WO2007037368A1 - Composition durcissable de type composition monocomposant - Google Patents

Composition durcissable de type composition monocomposant Download PDF

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WO2007037368A1
WO2007037368A1 PCT/JP2006/319457 JP2006319457W WO2007037368A1 WO 2007037368 A1 WO2007037368 A1 WO 2007037368A1 JP 2006319457 W JP2006319457 W JP 2006319457W WO 2007037368 A1 WO2007037368 A1 WO 2007037368A1
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group
titanium
polymer
curable composition
weight
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PCT/JP2006/319457
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Japanese (ja)
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Ayako Yano
Toshihiko Okamoto
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Kaneka Corporation
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Priority to JP2007537698A priority Critical patent/JP5161578B2/ja
Publication of WO2007037368A1 publication Critical patent/WO2007037368A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/243—Two or more independent types of crosslinking for one or more polymers
    • 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
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Definitions

  • the present invention includes a hydrogen-containing group or a hydrolyzable group bonded to a silicon atom, and can be crosslinked by forming a siloxane bond (hereinafter also referred to as "reactive key group"). It relates to a curable composition containing an organic polymer having
  • An organic polymer containing at least one reactive cage group in a molecule is crosslinked at room temperature by forming a siloxane bond accompanying a hydrolysis reaction of the reactive cage group by moisture or the like.
  • a rubber-like cured product it is known to have a natural property.
  • organic polymers whose main chain skeleton is a polyoxyalkylene polymer or a meth (acrylic acid) ester polymer are disclosed in Patent Document 1 and Patent Document 2, etc., have already been industrially produced, and are widely used in applications such as sealants, adhesives, and paints.
  • a curable composition containing an organic polymer having these reactive cage groups is cured using a silanol condensation catalyst, and is usually dibutyltin bis (acetylacetate) or dibutyl.
  • a silanol condensation catalyst is usually dibutyltin bis (acetylacetate) or dibutyl.
  • Organotin compounds having a carbon-tin bond such as tin dilaurate, are widely used.
  • organotin compounds are concerned about toxicity to living organisms as endocrine disruptors, and there has been a demand for the development of a catalyst having a practical curing rate to replace them.
  • Patent Document 6 Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent It is disclosed in Reference 11, Patent Document 12, Patent Document 13, Patent Document 14, and Patent Document 15.
  • a curable composition containing an organic polymer containing a reactive cage group In many cases, bonding to various types of substrates is required. In order to ensure this adhesiveness, so-called aminosilane having a primary amino group and an alkoxy group in the molecule is usually used. However, when a one-component curable composition is prepared by adding aminosilane using an organic polymer containing a reactive cage group and a titanium catalyst, the adhesive is good, but after storage for a certain period of time. In this case, the viscosity of the composition is improved. In severe cases, the composition hardens in the container and may not be used. Sealing materials and adhesives are not always used immediately after production, but are often stored for several months in warehouses or stores, and their curability and viscosity are constant before and after storage. Is desired.
  • Patent Document 1 Japanese Patent Laid-Open No. 52-73998
  • Patent Document 2 Japanese Patent No. 1780140
  • Patent Document 3 Japanese Patent Publication No. 39-27643
  • Patent Document 4 U.S. Pat.No. 3,175,993
  • Patent Document 5 U.S. Pat.No. 3334067
  • Patent Document 6 Japanese Patent Laid-Open No. 58-17154
  • Patent Document 7 JP-A-11-209538
  • Patent Document 8 Japanese Patent Laid-Open No. 5-311063
  • Patent Document 9 JP 2001-302929 A
  • Patent Document 10 JP 2001-302930 A
  • Patent Document 11 Japanese Patent Laid-Open No. 2001-302931
  • Patent Document 12 Japanese Patent Laid-Open No. 2001-302934
  • Patent Document 13 Japanese Patent Laid-Open No. 2001-348528
  • Patent Document 14 Japanese Unexamined Patent Application Publication No. 2002-249672
  • Patent Document 15 Japanese Unexamined Patent Publication No. 2003-165916
  • the present invention is a curable composition mainly composed of an organic polymer having a reactive cage group, and has good curability and adhesiveness without using an organic tin compound that has been pointed out to be toxic. And providing a curable composition that maintains good workability even after storage for a long period of time. Objective.
  • main chain skeleton of the organic polymer (A) having a reactive cage group used in the present invention those having various main chain skeletons without particular limitation can be used.
  • polyoxyalkylene-based polymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene polyoxypropylene copolymer, polyoxypropylene polyoxybutylene copolymer, etc.
  • Copolymer Ethylene Propylene copolymer, polyisobutylene, copolymer of isobutylene and isoprene, etc., copolymer of polychloroprene, polyisoprene, isoprene or butadiene and tali-tolyl and Z or styrene , Polybutadiene, isoprene or copolymers of butadiene with acrylonitrile, styrene, etc., hydrocarbon polymers such as hydrogenated polyolefin polymers obtained by hydrogenating these polyolefin polymers; adipic acid, etc.
  • Dibasic acid and Dalicol Polyester polymers obtained by condensation of or by ring-opening polymerization of latatones; (meth) acrylic acid esters obtained by radical polymerization of monomers such as ethyl (meth) acrylate and butyl (meth) acrylate Polymers: Vinyl polymers obtained by radical polymerization of monomers such as (meth) acrylic acid ester monomers, butyl acetate, acrylonitrile, styrene, etc .; obtained by polymerizing vinyl monomers in the organic polymer Graft polymer; Polysulfide polymer; ⁇ Nylon 6 by ring-opening polymerization of one-strength prolatatam, Nylon 6 ⁇ 6 by condensation polymerization of hexamethylene diamine and adipic acid, hexamethylene diamine and sebacic acid Nylon 6 ⁇ 10 by condensation polymerization, Nylon 11, by condensation polymerization of ⁇ -aminoundecanoic acid Nai by polymer
  • polyoxyalkylene polymers and (meth) acrylic acid ester polymers are more preferable because cured products obtained with a relatively low glass transition temperature are excellent in cold resistance.
  • the glass transition temperature of the organic polymer as component (A) is not particularly limited, but it is preferably 20 ° C or lower, more preferably 0 ° C or lower. It is particularly preferable that the temperature is not higher than ° C. If the glass transition temperature exceeds 20 ° C, the viscosity in winter or in cold regions may increase and workability may deteriorate, and the flexibility of the cured product may decrease and elongation may decrease.
  • the glass transition temperature is a value obtained by DSC measurement.
  • the (B) titanium catalyst and (C) the silane compound having an epoxy group and an alkoxy group of the present invention have a reduced deep curability of the composition obtained depending on the amount of addition.
  • polyoxyalkylene polymers and (meth) acrylic acid ester polymers are particularly preferred because they are highly moisture permeable and have excellent deep curability.
  • the curable composition containing a (meth) acrylic acid ester-based polymer is preferable because adhesiveness is excellent in weather resistance. Considering the above balance, it is most preferable to use a polyoxyalkylene polymer and a (meth) acrylate polymer in combination.
  • the reactive cage group contained in the organic polymer having a reactive cage group of the present invention has a hydroxyl group or a hydrolyzable group bonded to the silicon atom and is accelerated by the curing catalyst. It is a group that can be cross-linked by reaction.
  • Reactive key groups include general formula (4):
  • each R 6 independently represents 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 (R ′) SiO— ( R 'it
  • X is independently a hydroxyl group or a hydrolyzable group.
  • a is a group represented by 1), 2 or 3).
  • the hydrolyzable group is not particularly limited as long as it is a conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group.
  • alkoxy groups are particularly preferred.
  • the hydrolyzable group or hydroxyl group can be bonded to one key atom in the range of 1 to 3, and two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive key group. In some cases, they may be the same or different.
  • a is preferably 2 or 3, more preferably 3 from the viewpoint of curability.
  • R 6 in the general formula (4) include, for example, an alkyl group such as a methyl group and an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, benzyl
  • an aralkyl group such as a group, or R, is a methyl group, a phenyl group, etc. (R,) SiO—
  • More specific examples of reactive silicon groups include trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, diisopropoxymethyl.
  • a silyl group is mentioned.
  • a trimethoxysilyl group, particularly preferably a trimethoxysilyl group, a triethoxysilyl group or a dimethoxymethylsilyl group is particularly preferred because of its high activity and good curability.
  • a dimethoxymethylsilyl group is particularly preferable from the viewpoint of storage stability.
  • the triethoxysilyl group is particularly preferable because it is an alcoholic ethanol produced by the hydrolysis reaction of the reactive silicon group and has higher safety.
  • Introduction of the reactive cage group may be performed by a known method. That is, for example, the following method can be mentioned.
  • An organic polymer having a functional group such as a hydroxyl group in the molecule reacts with the functional group.
  • An organic compound having an unsaturated group is obtained by reacting an organic compound having an active group and an unsaturated group exhibiting properties.
  • an unsaturated group-containing organic polymer is obtained by copolymerization with an unsaturated group-containing epoxy compound.
  • the reaction product obtained in step 2 is hydrosilylated by the action of a hydrosilane having a reactive silicon group.
  • the method (i) or the method (c) in which the polymer having a hydroxyl group at the terminal is reacted with a compound having an isocyanate group and a reactive group is relatively short. It is preferable because a high conversion rate can be obtained in the reaction time. Furthermore, the organic polymer having a reactive group obtained by the method (i) is a curable composition having a lower viscosity and better workability than the organic polymer obtained by the method (c). In addition, since the organic polymer obtained by the (mouth) method has a strong odor based on mercaptosilane, the method (i) is particularly preferred.
