sufficient flame retarding effect cannot be imparted, and when it exceeds 400 parts by weight, the physical properties and adhesiveness of the cured product are inferior. In this case, the final composition viscosity increases due to the thickening effect of the powder, and the workability tends to be remarkably deteriorated.
  • Hijilite H34HL (manufactured by Showa Denko KK: treated with aluminum hydroxide powder linseed oil having an average particle size of 4.0 ⁇ m)
  • Heidilite H42S (manufactured by Showa Denko KK: treated with aluminum hydroxide powder stearic acid having an average particle size of 1.1 ⁇ m)
  • Heidilite H42T (manufactured by Showa Denko KK: treated with aluminum hydroxide powder titanium coupling agent having an average particle size of 1.1 ⁇ m)
  • B103T (manufactured by Nippon Light Metal Co., Ltd .: treated with an aluminum hydroxide powder titanium coupling agent having an average particle diameter of 8 ⁇ m)
  • Kisuma 5Q (manufactured by Kyowa Chemical Industry Co., Ltd .: magnesium hydroxide powder with an average particle size of 1 ⁇ m)
  • Kisuma 5P (manufactured by Kyowa Chemical Industry Co., Ltd .: treated with magnesium hydroxide powder silane coupling agent having an average particle size of 1 ⁇ m)
  • Kisuma 5L (manufactured by Kyowa Chemical Industry Co., Ltd .: treated with magnesium hydroxide powder silane coupling agent having an average particle size of 1 ⁇ m)
  • the aminosilane compound (C) is a compound having an amino group and a hydrolyzable silicon group in the molecule.
  • a low molecular aminosilane compound having an ⁇ -silane structure is highly toxic. Therefore, the aminosilane compound does not have an ⁇ -silane structure, that is, a nitrogen atom of an amino group and silicon of a hydrolyzable silicon group.
  • An aminosilane compound in which two or more carbon atoms are bonded to the atom is more preferable.
  • Examples of the aminosilane compound (C) include an aminosilane compound (c1) represented by the following general formula (3), a condensation reaction product of the aminosilane compound (c1) alone, or an aminosilane compound (c1) and the following general formula (4).
  • Examples thereof include condensation reaction products with other silane compounds as exemplified by the silane compound (c2) represented by Among these, the aminosilane compound (c1) or the condensation reaction product of the aminosilane compound (c1) alone is more preferable because the effect of the amino group in the aminosilane compound (C) can be expressed more easily.
  • R 5 and R 6 are organic groups or hydrogen atoms
  • R 7 is an organic group
  • R 8 is a hydrocarbon group having 1 to 20 carbon atoms
  • R 9 is an organic group having 1 to 20 carbon atoms ( This is a group selected from an aryl group such as a phenyl group, an alkyl group having 1 to 20 carbon atoms, and an alkoxyalkyl group such as a 2- (butoxy) ethyl group), and c is 0, 1 or 2 is shown)
  • R 10 , R 11 and R 12 are organic groups having a molecular weight of 500 or less (this includes a phenyl group, an alkyl group having a molecular weight of 500 or less, a mercaptopropyl group, a ureidopropyl group, a phenoxy group, and carbon.
  • Each represents a group selected from an alkoxyl group having 1 to 6 carbon atoms and a 2- (butoxy) ethoxy group), and R 13 is an organic group having 1 to 20 carbon atoms (which includes a phenyl group and a carbon number) A group selected from 1 to 6 alkyl groups and 2- (butoxy) ethyl group)
  • the amino group contained in the aminosilane compound (C) may be any of primary, secondary, and tertiary amino groups, but the curable silicone resin composition according to the present invention may be used as an adhesive or sealing. In the case where it is used for applications requiring adhesion such as materials and pressure-sensitive adhesives, primary or secondary amino groups that are more likely to exhibit the adhesion-imparting effect are preferred, and primary amino groups are particularly preferred. Moreover, the amino group contained in the said aminosilane compound (C) may be one, and may be two or more.
  • the number of hydrolyzable silicon groups contained in the aminosilane compound (C) may be one, or two or more.
  • aminosilane compound (c1) Specific examples of the aminosilane compound (c1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (6 -Aminohexyl) aminomethyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutyl
  • a ketimine silane compound such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine also generates a primary amino group by moisture, so that the aminosilane compound (c1) is substantially free from the aminosilane compound (c1).
  • the use of 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-aminopropyltrimethoxysilane is easy to obtain and has a high curing acceleration effect. It is preferable from the point. Further, it is known that a cured product in which an aminosilane compound is blended is generally easily yellowed by heat or light.
  • Use of a compound is preferable because yellowing is reduced.
  • silane compound (c2) Specific examples of the silane compound (c2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, tetraethoxysilane, Examples include dimethoxydiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the aminosilane compound (c1).
  • the aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) can be synthesized by a conventionally known method. Specifically, a method of reacting the aminosilane compound (c1) with water or a method of reacting the aminosilane compound (c1) and the silane compound (c2) with water can be mentioned.
  • the aminosilane compound (c1) alone or the condensation reaction product of the aminosilane compound (c1) and the silane compound (c2) is commercially available, and these can be used in the present invention.
  • MS3301 trade name, manufactured by Chisso Corporation
  • MS3302 trade name, manufactured by Chisso Corporation
  • X-40-2651 trade name, manufactured by Shin-Etsu Chemical Co., Ltd.
  • the aminosilane compound (C) may be appropriately selected in order to obtain desired cured film properties and / or curing speed, and may be used alone or in combination of two or more.
  • aminosilane compounds (C) 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyl Triethoxysilane, N-ethylaminoisobutyltrimethoxysilane and condensation reaction products derived therefrom are preferred because they
  • aminosilane compound (C) is used in an amount of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, particularly 100 parts by weight of the total of the curable silicone resins (A-1) and (A-2). 1 to 10 parts by weight is preferred).
  • any conventionally known compound or substance can be blended within a range not impeding the effects of the present invention such as flame retardancy.
  • a conventionally known curable resin calcium carbonate powder, hydrophilic or hydrophobic silica powder, clay powder, acrylic organic powder, organic / inorganic balloon filler, phenol, etc.
  • Tackifiers such as resins, thixotropic agents such as amide wax, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants other than metal hydroxide powders, functional oligomers, hindered amine compounds, hindered phenols Compounds, anti-aging agents such as 3- (2,2,6,6-tetramethylpiperidi-4-yloxy) propyltriethoxysilane, ultraviolet absorbers such as benzotriazole compounds, pigments, titanate coupling agents, Aluminum coupling agents, silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, chlorinated polypropylene, maleic anhydride Polar group-containing polyolefin to improve adhesion to low polarity adherends such as modified polypropylene, improving water resistance agent such as blocked polyisocyanate can be blended with drying oils or the like.
  • dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants other than
  • a titanium-based catalyst As a curing catalyst, a titanium-based catalyst, a zirconium-based catalyst, an aluminum-based catalyst, an organic light metal-based catalyst represented by a bismuth-based catalyst, boron trifluoride and / or a complex thereof, a fluorinating agent, and a fluorine-based inorganic acid
  • a titanium-based catalyst As a curing catalyst, a titanium-based catalyst, a zirconium-based catalyst, an aluminum-based catalyst, an organic light metal-based catalyst represented by a bismuth-based catalyst, boron trifluoride and / or a complex thereof, a fluorinating agent, and a fluorine-based inorganic acid
  • Conventionally known compounds such as fluorine compounds selected from the group consisting of alkali metal salts can be used.
  • the flame-retardant moisture-curable composition of the present invention is easy to manufacture because it does not cure during its manufacture, particularly during the heating and dehydration process.