  • hydrosilane compounds used in the method (i) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; , Triethoxysilane, methyljetoxysilane, methyldimethoxysilane, phenyldimethoxysilane, 1- [2- (trimethoxysilyl) ethyl] -1, 1, 3, 3-tetraalkoxy such as tetramethyldisiloxane Silanes; acyl silanes such as methyl diacetoxy silane, and phenyl diacetoxy silane; methoxy silanes such as bis (dimethyl ketoximate) methyl silane and bis (cyclohexyl ketoximate) methyl silane It is not limited to.
  • halogenated silanes and alkoxysilanes are particularly preferable.
  • alkoxysilanes are most preferable because the resulting curable composition has a mild hydrolyzability and is easy to handle.
  • methyldimethoxysilane is a curable composition containing an organic polymer that can be easily obtained.
  • trimethoxysilane and 1- [2- (trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane are preferred titanium catalysts, which are preferable curing catalysts because they can accelerate the curing rate. It is preferable because the amount of use can be reduced.
  • (Mouth) can be synthesized, for example, by subjecting a compound having a mercapto group and a reactive silicon group to an organic polymer by radical addition reaction in the presence of a radical initiator and Z or a radical source.
  • a radical initiator and Z or a radical source examples include introduction to an unsaturated binding site, but it is not particularly limited.
  • Specific examples of the compound having a mercapto group and a reactive silicon group include, for example, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropylmethylmethyldimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, and ⁇ -mercaptopropyl. Examples thereof include, but are not limited to, methyl jetoxy silane and mercaptomethyl triethoxy silane.
  • a disproportionation reaction may proceed in some silane compounds. As the disproportionation reaction proceeds, a rather dangerous compound such as dimethoxysilane is formed. However, such disproportionation reaction does not proceed with ⁇ -mercaptopropyltrimethoxysilane or ⁇ -isocyanatopropyltrimethoxysilane. For this reason, when three hydrolyzable groups such as trimethoxysilyl group are bonded to one key atom as the group containing a group, and the group is used, the synthesis method of (mouth) or (c) is used. It is preferable to use it.
  • R 7 s are each independently a monovalent hydrocarbon group.
  • a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferable, and a monovalent hydrocarbon group having 1 to 8 carbon atoms is more preferable.
  • the monovalent hydrocarbon group is particularly preferable.
  • R 8 is a divalent organic group. From the viewpoint of availability and cost, a divalent hydrocarbon group having 2 to 8 carbon atoms is preferred because of a divalent hydrocarbon group having 1 to 12 carbon atoms. A more preferred divalent hydrocarbon group having 2 carbon atoms is particularly preferred.
  • M is an integer from 0 to 19, and 1 is preferable from the viewpoint of availability and cost.
  • the silane compound represented by) does not proceed with the disproportionation reaction. For this reason, when a group in which three hydrolyzable groups are bonded to one silicon atom is introduced by the synthesis method (ii), a silane compound represented by the general formula (5) is used. I prefer that.
  • Specific examples of the silane compound represented by the general formula (5) include 1 [2- (trimethoxysilyl) ethyl] 1, 1, 3, 3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) ) Propyl] —1, 1, 3, 3-tetramethyldisiloxane, 1- [2- (trimethoxysilyl) hexyl] 1,1,3,3-tetramethyldisiloxane and the like.
  • the organic polymer having a reactive cage group may be linear or branched, and its number average molecular weight is about 500 to 100,000 in terms of polystyrene in GPC, more preferably ⁇ It is 1,000 to 50,000, particularly preferred ⁇ is 3,000 to 30,000. If the number average molecular weight is less than 500, the cured product tends to be inconvenient in terms of elongation characteristics, and if it exceeds 100,000, the viscosity tends to be inconvenient because of high viscosity. Although not particularly limited, specifically, the number average molecular weight and molecular weight distribution are, for example,
  • Liquid feeding system HLC-8120GPC manufactured by Tosoh Corporation
  • the reactive cage group contained in the organic polymer has an average of at least 1 in one molecule of the polymer. There are preferably 1 to 5 pieces. If the number of reactive cage groups contained in the molecule is less than 1 on average, the curability will be insufficient and good rubber elastic behavior will be exhibited.
  • the reactive cage group is at the end of the main chain of the organic polymer molecular chain! Or at the end of the side chain. Or both.
  • the reactive cage group when the reactive cage group is only at the end of the main chain of the molecular chain, the effective network length of the organic polymer component contained in the finally formed cured product is increased, so that high strength and high elongation are achieved. Thus, it becomes easy to obtain a rubber-like cured product having a low elastic modulus.
  • the polyoxyalkylene polymer essentially has the general formula (6):
  • R 9 is a linear or branched alkylene group having 1 to 14 carbon atoms
  • R 9 in the general formula (6) is the number of carbon atoms. 2 to 4 linear or branched alkylene groups are preferred.
  • the repeating unit represented by the general formula (6)
  • the main chain skeleton of the polyoxyalkylene polymer may have only one type of repeating unit force or two or more types of repeating unit forces.
  • a (co) polymer-based component mainly composed of a propylene oxide monomer unit such as a polyoxypropylene polymer is amorphous or compared. Preferred because of its low viscosity.
  • a method for synthesizing a polyoxyalkylene polymer for example, a polymerization method using an alkali catalyst such as KOH, an organoaluminum compound disclosed in JP-A-61-215623 and a porphyrin can be obtained.
  • Transition metal compounds such as the complex to be synthesized -Bolphyrin complex-catalyzed polymerization method, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3278459, U.S. Pat.No. 3,427,256, U.S. Pat.No. 3,427,334, U.S.
  • a polymerization method using a double metal cyanide complex catalyst JP-A-10-273512
  • a polymerization method using a catalyst that also becomes a polyphosphazene salt exemplified in Japanese Patent Publication No. 11-060722 and a polymerization method using a catalyst that also has a phosphazene compound strength exemplified in Japanese Patent Laid-Open No. 11-060722 It is, but not particularly limited.
  • the process for producing a polyoxyalkylene polymer having a reactive cage group of the present invention is characterized by JP 45-36319, 46-12154, JP 50-156599, 54-6096, 55-13767, 55-13468, 57-16412 3 No. 3-2450, US Pat. No. 3,632,557, US Pat. No. 4,345053, US Pat. No. 4,366,307, US Pat. No. 4,960,844, etc.
  • JP 61-197631, 61-21 5622, 61-215623, 61-218632, JP 3-72527, JP 3-47825
  • Examples thereof include polyoxyalkylene polymers having a high molecular weight with a number average molecular weight of 6,000 or more, MwZMn of 1.6 or less, and a narrow molecular weight distribution, which are proposed in JP-A-8-231707. Power Not particularly limited to these.
  • polyoxyalkylene polymer having a reactive silicon group may be used alone or in combination of two or more.
  • the (meth) acrylic acid ester monomer constituting the main chain of the (meth) acrylic acid ester polymer is not particularly limited, and various types can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, n-octyl (meth) acrylate, 2-methylhexyl (meth) acrylate, noel (meth) acrylate, decyl (meth)
  • Acrylic acid monomers In the (meth) acrylic acid ester polymer, the following bull monomers can be copolymerized with the (meth) acrylic acid ester monomer.
  • the vinyl-based monomer include styrene-based monomers such as styrene, vinylenorenorene, a -methino styrene, chronole styrene, styrene sulphonic acid, and salts thereof; perfluoroethylene, perfluoropropylene, Fluorine-containing butyl monomers such as vinylidene fluoride; benzene-containing butyl monomers such as butyltrimethoxysilane and butyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, Monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide,
  • a polymer composed of a styrene monomer and a (meth) acrylic acid monomer is preferred in view of the physical properties of the product. More preferably, it is a (meth) acrylic polymer that also has an acrylic ester monomer power and a methacrylic ester monomer strength, and an acrylic polymer that also has an acrylic ester monomer strength is particularly preferable.
  • a butyl acrylate monomer is more preferred because physical properties such as low viscosity of the compound, low modulus of the cured product, high elongation, weather resistance, and heat resistance are required.
  • copolymers based on ethyl acrylate are more preferred.
  • This polymer mainly composed of ethyl acrylate is excellent in oil resistance but tends to be slightly inferior in low-temperature characteristics (cold resistance). Therefore, in order to improve the low-temperature characteristics, a part of the ethyl acrylate is acrylic acid. It is also possible to replace it with butyl. However, as the proportion of acrylic acid is increased, its good oil resistance is impaired! /, So it is preferable that the ratio be 40% or less for applications that require oil resistance. Further, it is more preferable to make it 30% or less.
  • the ratio is preferably 40% or less when heat resistance is required.
  • these preferable monomers may be copolymerized with other monomers, and further block copolymerized. In this case, it is preferable that these preferable monomers are contained in an amount of 40% or more by weight.
  • (meth) acrylic acid means acrylic acid and ⁇ means methacrylic acid.
  • the method for synthesizing the (meth) acrylic acid ester polymer is not particularly limited, and may be carried out by a known method.
  • a polymer obtained by a normal free radical polymerization method using an azo compound or a peroxide as a polymerization initiator has a problem that the molecular weight distribution is generally as large as 2 or more and the viscosity becomes high. Have. Therefore, in order to obtain a (meth) acrylate polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio. For this, it is preferable to use a living radical polymerization method.
  • “living radical polymerization methods” there are organic halides, or halogenated sulfone compounds as initiators, and transition metal complexes as catalysts to polymerize (meth) acrylic acid ester monomers.
  • “Radical polymerization method” is a special feature of the above "living radical polymerization method”.
  • (meth) acrylic acid ester series having specific functional groups because it has halogen at the terminal, which is relatively advantageous for functional group conversion reactions, and has a high degree of freedom in designing initiators and catalysts.