  • the flame-retardant moisture-curable composition of the present invention is cured by condensation polymerization of alkoxysilyl groups in the presence of moisture. Therefore, when used as a one-pack type, it is handled in an airtightly sealed state so as not to come into contact with air (water in the air) during storage or transportation. And if it opens at the time of use and it applies to arbitrary places, it will contact with the water
  • the flame-retardant moisture-curable composition according to the present invention can be used as a two-component type.
  • the curable silicone resins (A-1) and (A-2) according to the present invention have high reactivity (curability), it is necessary to devise such that they do not cure during storage or transportation.
  • a curing agent containing a curing catalyst or the like is mixed with a main agent containing the curable silicone resins (A-1) and (A-2) and applied to any location, moisture in the air and adhesion
  • the flame retardant moisture curable composition is cured by reacting with moisture contained in the agent composition.
  • the flame-retardant moisture-curable composition of the present invention is premised on exhibiting flame retardancy equivalent to UL94V-0 (sample thickness of 1.5 mm or more).
  • the flame retardant regulation for home appliances is based on the US UL standard, and many products are subject to regulation.
  • UL abbreviation of Underwriters laboratories Inc.
  • UL94 is a private organization in the United States, which is a safety standards development organization and product testing / certification organization for materials, products, equipment, systems, etc.
  • the UL94 standard evaluates the flame retardancy of plastic materials, and UL94V-0 is defined as the class with the highest flame retardancy.
  • composition of the present invention since the composition of the present invention has good curability, it may contain essentially no organic tin-based catalyst, or the content of the organic tin-based catalyst may be less than 1000 ppm. Therefore, the content of the organic heavy metal catalyst having a high environmental load can be extremely reduced.
  • the flame-retardant moisture-curable resin composition of the present invention may be prepared by a conventionally known production method. For example, a curable silicone resin, metal hydroxide powder, other non-reactive components, etc. are charged in an airtight container equipped with a stirrer and heated appropriately while kneading to remove moisture contained in the system. After performing vacuum dehydration, this can be obtained by cooling to near room temperature and further adding and mixing an aminosilane compound, other reactive components (coupling agent, etc.) and other additives.
  • the flame-retardant moisture-curable resin composition of the present invention can be used for all applications to which conventional curable resins have been applied.
  • it can be used as an adhesive, sealant, pressure-sensitive adhesive, paint, coating material, sealing material, casting material, coating material, and the like.
  • the flame-retardant moisture-curable resin composition according to the present invention as a main component, it is possible to provide a flame-retardant composition having a low environmental load, high safety, and a high curing rate. Therefore, it can be suitably used for applications such as a sealant or an adhesive composition that requires a reduction in working time.
  • the “main body” means that a crosslinked network structure formed by condensation of a crosslinkable silyl group of the curable resin composition is a main component in the crosslinked network structure when the composition is cured.
  • the present invention relates to a flame retardant moisture curable adhesive comprising the flame retardant moisture curable resin composition as an active ingredient.
  • the flame retardant moisture curable resin composition can be suitably used as a flame retardant moisture curable adhesive.
  • Adhesion method and product obtained thereby The present invention uses the flame retardant moisture-curing adhesive to bond components in the electrical / electronic market, the automotive parts market, the construction market, the civil engineering market, etc.
  • the present invention relates to a method for bonding components and the like.
  • the present invention also relates to an electrical product, a precision instrument, an automobile part, or the like obtained by bonding constituent members using this flame retardant moisture curable adhesive.
  • the present invention also relates to a flame retardant moisture curable sealant composition comprising the flame retardant moisture curable resin composition as an active ingredient, and a flame retardant moisture curable pressure sensitive adhesive precursor composition.
  • a pressure-sensitive adhesive precursor composition can be obtained by further blending and uniformly mixing a tackifying resin with the flame retardant moisture-curable resin composition. it can.
  • a flame-retardant moisture hardening type composition and tackifying resin uniformly, for example, when compatibility of both is inadequate, you may use an organic solvent.
  • organic solvent alcohols such as ethanol, ethyl acetate, toluene, methylcyclohexane and the like are used.
  • the organic solvent may not be used in the case where the compatibility between the flame-retardant moisture-curable composition and the tackifier resin is good or in applications where the organic solvent is not preferred.
  • an adhesive precursor composition can also be obtained without using tackifying resin for the use for which weak adhesiveness is calculated
  • a pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive precursor composition thus obtained to the surface (one side or both sides) of a conventionally known tape base or sheet base and curing it. And an adhesive tape or an adhesive sheet is obtained.
  • curable silicone resin (A-1) As the curable silicone resin (A-1), GENIOSIL STP-E10 (manufactured by Wacker Chemie AG: curable silicone resin which is a reaction product of polyoxypropylene and isocyanate methylmethyldimethoxysilane) was prepared.
  • curable silicone resin (A-2) The following five types of resins were prepared as the curable silicone resin (A-2).
  • Excestar S2420 (manufactured by Asahi Glass Co., Ltd .: curable silicone resin having a main chain structure of polyoxypropylene and having a methyldimethoxysilyl group at the end);
  • Silyl SAX 580 (manufactured by Kaneka Corporation: curable silicone resin having a main chain structure of polyoxypropylene and having a trimethoxysilyl group at the end);
  • Excestar AX2551 (Asahi Glass Co., Ltd .: curable silicone resin that is a reaction product of polyoxypropylene and isocyanate propyltrimethoxysilane);
  • ARUFON US6110 manufactured by Toa Gosei Co., Ltd .: curable silicone resin having a main chain structure of polyacrylate and having a trimethoxysilyl group in the molecule);
  • KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd .: N- (2-aminoethyl) -3-aminopropyltrimethoxysilane); and KBM-903 (manufactured by Shin-Etsu Chemical Co., Ltd .: 3-aminopropyltrimethoxysilane) as aminosilane compounds Prepared.
  • silane compound SE-1 (8.90 parts by mass) was added, and while stirring and mixing in a nitrogen atmosphere, the isocyanate group in the urethane resin and the secondary amino group in the silane compound SE-1 were added. Is cured at 80 ° C. for 1 hour so that the main chain is an oxyalkylene polymer, the urethane bond in the molecule, a urea bond in which one active hydrogen is substituted, and a curable silicone having a trimethoxysilyl group A system resin SU-1 was obtained. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁇ 1 ) attributed to the isocyanate group was observed.
  • the reaction vessel was charged with the curable silicone resin SU-1 (100 parts by mass) and heated to 80 ° C. in a nitrogen atmosphere. There, 37.5 parts by mass of methyl methacrylate, 25 parts by mass of lauryl methacrylate, 3.0 parts by mass of 3-methacryloxypropyltrimethoxysilane, 7.0 parts by mass of 3-mercaptopropyltrimethoxysilane, and 2,2 A monomer mixture mixed with 0.50 parts by mass of '-azobis (2,4-dimethylvaleronitrile) was added dropwise over 30 minutes to carry out a polymerization reaction. Furthermore, after reacting at 80 ° C.
  • Example 1 A 3L planetary mixer is charged with GENIOSIL STP-E10 (100 parts by mass) of curable silicone resin (A-1) and Heidilite H21 (200 parts by mass) of metal hydroxide powder (B-1). In order to remove moisture contained in the system, vacuum dehydration was performed at 120 ° C. for 2 hours while kneading until uniform. Thereafter, the contents were cooled to near room temperature, and after adding KBM603 (4 parts by mass), the contents were kneaded until uniform to obtain a moisture curable resin composition.
  • KBM603 4 parts by mass
  • the obtained moisture curable resin composition was subdivided and filled into a 120-ml laminated tube, and the ends were heat-sealed and sealed so that no voids were formed in the tube.
  • the number required for the following test was prepared.