  • Further preferred as a method for producing a polymer As this atom transfer radical polymerization method, for example, Matyjaszewski et al., Journal 'Ob' American 'Chemical Society (J. Am. Chem. Soc.) 1995, 117, p.
  • Examples of the method for producing a (meth) acrylic acid ester-based polymer having a reactive cage group include Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, and Japanese Patent Publication No. Hei 6-212922. Discloses a production method using a free radical polymerization method using a chain transfer agent. Further, the power disclosed in JP-A-9-272714 and the like using a method using an atom transfer radical polymerization method is not particularly limited thereto.
  • the (meth) acrylic acid ester-based polymer having a reactive cage group may be used alone or in combination of two or more.
  • organic polymers having reactive cage groups may be used alone or in combination of two or more. Specifically, an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive cage group and a (meth) acrylic acid ester polymer having a reactive cage group can also be used.
  • a method for producing an organic polymer obtained by blending a polyoxyalkylene polymer having a reactive cage group and a (meth) acrylate polymer having a reactive cage group is disclosed in JP —Proposed in JP-A-122541, JP-A-63-112642, JP-A-6-172631, and JP-A-11-116763, but is not limited thereto.
  • Preferred specific examples include a reactive chain group and a molecular chain substantially having the following general formula (7):
  • R 1G represents a hydrogen atom or a methyl group
  • R 11 represents an alkyl group having 1 to 8 carbon atoms
  • a (meth) acrylate ester having an alkyl group having 1 to 8 carbon atoms
  • R 1C> is the same as above, R 12 represents an alkyl group having 9 or more carbon atoms
  • This is a method for producing a (meth) acrylic acid ester monomer unit copolymer having an alkyl group having 9 or more carbon atoms by blending a polyoxyalkylene polymer having a reactive cage group. .
  • R 11 in the general formula (7) is, for example, 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an n-propyl group, a t-butyl group, and a 2-ethylhexyl group, preferably Includes 1 to 4, more preferably 1 to 2 alkyl groups.
  • the alkyl group of R 11 may be used alone or in combination of two or more.
  • R 12 in the general formula (8) is, for example, 9 or more carbon atoms such as lauryl group, tridecyl group, cetyl group, stearyl group, and beryl group, usually 10 to 30, preferably Includes 10 to 20 long-chain alkyl groups.
  • the alkyl group for R 12 may be used alone or in a mixture of two or more as in the case of R 11 .
  • the molecular chain of the (meth) acrylic acid ester-based copolymer also has a monomer unit force of the formula (7) and the formula (8).
  • “substantially” means It means that the total of the monomer units of formula (7) and formula (8) present in the copolymer exceeds 50% by weight.
  • the total of the monomer units of formula (7) and formula (8) is preferably 70% by weight or more.
  • the abundance ratio of the monomer unit of the formula (7) and the monomer unit of the formula (8) is preferably 95: 5-40: 60 force, and 90: 10-60: 40 force in weight ratio. Further preferred.
  • the monomer unit contained in the copolymer may be! / ⁇ other than formula (7) and formula (8), for example, acrylic acid such as acrylic acid and methacrylic acid; acrylamide, Contains amide groups such as methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, and amino groups such as jetylaminoethyl acrylate and jetylaminoethyl methacrylate Monomers; Others include monomer units derived from acrylonitrile, styrene, ⁇ -methylstyrene, alkyl butyl ether, butyl chloride, butyl acetate, butyl propionate, ethylene and the like.
  • the main chain skeleton of the organic polymer of the present invention may contain other components such as a urethane bond component as long as the effects of the invention are not significantly impaired.
  • the urethane bond component is not particularly limited, and examples thereof include a group (hereinafter also referred to as an amide segment) generated by a reaction between an isocyanate group and an active hydrogen group.
  • the amide segment has the general formula (9):
  • R 13 represents a hydrogen atom or a substituted or unsubstituted organic group.
  • a urethane group generated by a reaction of an isocyanate group and a hydroxyl group a urea group generated by a reaction of an isocyanate group and an amino group
  • a reaction of an isocyanate group and a mercapto group a group formed by further reacting an active hydrogen in the urethane group, urea group and thiourethane group with an isocyanate group is also included in the group of the general formula (9).
  • An example of an industrially easy method for producing an organic polymer having an amide segment and a reactive silicon group is as follows. To an organic polymer having an active hydrogen-containing group at the terminal, an excess polyisocyanate compound is combined. After reacting to form a polymer having an isocyanate group at the end of the polyurethane main chain, or at the same time, all or part of the isocyanate group may be represented by the general formula (10) WR 14 -SiR 6 X (10)
  • R 14 is a divalent organic group, more preferably a substituted or unsubstituted divalent hydrocarbon having 1 to 20 carbon atoms.
  • W is an active hydrogen-containing group selected from a hydroxyl group, a forcel-poxyl group, a mercapto group, and an amino group (unsubstituted or mono-substituted).
  • Examples of known production methods for organic polymers related to this production method include Japanese Patent Publication No. 46-12154 (US Pat. No. 3,632,557) and Japanese Patent Publication No. 58-109529 (US Pat. No. 4,374,237). Description), Japanese Patent Application Laid-Open No.
  • organic polymer having an active hydrogen-containing group at the terminal is represented by the general formula (11)
  • R 6 , R 14 , X, and c are the same as described above, and those produced by reacting with a reactive silicon group-containing isocyanate compound.
  • Examples of known production methods for organic polymers related to this production method include JP-A-11 279249 (US Pat. No. 5,990,257) and JP-A 2000-119365 (US Pat. No. 6046270). ), JP-A-58-29818 (U.S. Pat. No. 4345053), JP-A-3-47825 (U.S. Pat. No. 5,068,304), JP-A-11-60724, JP-A-2002- No. 155145, JP 2002-249538 A, pamphlet of International Publication No. 03Z018658, pamphlet of International Publication No. 03/059981, and the like.
  • Examples of the organic polymer having an active hydrogen-containing group at the terminal include an oxyalkylene polymer (polyether polyol) having a hydroxyl group at the terminal and a polyacrylic polyol.
  • polyether polyols are more preferable because the resulting organic polymer has low viscosity and good workability, and good adhesion and deep part curability.
  • Polyacryl polyol is more preferred because the cured product of the resulting organic polymer has good weather resistance and heat resistance.
  • polyether polyol those produced by any production method can be used, but those having at least 0.7 hydroxyl groups per molecular terminal in terms of the total molecular average are preferred.
  • the polymerization method using a double metal cyanide complex is a low unsaturation, low molecular weight distribution, low viscosity, high acid resistance, and high weather resistance. It is preferable because a rualkylene polymer can be obtained.
  • Examples of the polyacrylic polyol include a polyol having a (meth) acrylic acid alkyl ester (co) polymer as a skeleton and having a hydroxyl group in the molecule.
  • the polymer synthesis method is more preferably an atom transfer radical polymerization method, which is preferred to a living radical polymerization method, because the molecular weight distribution is narrow and low viscosity can be achieved.
  • Specific examples include Alfon UH 2000 and UH-2130 manufactured by Toagosei Co., Ltd.
  • polyisocyanate compound examples include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; Examples thereof include aliphatic polyisocyanates such as cyanate and hexamethylene diisocyanate.
  • the key compound of the general formula (10) is not particularly limited, but specific examples include ⁇ -aminopropyltrimethoxysilane, ⁇ - ( ⁇ -aminoethyl) ⁇ -aminopropyltrimeth Xysilane, ⁇ - ( ⁇ -phenol) aminopropyltrimethoxysilane, ⁇ ethylaminoisobutyltrimethoxysilane, ( ⁇ cyclohexylaminomethyl) triethoxysilane, ( ⁇ -cyclohexylaminomethyl) diethoxymethylsilane, Amino group-containing silanes such as ( ⁇ -phenolaminomethyl) trimethoxysilane; hydroxy group-containing silanes such as y-hydroxypropyltrimethoxysilane; mercapto group-containing silanes such as y-mercaptopropyltrimethoxysilane; Is mentioned.
  • JP-A-6-211879 (U.S. Pat. No. 53 64955), JP-A-10-53637 (U.S. Pat. No. 5756751), JP-A-10-204144 (European Patent Application Publication No. No. 0831108), JP-A 2000-169544, JP-A 2000-169545, various ⁇ , ⁇ -unsaturated carbonyl compounds, primary amino group-containing silanes, Michael addition reaction Or a Michael addition reaction product of various (meth) atalyloyl group-containing silanes with primary amino group-containing compounds can also be used as the key compound of the general formula (10).
  • the reactive silicon group-containing isocyanate compound of the general formula (11) is not particularly limited, but specific examples include ⁇ -trimethoxysilylpropyl isocyanate, ⁇ -triexylsilylpropyl isocyanate. And ⁇ -methyldimethoxysilylpropyl isocyanate, ⁇ and dimethoxymethylsilylmethyl isocyanate, and the like. Further, as described in JP-A No. 2000-1 19365 (US Pat. No. 6046270), a silicon compound of the general formula (10) and an excess of the polyisocyanate ich compound are used. The compound obtained by the reaction can also be used as a reactive silicon group-containing isocyanate compound of the general formula (11).
  • the main chain skeleton of the organic polymer of the present invention contains a large number of amide segments, the viscosity of the organic polymer may increase and the composition may have poor workability.
  • the amide segment in the main chain skeleton of the organic polymer tends to improve the curability of the composition of the present invention.
  • the composition combined with the component ( ⁇ ) of the present invention has a faster curing property while using a non-organotin catalyst. Therefore, it is preferable.
  • the average number of amide segments per molecule is 1 to 10 and 1.5 to 7 is more preferable 2 to 5 Is particularly preferred.
  • the number is less than 1, the curability may not be sufficient.
  • the organic polymer may have a high viscosity, resulting in a poor workability composition.
  • a titanium catalyst is used as the component (ii). This titanium catalyst functions as a curing catalyst for the organic polymer as component (ii).
  • organotin compounds such as dibutyltin dilaurate and dibutyltin diacetylacetonate have been used as curing catalysts for organic polymers having a reactive cage group as component (ii).
  • the toxicity of organotin compounds has been pointed out. Since the organotin compound increases the toxicity or the burden on the environment depending on the amount of the organotin compound, the composition of the present invention is characterized by substantially containing the organotin compound in the composition. To do.
  • substantially “Not contained in” means that the content of the organic tin compound is 0.5 parts by weight or less based on 100 parts by weight of the organic polymer (A).
  • the content of the organotin compound is preferably 0.1 parts by weight or less, and more preferably 0.01 parts by weight or less. It is particularly preferable that no organic tin compound is contained.
  • the titanium catalyst (B) of the present invention By using the titanium catalyst (B) of the present invention, a curable composition having substantially the same curing characteristics as when an organotin compound is used can be obtained. Further, compared to the case of using another curing catalyst such as an organic tin catalyst, it is possible to improve the adhesion to a difficult-to-adhere organic adherend such as an acrylic resin.
  • a compound such as TiO that does not function as a curing catalyst for component (A) is a component (B) of the present invention.
  • the titanium catalyst is a compound having a titanium atom bonded to a hydroxyl group or a substituted or unsubstituted alkoxy group.
  • Preferred specific examples of the titanium catalyst include a compound represented by the general formula (1):
  • R 1 is an organic group, more preferably a monovalent hydrocarbon group in the substituted or Hi ⁇ conversion 1 to 20 carbon atoms.
  • the four R 1 may be identical to each other , Which may be different from each other).
  • titanium alkoxide can be exemplified as a typical compound.
  • a part or all of four OR 1 groups in the general formula (1) may be represented by the general formula (12):
  • R 17 is an organic group, more preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • titanium catalysts other than the titanium catalyst represented by the general formula (1) include those represented by the general formula (13).
  • X 1 is a halogen atom, and (4 ⁇ a) pieces of X 1 may be the same or different from each other.
  • R 18 is an organic group, more preferably the number of carbon atoms. It is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 20, and a R 18 may be the same or different from each other, and a is 1, 2, or 3. .) Is a halogenated titanium alkoxide.
  • titanium alkoxide is preferable from the viewpoints of stability to moisture and curability.
  • the titanium chelate is preferred, but the general formula (2):
  • n R 2 s are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • (4-n) R 3 s are each independently a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
  • (4 11) 8 1 and (4—n) A 2 are each independently —R 4 or —OR 4 (where R 4 is a substitution of 1 to 8 carbon atoms or An unsubstituted monovalent hydrocarbon group).
  • n is 0, 1, 2, or 3.
  • R 3 and A ⁇ A 2 are the same as described above.
  • R 5 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
  • Chelates are more preferable from the viewpoint of compatibility with the component (A), high catalytic activity, and storage stability. Titanium chelates of general formula (2) are particularly preferred because of their high catalytic activity. A titanium chelate having n of 2 in the general formula (2) is most preferred because of its relatively low crystallinity (melting point), good workability and high catalytic activity.
  • titanium alkoxides are specifically exemplified by titanium tetramethoxide, titanium tetraethoxide, titanium tetraaryloxide, titanium tetra n-propoxide, titanium.
  • Tetraisopropoxide Titanium tetra n-butoxide, Titanium tetraisobutoxide, Titanium tetra sec-Butoxide, Titanium tetra tert-butoxide, Titanium tetra n-pentyloxide, Titanium tetracyclopentyloxide, Titanium tetrahexoxide, Titanium tetracyclo Hexyloxide, Titanium tetrabenziloxide, Titanium tetraoctyloxide, Titanium tetrakis (2-Ethylhexyloxide), Titanium tetradecyloxy , Titanium tetradodecyloxide, titanium tetrastearyloxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyloxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolate), Titan
  • titanium-carboxylates in which some or all of the four OR 1 groups in the general formula (1) are groups represented by the general formula (12) Rate triisoprovo Such as oxide, titanium metatalylate triisopropoxide, titanium dimethacrylate diisopropoxide, titanium isopropoxide trimetatalylate, titanium hexanoate triisopropoxide, titanium stearate triisopropoxide, etc. .
  • halogenated titanium alkoxides of the general formula (13) include titanium chloride triisopropoxide, titanium dichloride diisopropoxide, titanium sopropoxide trichloride, titanium bromide triisopropoxide, titanium. Fluoride triisopropoxide, titanium chloride triethoxide, titanium chloride tributoxide, and the like.
  • titanium chelate of the general formula (2) or the general formula (3) include titanium dimethoxide bis (ethinoreacetoacetate), titanium dimethodobis (acetinoreacetonate), Titanium diethoxide bis (ethylacetoacetate), Titanium diethoxide bis (acetylacetonate), Titanium diisopropoxide bis (ethylacetoacetate), Titanium diisopropoxide bis (methylacetoacetate) ), Titanium diisopropoxide bis (t-butylacetoacetate), titanium diisopropoxide bis (methyl-3-oxo-4,4-dimethylhexanoate), titanium diisopropoxide bis (ethyl 1-oxo) 4, 4, 4—trifluorobutanoate), titanium diisopropoxide Bis (acetylacetonate), Titanium diisopropoxide bis (2, 2, 6, 6-tetramethyl-3,5-heptanedionate), Titanium di-n-
  • Titanium diisopropoxide bis (ethylacetoacetate) is commercially available from Matsumoto Pharmaceutical Co., Ltd. under the trade name Olga-Tix TC-750, and from DuPont Co., Ltd. under the trade name Tyza 1 DC, and is readily available. .
  • titanium catalysts other than the above include titanium tris (dioctyl phosphate) isopropoxide, titanium tris (dodecylbenzene sulfonate) isopropoxide, dihydroxy titanium bislatate, and the like.
  • the chelating reagent capable of forming the chelate ligand of the titanium chelate include ⁇ -diketones such as acetylacetone, 2,2,4,4-tetramethyl-3,5 heptanedione; Methyl acetate, ethyl acetate, tert-butyl acetate, acetoacetate allyl, acetoacetate (2-methacryloxychetyl), 3-oxo-4,4-dimethylhexanoic acid methyl, 3-oxo-4, 4, 4 From the viewpoint of curability, j8-ketoesters such as ethyl trifluorobutanoate; 13-esters such as dimethyl malonate and jetyl malonate are preferred.
  • ⁇ -diketones such as acetylacetone, 2,2,4,4-tetramethyl-3,5 heptanedione
  • ⁇ -diketone and j8-ketoester are curable and stored.
  • ⁇ -ketoesters are also particularly preferred because they are more stable in terms of stability.
  • acetoacetate particularly preferred is acetoylacetone, methyl acetoacetate and ethyl acetoacetate.
  • each chelate ligand may be the same or different.
  • a titanium compound capable of reacting with a chelating reagent such as titanium tetraisopropoxide or titanium dichloride disopropoxide
  • a method in which a chelating reagent such as ethyl acetate is added to the composition of the present invention and chelated in the composition can also be applied.
  • the amount of the titanium catalyst ( ⁇ ) is preferably about 2 to 20 parts by weight, more preferably about 4 to 15 parts by weight with respect to 100 parts by weight of the organic polymer ( ⁇ ). Particularly preferred is about LO parts by weight. If the blending amount of the component (ii) is less than 2 parts by weight, a practical curing rate may not be obtained and the curing reaction may not proceed sufficiently. On the other hand, when the blending amount of the component (ii) exceeds 20 parts by weight, the work life tends to be too short and workability tends to deteriorate.
  • a titanium catalyst is used as the curing catalyst of the present invention
  • other curing catalysts may be used in combination so as not to reduce the effects of the present invention.
  • Specific examples include carboxylic acid metal salts such as tin 2-ethylhexanoate, tin versatate, and bismuth 2-ethylhexanoate.
  • 2-Ethylhexanoic acid tin and versatic acid tin are divalent inorganic tins, not organic tin compounds.
  • a silane compound having an epoxy group and an alkoxy group is used as the component (C).
  • the alkoxy group is present on a silicon atom.
  • Specific examples of the component (C) include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, j8 (3, 4 epoxycyclohexenole) ethino Examples include epoxy group-containing silanes such as letrimethoxysilane and j8 (3,4-epoxycyclohexyl) ethyltriethoxysilane.
  • ⁇ -glycidoxypropyltrimethoxysilane ⁇ -glycidoxypropinoletriethoxysilane, and ⁇ -glycidoxypropylmethyldimethoxysilane are used.
  • ⁇ -glycidoxypropyltrimethoxysilane is especially preferred Is preferred.
  • the amount of the silane compound having an epoxy group as the component (C) is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer as the component (A). ⁇ : LO parts by weight are more preferred.
  • the blending amount of component (C) is less than 0.1 parts by weight, it is difficult to obtain sufficient adhesion, while when it exceeds 20 parts by weight, the curability becomes too long.
  • a silane coupling agent in addition to the component (C), a silane coupling agent, a reaction product of the silane coupling agent, or a compound other than the silane coupling agent can be added to the composition of the present invention as an adhesion promoter.
  • the silane coupling agent include ⁇ -isocyanate propyltrimethoxysilane, ⁇ —isocyanate propyltriethoxysilane, ⁇ —isocyanate propylmethyl jetoxysilane, and ⁇ -isocyanate propylmethyldimethoxy.