  • the curing rate of the moisture curable resin composition obtained above was measured.
  • the cure rate was measured using the skinning time.
  • the skinning time was defined as the start time immediately after exposure to an atmosphere having a relative humidity of 50 ⁇ 5% at 23 ⁇ 2 ° C. and the time until a cured film was formed on the surface.
  • the time when the cured film was formed was a time when the surface of the moisture curable resin composition exposed with the metal spatula was touched and each curable resin composition was not attached to the spatula.
  • the skinning time was 18 minutes and was a practical curing rate.
  • a curable composition is molded to a thickness of 1.5 mm on a polypropylene plate, cured for 3 weeks in an atmosphere of 23 ⁇ 2 ° C. and relative humidity of 50 ⁇ 5%, and then the cured product is used.
  • An UL94V-0 (sample thickness of 1.5 mm) equivalent test was performed for evaluation.
  • the moisture curable resin composition is highly safe because it does not use highly toxic flame retardants and organic heavy metal catalysts.
  • Examples 2 to 6 and Comparative Examples 1 to 4 The moisture curable resin compositions of Examples 2 to 6 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1 at the blending ratios shown in Table 1, and their safety, curing speed, and flame retardancy were prepared. evaluated. In any of the examples and comparative examples, since the untreated metal hydroxide powder was used, the production of the moisture curable composition itself could be performed without any problem.
  • the evaluation criteria for curability in Table 1 are as follows: skinning time is within 1 hour; 1 hour or more but skinning is confirmed within 2 days; Those that could not be confirmed were marked with x.
  • Example 7 A 3L planetary mixer is charged with GENIOSIL STP-E10 (100 parts by mass) of curable silicone resin (A-1) and Heidilite H32ST (200 parts by mass) of metal hydroxide powder (B-2). In order to remove moisture contained in the system, vacuum dehydration was performed at 120 ° C. for 2 hours while kneading until uniform. Thereafter, the contents were cooled to near room temperature, and after addition of KBM603 (4 parts by mass) of aminosilane compound (C) and Shellsol TK (10 parts by weight: isoparaffin-based diluent manufactured by Shell Chemicals Japan) as a diluent, the mixture was uniform. The mixture was kneaded until a moisture curable composition was obtained.
  • the obtained moisture curable composition was filled into a 120-ml laminate tube in small portions, and the ends were heat-sealed and sealed so that no voids were formed in the tube. A necessary number of these were prepared for the following tests.
  • the curing rate of the curable resin composition was measured.
  • the cure rate was measured using the skinning time.
  • the skinning time was defined as the start time immediately after exposure to an atmosphere having a relative humidity of 50 ⁇ 5% at 23 ⁇ 2 ° C. and the time until a cured film was formed on the surface.
  • the time when the cured film was formed was a time when the surface of the curable resin composition exposed with the metal spatula was touched and each curable resin composition was not attached to the spatula.
  • the skinning time was 20 minutes and was a practical curing rate.
  • a curable composition is molded to a thickness of 1.5 mm on a polypropylene plate, cured for 3 weeks in an atmosphere of 23 ⁇ 2 ° C. and relative humidity of 50 ⁇ 5%, and then the cured product is used.
  • An UL94V-0 (sample thickness of 1.5 mm) equivalent test was performed for evaluation.
  • the said curable composition does not use a highly toxic flame retardant and an organic heavy metal catalyst, it is highly safe.
  • Examples 8 to 14, Comparative Examples 5 to 8 and Reference Examples 1 to 4 The curable resin compositions of Examples 8 to 14, Comparative Examples 5 to 8 and Reference Examples 1 to 4 were produced in the same manner as in Example 7 according to the blending ratios in Table 1, and various evaluations were performed.
  • the evaluation criteria for each evaluation item described in Table 2 were the same as in Table 1.