  • Isocyanate group-containing silanes such as silane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane, (isocyanatemethyl) triethoxysilane, (isocyanatemethyl) diethoxymethylsilane ⁇ —Mercaptopropyltrimethoxysilane , ⁇
  • Androgenic containing silanes can be mentioned tris (3-trimethoxysilylpropyl) I cios ⁇ isocyanurate silanes such as Isoshianureto like. Further, a condensate obtained by partially condensing the above silanes can also be used.
  • the reaction product of the silane coupling agent include a reaction product of aminosilane and epoxysilane, a reaction product of aminosilane and isocyanate silane, and a partial condensate of various silane coupling agents. It is necessary to prevent the secondary amino group from remaining.
  • a silane compound having a primary amino group and an alkoxy group in the molecule is used as an adhesiveness-imparting agent for a sealing material, but in the composition of the present invention, storage stability It is not practically used because it lowers. However, it can be used as long as the storage stability is not lowered.
  • the amount of the silanic compound having a primary amino group and an alkoxy group is based on 100 parts by weight of the organic polymer (A). 0.5 parts by weight or less is preferred 0.1 parts by weight or less is more preferred 0.01 parts by weight or less is more preferred. Particularly preferably, it is not contained.
  • a silane coupling agent having a secondary amino group and a Z or tertiary amino group is preferably used because it can improve adhesion to the base without deteriorating storage stability.
  • Emission type silanes and the like can be used.
  • bis (3-trimethoxysilylpropyl) amine and N-ethyl-1-yaminoisobutyltrimethoxysilane are particularly preferred from the viewpoint of further improving curability.
  • the silane coupling agent, the reaction product of the silane coupling agent, or the compound other than the silane coupling agent used in the present invention is usually based on 100 parts by weight of the organic polymer having a reactive key group (A). Used in the range of 0.1 to 20 parts by weight. In particular, it is preferably used in the range of 0.5 to 10 parts by weight. If the amount of the silane coupling agent used is less than 0.1 part by weight, the viscosity of the one-component curable composition may increase in the container or become hard to use when stored for a long period of time. If it exceeds 20 parts by weight, the curing rate may become very slow.
  • the effects of the silane coupling agent added to the curable composition of the present invention include various adherends, That is, when used on inorganic substrates such as glass, aluminum, stainless steel, zinc, copper, mortar, and organic substrates such as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, polycarbonate, etc., under non-primer conditions or primer treatment conditions It shows a remarkable adhesion improvement effect. When used under non-primer conditions, the effect of improving the adhesion to various adherends is particularly remarkable.
  • Specific examples of the compound other than the silane coupling agent are not particularly limited, and examples thereof include epoxy resin, phenol resin, sulfur, alkyl titanates, and aromatic polyisocyanate.
  • the adhesiveness-imparting agent may be used alone or in combination of two or more. By adding these adhesiveness-imparting agents, the adhesion to the adherend can be improved.
  • compounds having only a hydrolyzable cage group as a functional group can be used, and these are compounds that can function as a dehydrating agent, a crosslinking agent, a physical property adjusting agent, or the like.
  • this component various compounds having no particular limitation can be used as long as they have only a reactive group as a functional group and have a molecular weight of 100 to LOOO.
  • tetramethoxysilane tetraethoxysilane, ethoxytrimethoxysilane, dimethoxydiethoxysilane, methoxytriethoxysilane, tetra-n-propoxysilane, tetra-1-i-propoxysilane, tetra-1-n-butoxysilane, Tetraalkoxysilanes (tetraalkyl silicates) such as tetra-i-butoxysilane and tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltriphenoxysilane, etyltri Trianolecoxysilanes such as methoxysilane, butyltrimethoxysilane, and phenyltrimethoxysilane; dialkoxy such as dimethinoresimethoxymethoxy, jetinores
  • the partially hydrolyzed condensate of the organosilicate compound a commercially available product can be used.
  • examples of such condensates include methyl silicate 51, ethyl silicate 40 (both manufactured by Colcoat Co., Ltd.) and the like.
  • a compound containing a primary amino group is substantially not used.
  • substantially means an amount that does not decrease the storage stability of the curable composition of the present invention.
  • the organic polymer (A) is a first grade with respect to 100 parts by weight. It means that the content of the compound having an amino group is 0.5 parts by weight or less.
  • the content of the compound having a primary amino group is preferably 0.1 parts by weight or less, and more preferably 0.01 parts by weight or less. Particularly preferably, it is not contained at all.
  • a filler may be added to the composition of the present invention.
  • reinforcing fillers such as fumed silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous key acid, hydrous key acid, and carbon black; heavy calcium carbonate, calcium carbonate carbonate, Magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenol ⁇ Examples of such fillers include organic microballoons of fatty acid salt vinylidene resin, PVC powder, filler powder such as PMMA powder, and fibrous fillers such as asbestos, glass fiber, and filament.
  • the amount used is 1 to 250 parts by weight, preferably 10 to 200 parts by weight, per 100 parts by weight of the poly
  • the filler is uniformly mixed with a dehydrating agent such as acid calcium, and then sealed in a bag made of an airtight material. It is also possible to dehydrate and dry in advance by leaving it for an appropriate time. By using this low water content filler, the storage stability can be further improved.
  • a dehydrating agent such as acid calcium
  • a polymer powder using a polymer such as methyl methacrylate as a raw material, Amorphous silica or the like can be used as a filler.
  • hydrophobic silica which is a fine powder of silicon dioxide silicon dioxide having a hydrophobic group bonded to the surface thereof, as a filler makes it possible to achieve transparency.
  • a high composition can be obtained.
  • the surface of the silicon dioxide fine powder is generally a silanol group (—SiOH).
  • Hydrophobic silica is a product in which (SiO—hydrophobic group) is generated. More specifically, dimethylsiloxane, hexamethyldisiloxane is added to silanol groups present on the surface of silicon dioxide fine powder. This is a reaction-bonded silazane, dimethyldichlorosilane, trimethoxyoctylsilane, trimethylsilane, etc.
  • the silicon dioxide fine powder whose surface is formed of silanol groups (—SiOH) is called hydrophilic silica fine powder.
  • calcium carbonate such as titanium oxide and heavy calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon
  • the filler selected from the above is used in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive cage group, preferable results are obtained.
  • the larger the specific surface area of calcium carbonate the greater the effect of improving the breaking strength, breaking elongation and adhesion of the cured product.
  • these fillers may be used alone or in combination of two or more.
  • the surface treatment in which the particle diameter of the surface-treated fine calcium carbonate is preferably 0.5 m or less, is preferably treated with a fatty acid or a fatty acid salt.
  • the particle size of calcium carbonate having a large particle size is preferably 1 ⁇ m or more and can be used after being surface-treated.
  • an organic balloon or inorganic balloon additive is preferred. These fillers can be surface-treated, and may be used alone or in combination of two or more.
  • the balloon particle size is preferably 0.1 mm or less. In order to make the surface of the cured product matt, 5 to 300 m is preferable.
  • the composition of the present invention has good chemical resistance of the cured product, for example, saizin board, especially ceramic sizing board, etc. Suitable for adhesives that remain on the joints
  • high-quality outer walls are being used as outer walls due to the inclusion of spatter paint, colored aggregates, and the like.
  • the composition of the present invention contains a scaly or granular substance having a diameter of 0.1 mm or more, preferably about 0.1 to 5 Omm
  • the cured product has such a high-grade outer wall. Because of the harmony and chemical resistance, the appearance of this cured product is an excellent composition that lasts for a long time.
  • a granular material it has a sanding tone! When it comes to a sandstone-like rough surface, if it uses a scale-like material, it becomes an uneven surface due to the scale shape.
  • Preferred diameters, blending amounts, materials, and the like of the scaly or granular substance are as follows as described in JP-A-9-53063.
  • the diameter is 0.1 mm or more, preferably about 0.1 to 5. Omm, and one having an appropriate size is used according to the material and pattern of the outer wall. Those of about 0.2 mm to 5. Omm and about 0.5 mm to 5. Omm can also be used. In the case of a scale-like substance, the thickness is about 1Z 10 to lZ5 of the diameter (about 0.01 to 1.00 mm). The scale-like or granular substance is mixed in advance in the main sealing material and transported to the construction site as a sealing material, or mixed into the main sealing material at the construction site for use.
  • the scale-like or granular substance is blended in an amount of about 1 to 200 parts by weight per 100 parts by weight of a composition such as a sealing material composition or an adhesive composition.
  • the amount to be blended is appropriately selected according to the size of each scale-like or granular substance, the material of the outer wall, the pattern, and the like.
  • the scale-like or granular substance natural substances such as key sand and my strength, synthetic rubbers, synthetic resins, and inorganic substances such as alumina are used. In order to improve the design when filling the joints, it is colored in an appropriate color according to the material and pattern of the outer wall.
  • a balloon preferably having an average particle size of 0.1 mm or more
  • the surface becomes sandy or sandstone rough, and light weight can be achieved. it can.
  • preferred diameters, blending amounts, materials, and the like of the balloon are as follows.
  • the balloon is a spherical filler with a hollow inside.
  • the balloon material includes inorganic materials such as glass, shirasu, and silica, phenol resin, urea resin, Forces that include organic materials such as polystyrene and saran.
  • Inorganic materials and organic materials that are not limited to these materials can be combined, or multiple layers can be formed by stacking them. You can also Inorganic or organic balloons or a combination of these can be used.
  • the same balloon may be used, or a mixture of different types of balloons may be used.
  • a balloon whose surface is processed or coated can be used, and a balloon whose surface is treated with various surface treatment agents can also be used.
  • an organic balloon may be coated with calcium carbonate, talc, oxytitanium, or the like, or an inorganic lane may be surface-treated with a silane coupling agent.
  • the balloon preferably has a particle size of 0.1 mm or more. Those of about 0.2 mm to 5. Omm and about 0.5 mm to 5. Omm can also be used. If it is less than 0. lmm, even if it is added in a large amount, the viscosity of the composition is only increased, and a rough feeling may not be exhibited. The amount of nolane can be easily determined according to the desired degree of sanding or sandstone roughness. In general, it is desirable to blend those having a particle size of 0.1 mm or more in a ratio of 5 to 25 vol% by volume concentration in the composition.
  • volume concentration of the balloon When the volume concentration of the balloon is less than 5 vol%, the feeling of roughness does not occur.When the volume concentration exceeds 25 vol%, the viscosity of the adhesive becomes high and the modulus of the cured product becomes poor, and the modulus of the cured product becomes high. The basic performance of the agent tends to be impaired. The balance with the basic performance of the sealing material is particularly preferred, and the volume concentration is 8-22 vol%.
  • balloons include JP-A-2-129262, JP-A-4-8788, JP-A-4173867, JP-A-5-1225, JP-A-7-113073, JP-A-9. — 53063, JP-A-10-251618, JP-A-2000-154368, JP2001-164237, WO97 / 05201, etc.
  • thermally expandable fine particle hollow body described in JP-A-2004-51701 or JP-A-2004-66749 can be used.
  • Thermally expandable fine hollow body is the number of carbon atoms Low-boiling compounds such as 1 to 5 hydrocarbons in a spherical shape with a polymer outer shell (salt-vinylidene copolymer, acrylonitrile copolymer, or salt-vinyl-linden acrylonitrile copolymer) It is an encased plastic sphere.
  • the gas pressure in the shell of the thermally expandable fine hollow body increases, and the volume of the polymer outer shell material softens, so that the volume expands dramatically. And serves to peel the adhesive interface.
  • heat-expandable fine-grain hollow bodies an adhesive composition that can be peeled off without breaking the material simply by heating when not needed, and can be peeled off without using any organic solvent is obtained. It is possible.
  • the composition of the present invention contains particles of cured sealant
  • the cured product can form irregularities on the surface and improve the design.
  • preferred diameters, blending amounts, materials and the like of the cured sealant particles are as follows.
  • the diameter is preferably about 0.1 mm to Lmm, and the thickness is preferably about 0.2 to 0.5 mm.
  • the blending amount is preferably 5 to L00% by weight, more preferably 20 to 50% by weight in the curable composition.
  • the material include urethane resin, silicone, modified silicone, polysulfur rubber, and the like. The material is not limited as long as it is used as a sealing material, but a modified silicone-based sealing material is preferable.
  • a tackifier can be added to the composition of the present invention.
  • the tackifier resin is not particularly limited, and any commonly used solid or liquid at normal temperature can be used. Specific examples include styrenic block copolymers, hydrogenated products thereof, phenolic resins, modified phenolic resins (for example, cache oil modified phenolic resins, tol oil modified phenolic resins), terpene phenolic resins, and the like.
  • Styrene block copolymers and their hydrogenated products include styrene butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer. (S), styrene ethylene butylene styrene block copolymer (SEBS), styrene-ethylene propylene styrene block copolymer (SEPS), styrene isobutylene styrene block copolymer (SIBS) and the like.
  • SBS styrene butadiene-styrene block copolymer
  • SEBS styrene ethylene butylene styrene block copolymer
  • SEPS styrene-ethylene propylene styrene block copolymer
  • SIBS styrene isobutylene styrene block copolymer
  • the tackifier resin is used in the range of 5 to 1,000 parts by weight, preferably 10 to L00 parts by weight with respect to 100 parts by weight of the organic polymer (A).
  • a plasticizer may be added to the composition of the present invention.
  • a plasticizer By adding a plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted.
  • plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, succinate
  • Non-aromatic dibasic acid esters such as isodecyl acid; Aliphatic esters such as ptyl oleate and methyl acetyl glycylic acid; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters Chlorinated paraffins; hydrocarbon oils such as alkyl diphenols and partially hydrogenated terfals; process oils; epoxy plasticizers such as epoxy soybean oil and benzyl epoxy stearate.
  • a polymer plasticizer can be used.
  • the initial physical properties are maintained for a long period of time compared to the case of using a low-molecular plasticizer that is a plasticizer that does not contain a polymer component in the molecule.
  • the drying property also referred to as paintability
  • the polymer plasticizer include a bull polymer obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycol such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester.
  • Polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol having a molecular weight of 500 or more and even 1000 or more
  • polyethers such as derivatives in which the hydroxyl groups of these polyether polyols are converted to ester groups, ether groups, etc .
  • polystyrenes such as polystyrene and poly- a -methylstyrene
  • polybutadiene, polybutene, polyisobutylene, butadiene acrylonitrile Forces such as PVC mouth-opening are not limited to these.
  • polyethers and vinyl polymers are preferable.
  • polypropylene glycol is more preferable because it improves surface curability and deep part curability and does not cause curing delay after storage.
  • a bull polymer is preferable from the viewpoint of compatibility, weather resistance, and heat resistance.
  • acrylic polymers such as polyacrylic acid alkyl esters, which are preferred to acrylic polymers and Z or methacrylic polymers, are more preferred.
  • the polymer transfer method is more preferably an atom transfer radical polymerization method in which a living radical polymerization method is preferred because the molecular weight distribution is narrow and low viscosity can be achieved. Further, it is preferable to use a polymer obtained by so-called SGO process obtained by continuous bulk polymerization of an alkyl acrylate monomer as described in JP-A-2001-207157 at high temperature and high pressure. Specifically, Alfon UP-1000, UP-1010, UP-1020, UP-1110, etc. manufactured by Toagosei Co., Ltd. may be mentioned.
  • the number average molecular weight of the polymer plasticizer is preferably a force of 500-15000, more preferably
  • the molecular weight distribution of the polymer plasticizer is not particularly limited, but it is preferable that the molecular weight distribution is narrow. Specifically, the value of Mw ZMn (weight average molecular weight Z number average molecular weight) is preferably less than 1.80. The value of M wZMn is more preferably 1.70 or less. 1. More preferably, it is 50 or less, and 1. Most preferably, it is 30 or less.
  • the number average molecular weight is measured by a GPC method in the case of a vinyl polymer and by a terminal group analysis method in the case of a polyether polymer.
  • the molecular weight distribution (MwZMn) is determined by the GPC method (polystyrene). (In terms of conversion). Specifically, although not particularly limited, specifically, the number average molecular weight and molecular weight distribution are, for example,
  • Liquid feeding system HLC-8120GPC manufactured by Tosoh Corporation
  • the polymer plasticizer may not have a reactive group, but may have a reactive group.
  • it When it has a reactive cage group, it acts as a reactive plasticizer and can prevent migration of the plasticizer from the cured product.
  • the average number per molecule is preferably 1 or less, more preferably 0.8 or less.
  • the number average molecular weight must be lower than that of the polymer of component (A). .
  • the plasticizers may be used alone or in combination of two or more.
  • a low molecular plasticizer and a high molecular plasticizer may be used in combination. These plasticizers can be blended at the time of polymer production.
  • the plasticizer is used in an amount of 0 to 150 parts by weight, preferably 0 to 120 parts by weight, more preferably 0 to: LOO parts by weight based on 100 parts by weight of the polymer of component (A). . If the amount of plasticizer exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
  • the curable composition of the present invention may contain a compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis.
  • This compound has the effect of reducing the modulus of the cured product without deteriorating the stickiness of the surface of the cured product.
  • a compound that generates trimethylsilanol is preferable.
  • 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.
  • R 3 is a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
  • generates a copper compound can also be mentioned.
  • a polymer having a crosslinkable hydrolyzable silicon-containing group described in JP-A-6-279693 and a silicon-containing group that can be converted into a monosilanol-containing compound by hydrolysis can also be used.
  • the compound that generates a compound having a monovalent silanol group in the molecule by hydrolysis is 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer having a reactive cage group (A).
  • a thixotropic agent may be added to the curable composition of the present invention, if necessary, in order to prevent sagging and improve workability.
  • the anti-sagging agent is not particularly limited, and examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal stalates such as calcium stearate, aluminum stearate, and barium stearate.
  • rubber powder having a particle diameter of 10 to 500 ⁇ m, or organic fibers as described in JP-A-2003-155389 are used.
  • a composition having high thixotropy and good workability can be obtained.
  • thixotropic agents anti-sagging agents
  • the thixotropic agent is used in the range of 0.1 to 20 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive carbon group.
  • a photocurable material can be used in the composition of the present invention.
  • a photocurable material is used, a film of a photocurable material is formed on the surface of the cured product, and the stickiness and weather resistance of the cured product can be improved.
  • a photo-curing substance is a substance that undergoes a chemical change in its molecular structure within a short period of time due to the action of light, resulting in a change in physical properties such as curing. Many compounds such as organic monomers, oligomers, resin, and compositions containing them are known as this type of compound, and any commercially available compound can be adopted. Representative examples include unsaturated acrylic compounds, polycalyx butyls, azide resins and the like.
  • unsaturated acrylic compounds A monomer, oligomer or mixture thereof having one or several acrylic or methacrylic unsaturated groups, which is propylene (or butylene, ethylene) glycol di (meth) acrylate, neopentyl dalycol Monomers or molecular weights such as (meth) attalylate
  • Examples include oligoesters of 10,000 or less. Specifically, for example, special allyrate (bifunctional) Aronix M-210, Aronix M-215, Aronix M-220, A-Lux M-233, A-Lux-M-240, A-Lux-M — 245; (Trifunctional) M-305, A-M, M- 309, A-M, M- 310, A-M, M-315, Aronix, M- 320, Aronix, M— 325, and (polyfunctional) Aronix M-400, etc. can be exemplified, but a compound containing an acrylic functional group is particularly preferred, and a compound containing 3 or more same functional groups on average in one molecule. Favored ,. (All of Alonix is !, and all are products of Toagosei Co., Ltd.)