  • Reference Examples 1 to 4 were not tested in this production method because they were cured during the production. This is because the reaction between the moisture in the system and the curable resin is accelerated by heating when vacuum dehydration is performed at 120 ° C. for 2 hours while kneading until uniform to remove moisture contained in the system. This is thought to be due to the accident. Therefore, for example, if the metal hydroxide powder is dehydrated in advance in the absence of the curable resin, and then the curable resin is added to the powder, the curable resin composition can be obtained without such problems. Can do.
  • the moisture-curable composition according to the present invention has flame retardancy equivalent to UL94V-0 (sample thickness 1.5 mm), and cure speed / safety (specific) In other words, it is a combination of a highly toxic flame retardant and an organic heavy metal catalyst not used.
  • those lacking (A-1) or (C) (Comparative Examples 1 to 8) lacked any of curability, flame retardancy, and safety.
  • Example 3 Using the curable resin compositions obtained in Example 1 and Example 8, an adhesion test was performed. The results are shown in Table 3. The test method was performed according to JISK6850. Polycarbonate was selected as the adherend, the amount of adhesive applied was 150 g / mm 2, and after bonding, the test specimens were cured for 2 weeks before testing.
  • the flame retardant moisture curable resin composition is useful as an active ingredient of a sealant and an adhesive precursor.

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Abstract

La présente invention a pour objet une composition de résine ignifuge durcissable à l'humidité qui est respectueuse de l'environnement et qui possède d'excellentes capacités en tant qu'agent adhésif, agent de fixation, produit d'étanchéité, ou composition de précurseur d'adhésif, destinée à être utilisée dans l'assemblage d'appareils électroménagers, d'instruments de précision, de composants automobiles, ou analogues, lorsqu'un caractère ignifuge est requis. La présente invention concerne également un agent adhésif ignifuge durcissable à l'humidité utilisant ladite composition de résine ignifuge durcissable à l'humidité en tant que composant actif, et concerne un procédé de collage utilisant l'agent adhésif. La composition de résine ignifuge durcissable à l'humidité est caractérisée en ce qu'elle comprend un mélange d'une résine silicone durcissable (A-1) ayant une structure α-silane, d'une poudre d'hydroxyde métallique (B) possédant une taille moyenne de particule allant de 0,1 à 200 μm, et d'un composé aminosilane (C).
PCT/JP2011/050620 2010-01-20 2011-01-17 Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif WO2011089987A1 (fr)

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JP2015178634A (ja) * 2013-04-24 2015-10-08 Dic株式会社 無機微粒子複合体とその製造方法、組成物及び硬化物
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WO2019146565A1 (fr) * 2018-01-25 2019-08-01 セメダイン株式会社 Procédé de formation et composition thermofusible réactive durcissable à température et humidité ambiantes, à composant unique et ignifugée
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JPWO2019159753A1 (ja) * 2018-02-15 2021-01-28 株式会社スリーボンド 熱伝導性湿気硬化型樹脂組成物およびその硬化物
WO2019159753A1 (fr) * 2018-02-15 2019-08-22 株式会社スリーボンド Composition de résine durcissable par l'humidité thermiquement conductrice et produit durci de celle-ci
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JP7281263B2 (ja) 2018-09-27 2023-05-25 味の素株式会社 樹脂組成物、感光性フィルム、支持体付き感光性フィルム、プリント配線板及び半導体装置
CN109609053B (zh) * 2018-12-19 2020-09-08 广西华纳新材料科技有限公司 一种石材建筑密封胶用纳米碳酸钙的制备方法
CN109609053A (zh) * 2018-12-19 2019-04-12 广西华纳新材料科技有限公司 一种石材建筑密封胶用纳米碳酸钙及其制备方法
WO2022270196A1 (fr) 2021-06-22 2022-12-29 株式会社スリーボンド Composition de résine durcissable à l'humidité
WO2023145711A1 (fr) * 2022-01-31 2023-08-03 株式会社カネカ Composition durcissable et son utilisation

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