  • polyvinyl cinnamates examples include photosensitive rosin having a cinnamoyl group as a photosensitive group, and polybutyl alcohol esterified with cinnamate, as well as many polyvinyl cinnamate derivatives.
  • Azide resin is known as a photosensitive resin having an azide group as a photosensitive group. Usually, it is a rubber photosensitive solution containing a diazide compound as a photosensitive agent. (Published 17th of May, published by the Printing Society Press, pages 93-, 106-, 117-), these are detailed examples. These are used alone or in combination, and sensitizers are added as necessary. Can be used.
  • the photo-curing substance is an organic polymer having a reactive carbon group (A) 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight. If less than 1 part by weight, the effect of improving the weather resistance is not sufficient. If it exceeds 20 parts by weight, the cured product becomes too hard and tends to crack.
  • A reactive carbon group
  • An oxygen curable substance can be used in the composition of the present invention.
  • An example of the oxygen curable substance is an unsaturated compound that can react with oxygen in the air.
  • the oxygen curable substance reacts with oxygen in the air to form a cured film near the surface of the cured product, resulting in surface stickiness or the surface of the cured product. It acts to prevent dust from adhering to dust.
  • oxygen curable substance examples include drying oil typified by drill oil, Amani oil, etc., various alkyd oils obtained by modifying the compound, acrylic polymer modified with drying oil, epoxy System resin, silicone resin; Polymers such as 1,2 polybutadiene, 1,4 polybutadiene, and C5 to C8 polymers obtained by polymerizing or copolymerizing genic compounds such as ethylene, black-opened plane, isoprene, and 1,3 pentagene.
  • monomers such as talitol, nitrile, and styrene that are copolymerizable with these gen compounds so that the gen compound is the main component
  • various modified products thereof maleized modified products, boiled oil modified products, etc.
  • drill oil and liquid gen-based polymers are particularly preferred.
  • the use of a catalyst that promotes the oxidative curing reaction or a metal dryer may enhance the effect.
  • Examples of these catalysts and metal dryers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate.
  • the amount of the oxygen curable substance used is preferably 0.1 to 20 parts by weight, more preferably 0 to 100 parts by weight of the organic polymer (A) having a reactive key group. 5 to 10 parts by weight. If the amount used is less than 0.1 parts by weight, the contamination is not improved sufficiently, and if it exceeds 20 parts by weight, the tensile properties of the cured product tend to be impaired.
  • an oxygen curable substance is preferably used in combination with a photocurable substance.
  • an anti-oxidation agent in the composition of the present invention.
  • Use of an antioxidant can increase the heat resistance of the cured product.
  • the antioxidant are hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.
  • Specific examples of hindered phenolic antioxidants include IRGANOX 1010, IRGANOX 1076, IRGANOX 245 (all of which are manufactured by Chinoku Specialty Chemicals); ADK STAB AO-20, ADK STAB AO-40 (above Asahi Denka Kogyo Co., Ltd.).
  • Tinuvin 622LD, Tinuvin 144, CHIMASSORB 944FDL, CHIMAS SORB 119FL (all of these are manufactured by Chinoku Specialty Chemicals); Adecast LA-57, Adekastab LA-62, Adekastab LA-63, ADK STAB LA—67, ADK STAB LA—68 (all manufactured by Asahi Denki Kogyo Co., Ltd.); Sanol LS—770, Sanol LS—765, Sanol LS—292, Sanol LS—2626, Sanol LS—1114 , Sa Hinder Doamine-based light stabilizer shown in Nord LS-744 (above, manufactured by Sankyo Lifetech Co., Ltd.) and benzoate-type light stabilizer shown in TINUVIN 120 (made by Ciba 'Specialty' Chemicals Co., Ltd.) Can also be used.
  • the antioxidants and light stabilizers are used in an amount of 0.1 to L0 parts by weight per 100
  • An ultraviolet absorber can be used in the composition of the present invention.
  • Use of a UV absorber can improve the surface weather resistance of the cured product.
  • the UV absorber include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds. Particularly, benzotriazole-based is preferable.
  • the amount of the UV absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the organic polymer (A) having a reactive key group. 5 parts by weight. It is preferable to use a combination of a phenolic or hindered phenolic acid inhibitor, a hindered amine light stabilizer and a benzotriazole ultraviolet absorber.
  • An epoxy resin can be added to the composition of the present invention.
  • a composition to which epoxy resin is added is particularly preferred as an adhesive, particularly as an adhesive for exterior wall tiles.
  • Epoxy olefins such as epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin bisphenol F type epoxy resin, tetrabromobisphenol A glycidyl ether, flame retardant type epoxy resin, Novolac epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin with bisphenol A propylene oxide, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol Mono-epoxy epoxy resin, diaminodiphenole-epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidyl dilin, N, N-diglycidyl ro o-toluidine, Triglycidyl isocyanur
  • the known epoxy resin can be used.
  • the ability to contain at least two epoxy groups in the molecule is also preferred because it has high reactivity during curing and the cured product can easily form a three-dimensional network.
  • Even better Preferred examples include bisphenol A type epoxy resins or novolac type epoxy resins.
  • the preferred use ratio varies depending on the use of the curable resin composition, and cannot be determined unconditionally.
  • the component (A) is used in an amount of 1 to: L00 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the epoxy resin.
  • the strength of the cured product of component (A) 1 to 200 parts by weight, more preferably 5 to 100 parts by weight of epoxy resin per 100 parts by weight of component (A) is used. Good.
  • an epoxy resin is added, it goes without saying that a hardener that cures the epoxy resin can be used in combination with the composition of the present invention.
  • a hardener that cures the epoxy resin can be used in combination with the composition of the present invention.
  • an epoxy resin hardener generally used can be used, but a compound having a primary amino group cannot be used.
  • tripropylamine N, N-dimethylpropylamine, N, N, ⁇ ', ⁇ , -tetramethylhexamethylenediamine, ⁇ -methylpyrrolidine, ,, ⁇ , monodimethylbiperazine , Dimethyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, and tertiary amines, and salts of these tertiary amines; polyamide resins; imidazoles; dicyandiamides; Boron trifluoride complexes; carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride; alcohols; Examples of compounds such as phenols; carboxylic acids; diketone complex compounds of aluminum or zirconium are not limited thereto
  • the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of epoxy resin.
  • Ketimine can be used as a curing agent for epoxy resin.
  • Ketimine epoxy Well known as a latent curing agent for fats, it reacts with moisture in the air and decomposes to produce an amine compound.
  • Ketimines obtained by reacting a compound having a primary amino group with methylisoptyl ketone as a raw material are commercially available and can be easily obtained. Examples of ketimines include Epicure H-3, Epicure H-30 (above!
  • Ade force hardener EH— 235R Ade force hardener EH— 235R-2
  • Ade force hardener EH-235X Ade force hardener EH-235X (the above is a product of Asahi Denka Kogyo Co., Ltd.).
  • These ketimines may be used alone or in combination of two or more.
  • One hundred parts by weight of epoxy resin is used in an amount of 1 to: LOO parts by weight. It depends on the type of ketimine.
  • the curable composition of the present invention has a difficulty such as phosphorus plasticizers such as ammonium polyphosphate and tricresyl phosphate, aluminum hydroxide, magnesium hydroxide, and thermally expandable graphite.
  • a flame retardant can be added. The above flame retardants may be used alone or in combination.
  • the flame retardant is used in the range of 5 to 200 parts by mass, preferably 10 to LOO parts by mass with respect to 100 parts by mass of component (A).
  • a solvent can be used for the purpose of reducing the viscosity of the composition, increasing thixotropy, and improving workability.
  • the solvent various compounds with no particular limitation can be used. Specific examples include toluene, xylene, heptane, hexane, hydrocarbon solvents such as petroleum solvents, halogen solvents such as trichloroethylene, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, ether solvents, alcohol solvents such as methanol, ethanol and isopropanol, silicone solvents such as hexamethylcyclotrisiloxane, otamethylcyclotetrasiloxane and decamethylcyclopentasiloxane Is illustrated.
  • the boiling point of the solvent is preferably 150 ° C or higher, more preferably 200 ° C or higher, more preferably 250 ° C or higher, due to air pollution problems when the composition is used indoors. Especially preferred. These solvents may be used alone or in combination of two or more.
  • the blending amount of the solvent is (A) component
  • the amount is preferably 3 parts by weight or less based on 100 parts by weight of the organic polymer, more preferably 1 part by weight or less, and most preferably substantially free of solvent.
  • additives may be added to the curable composition of the present invention as necessary for the purpose of adjusting various physical properties of the curable composition or the cured product.
  • additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents. Ant-proofing agents, solvents, fungicides and the like.
  • flame retardants include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, ozone degradation inhibitors, phosphorus peroxide decomposers, lubricants, pigments, foaming agents.
  • Ant-proofing agents include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Laid-Open No. 63-254149, Japanese Patent Laid-Open No. 64- No. 22904, JP-A-2001-72854, etc.
  • the one-component curable composition of the present invention all the components are preliminarily blended and stored, and are cured by moisture in the air after application. Since it is a one-component curable composition in which all the ingredients are pre-blended, it is preferable that the ingredients containing moisture be dehydrated and dried before use, or dehydrated by vacuum during compounding and kneading. . Dehydration and drying methods include heat drying for solids such as powders, vacuum dehydration for liquids, or dehydration using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, etc. Is preferred.
  • isocyanate compound may be blended and the isocyanate group and water reacted to dehydrate.
  • an oxazolidin compound such as 3 ethyl 2-methyl 2- (3-methylbutyl) 1,3 oxazolidine may be blended and reacted with water for dehydration.
  • Lower alcohols such as methanol and ethanol in addition to the powerful dehydration drying method; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, methylsilicate, ethylsilicate, ⁇ mercaptopropylmethyldimethoxysilane,
  • an alkoxysilane compound such as ⁇ -mercaptopropylmethyljetoxysilane or ⁇ -glycidoxypropyltrimethoxysilane, the storage stability is further improved.
  • the amount of a dehydrating agent, particularly a key compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 with respect to 100 parts by weight of an organic polymer having a reactive key group. Part by weight, preferably in the range of 0.5 to 10 parts by weight.
  • the method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, a roll, a roll or the like at room temperature or under heating, or a suitable solvent. Ordinary methods such as using a small amount of the ingredients to dissolve and mixing the components may be employed.
  • the curable composition of the present invention When exposed to the atmosphere, the curable composition of the present invention forms a three-dimensional network structure by the action of moisture, and cures to a solid having rubbery elasticity.
  • the one-component curable composition of the present invention does not use a harmful organic tin compound, and is excellent in curability, adhesion, and storage stability.
  • methanol was distilled off by adding 1.2 times equivalent of a methanol solution of NaOMe to the hydroxyl group of this hydroxyl group-terminated polypropylene oxide (P-1). Was added to convert the terminal hydroxyl group to an aryl group. Unreacted salt aryl was removed by vacuum devolatilization. After mixing and stirring 300 parts by weight of n-hexane and 300 parts by weight of water with respect to 100 parts by weight of the obtained unpurified aryl group-terminated polypropylene oxide, water was removed by centrifugation, and the resulting hexane was obtained.
  • the average was 1.3.
  • the resulting trimethoxysilyl group-terminated polyoxypropylene polymer (A-2) has the following chemical formula:
  • the average number of trimethoxysilyl groups per molecule was about 1.2.
  • Example 1 except that 100 parts by weight of the trimethoxysilyl terminal polyoxypropylene polymer ( ⁇ -2) obtained in Synthesis Example 2 was used in place of the polymer (A-1) in Example 1. In the same manner, a curable composition was obtained.
  • Example 4 ⁇ ⁇ -ethyl-y-aminoisobutyltrimethoxysilane (manufactured by GE Silicones Corp., trade name: Silquest A-Linkl5) was used except that 1.24 parts by weight were used. A curable composition was obtained in the same manner as in Example 1. [0154] (Example 4)
  • Example 1 instead of A-1170 in Example 1, 1.43 parts by weight of (N-phenol- ⁇ -aminopropyl) trimethyoxysilane (manufactured by Dow Coung Co., Ltd., trade name: : -9669) was used. In the same manner as in Example 1, a curable composition was obtained.
  • (N-phenol- ⁇ -aminopropyl) trimethyoxysilane manufactured by Dow Coung Co., Ltd., trade name: : -9669
  • a curable composition was obtained in the same manner as in Example 1 except that A-1170 in Example 1 was not used.
  • Example 2 Similar to Example 1 except that 3 parts by weight of y-aminopropyltrimethoxysilane (manufactured by Toray Dow Cowing Co., Ltd., trade name: A-1110) was used instead of A-1170 in Example 1. Thus, a curable composition was obtained.
  • y-aminopropyltrimethoxysilane manufactured by Toray Dow Cowing Co., Ltd., trade name: A-1110
  • Example 1 a reaction product of y-glycidoxypropyltrimethoxysilane and ⁇ -aminopropinoletriethoxysilane (excess of ⁇ -aminopropyltriethoxysilane) ( A curable composition was obtained in the same manner as in Example 1, except that 4.4 parts by weight of Chisso Corporation, trade name: Silaace XS-1 104) was used.
  • a curable composition was obtained in the same manner as in Example 1 except that A-187 and A-1170 in Example 1 were not used.
  • Example 1 instead of using 4 parts by weight of vinyltrimethoxysilane (trade name: A-171 manufactured by Toray Dow Cowing Co., Ltd.) A curable composition was obtained in the same manner as in Example 1.
  • the above curable composition is stretched to a thickness of about 3 mm under conditions of 23 ° C and 50% RH, and the surface of the curable composition is sometimes lightly touched with a microspatella, and the composition adheres to the microspatella. The time until it stopped was measured. The results are shown in Tables 3 and 4.
  • each one-component curable composition put in a dryer at 50 ° C for 28 days, take it out and put it in 23 ° C 50% RH condition for one day or more, and then The hardenability was evaluated and compared with the initial value.
  • the value of the curability after storage does not change at all compared to the initial curability, that is, the rate of change is 1.0, ⁇ , the rate of change is from 0.7 to 1.3, and the rate of change is 0. .
  • Less than 7 or greater than 1.3 is denoted as ⁇ , and greater than 3.0 is denoted as X.
  • the curable composition at the initial stage and after storage was measured for 2 rpm viscosity at 23 ° C. using a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.) and rotor No. 7.
  • the value obtained by dividing the viscosity value after storage by the initial value is calculated as the rate of increase in viscosity after storage, and the viscosity increase rate from 1.0 to 1.4 is ⁇ , greater than 1.4. Less than ⁇ , 2.0 or more
  • composition (comparative example)
  • Example 16 As shown in 6, using (A) an organic polymer having a reactive cage group, (B) a titanium catalyst, and (C) an epoxy silane, and having no compound having a primary amino group.
  • the curable composition has a low viscosity change and good stability before and after storage, where the curability is fast.
  • the composition is also environmentally friendly because it has good properties and does not contain an organic tin compound.
  • Comparative Examples 1 to 4 to which a compound having a primary amino group is added have increased viscosity after storage and lack stability.
  • Comparative Example 5 containing no silane coupling agent the initial curability is fast, but the adhesion to the substrate is poor, and it is cured in the cartridge after storage, so the physical properties are poor.
  • Comparative Example 6 In Comparative Example 6 in which butylsilane was used instead of epoxysilane, the stability of physical properties before and after storage was good, but the adhesion to the substrate was poor. Comparative Example 7 using an organic tin compound has good curability and stability after storage, but has insufficient adhesiveness, has an environmental burden, and has poor environmental compatibility. Industrial applicability
  • the curable composition of the present invention comprises a pressure-sensitive adhesive, a sealing material for a building 'ship' automobile 'road, an adhesive, a mold preparation, a vibration-proofing material, a vibration-damping material, a sound-proofing material, a foamed material, and a paint. Can be used for spraying materials. Since a cured product obtained by curing the curable composition of the present invention is excellent in flexibility and adhesiveness, among these, it is more preferable to use it as a sealing material or an adhesive.
  • electrical / electronic component materials such as solar cell backside sealing materials, electrical insulation materials such as insulation coating materials for electric wires and cables, elastic adhesives, outer contour adhesives, spray-type sealing materials, and crack repairs Materials, tile adhesives, powder paints, casting materials, medical rubber materials, medical adhesives, medical equipment sealants, food packaging materials, sealing materials for joints of exterior materials such as sizing boards, coatings Materials, primers, conductive materials for shielding electromagnetic waves, thermal conductive materials, hot-melt materials, potting agents for electrical and electronic use, films, gaskets, various molding materials, and prevention of meshed glass and laminated glass end faces (cut parts) 'It can be used for various applications such as liquid sealants used in waterproof sealants, automotive parts, electrical parts, and various machine parts.
  • the curable composition of the present invention includes an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiles, an adhesive for stonework, an adhesive for ceiling finish, an adhesive for floor finish, and a wall finish.
  • Adhesives, vehicle panel adhesives, electrical 'electronic' precision equipment assembly adhesives, direct glazing seals It can also be used as a sealing material for double glazing, a sealing material for double-glazed glass, a sealing material for the SSG method, or a sealing material for single king joints in buildings.

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Abstract

Composition durcissable de type composition monocomposant laquelle ne contient pas de catalyseur organostannique et est satisfaisante en termes d'aptitude à durcir, d'adhérence et de stabilité au stockage. La composition durcissable de type composition monocomposant comprend (A) un polymère organique ayant un groupe contenant du silicium qui peut être réticulé en formant une liaison siloxane, (B) un catalyseur en titane et (C) un composé silane ayant un groupe époxy et un groupe alcoxy et elle est caractérisée en ce qu'elle ne comprend pratiquement pas de catalyseur organostannique et pratiquement pas de composé ayant un groupe amino primaire.
PCT/JP2006/319457 2005-09-30 2006-09-29 Composition durcissable de type composition monocomposant WO2007037368A1 (fr)

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JP2008303375A (ja) * 2007-05-07 2008-12-18 Momentive Performance Materials Japan Kk 硬化性組成物
JP2010215715A (ja) * 2009-03-13 2010-09-30 Shin-Etsu Chemical Co Ltd 接着促進剤及び硬化性樹脂組成物
JP2010285462A (ja) * 2009-06-09 2010-12-24 Konishi Co Ltd 難燃性湿気硬化型接着剤組成物
WO2012056850A1 (fr) * 2010-10-27 2012-05-03 セメダイン株式会社 Composition durcissable
WO2012057281A1 (fr) * 2010-10-27 2012-05-03 セメダイン株式会社 Composition durcissable
JP2013053272A (ja) * 2011-09-06 2013-03-21 Cemedine Co Ltd 硬化性組成物
JP2013060589A (ja) * 2011-08-25 2013-04-04 Cemedine Co Ltd 常温湿気硬化性接着剤組成物
WO2014175358A1 (fr) * 2013-04-24 2014-10-30 積水フーラー株式会社 Composition durcissable et structure de joint fabriquée à partir de la composition

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