WO2004108774A1 - Resine durcissable, son procede de production et composition contenant cette resine durcissable - Google Patents

Resine durcissable, son procede de production et composition contenant cette resine durcissable Download PDF

Info

Publication number
WO2004108774A1
WO2004108774A1 PCT/JP2004/007881 JP2004007881W WO2004108774A1 WO 2004108774 A1 WO2004108774 A1 WO 2004108774A1 JP 2004007881 W JP2004007881 W JP 2004007881W WO 2004108774 A1 WO2004108774 A1 WO 2004108774A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
curable resin
group
general formula
represented
Prior art date
Application number
PCT/JP2004/007881
Other languages
English (en)
Japanese (ja)
Inventor
Shinichi Sato
Yukihiro Nomura
Jun Inui
Original Assignee
Konishi Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konishi Co., Ltd. filed Critical Konishi Co., Ltd.
Priority to JP2005506803A priority Critical patent/JPWO2004108774A1/ja
Publication of WO2004108774A1 publication Critical patent/WO2004108774A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon

Definitions

  • the present invention relates to a curable resin, a method for producing the same, and a composition containing the curable resin. More specifically, the present invention relates to a curable resin suitable for applications such as an adhesive, a sealant, and a paint, a method for producing the same, and a curability thereof. The present invention relates to a composition containing a resin and exhibiting excellent adhesiveness for the above uses, and a curable resin composition containing a curable resin.
  • Japanese Unexamined Patent Publication No. Hei 8-337713 discloses a modified silicone resin in which the main chain skeleton is a polyalkylalkylene polymer.
  • this resin has a low viscosity, it does not have active hydrogen in the molecular skeleton, so that it is not a resin having sufficient adhesiveness, and it is desired to improve the adhesiveness.
  • the present invention relates to a curable resin having a silyl group at a terminal, a moisture-curable resin having excellent adhesiveness, a method for producing the same, a composition containing the same, and a curable resin containing the curable resin. It is intended to provide a composition.
  • the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer, and a resin having an aryl group at a terminal.
  • a thioether bond and a thiourethane and / or urea bond or a substituted urea bond into a molecule and introducing a hydrolyzable silyl group such as an alkoxysilyl group at the terminal.
  • the present invention has been completed. Disclosure of the invention
  • the present invention provides a compound having a silicon atom-containing group in which at least one hydrolyzable group selected from an alkoxy group, an acetyl group and an oxime group is directly bonded to a silicon atom at the molecular terminal,
  • a thioether bond, a thioethane bond and / or a urea bond or a substituted urea bond (2) a thioether bond, a hydroxyl group and a secondary or tertiary amino group or (3) a thioether bond and a secondary or tertiary bond
  • a curable resin having a primary amino group and having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer.
  • the curable resin of the present invention is characterized in that the hydrolyzable group is an alkoxy group.
  • the gist of the present invention is that the curable resin of the present invention is represented by the following general formula (1).
  • A is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer whose main chain skeleton is a reactive residue of a polyvalent aryl compound whose terminal is an aryl group, n is 1 to 20;
  • R 1 is a divalent organic group having a molecular weight of 100,000 or less;
  • R 2 is a divalent organic group having a molecular weight of 300 or less;
  • X is the following general formula (2) And groups represented by general formula (3), general formula (4), general formula (5) or general formula (6).
  • R is an alkyl group having 1 to 6 carbon atoms
  • R 3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • m is 1 to 3
  • R 4 has a side chain having 1 to 10 carbon atoms.
  • a good alkylene group or an arylene group R 5 is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms
  • R 6 is a hydrogen atom
  • a side chain having 1 to 10 carbon atoms Represents a good alkyl group or an aryl group, respectively.
  • D and E each represent a group represented by the following formula (7), (8), (9) or (10), and D and E may be the same or different.
  • R 7 is a hydrogen atom or a group represented by the formula —CO R 8 (R 8 is an alkyl group having 1 to 20 carbon atoms); R 9 is a hydrogen atom; one CH 2 COOH or a methyl group; An alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, Z is a hydrogen atom, ⁇ R 1 G , R 1 .
  • NH 2 and R 1 Q are a hydrogen atom, an organic group having a molecular weight of 500 or less or a group represented by the following general formula (11), and R 11 is a compound having a molecular weight of 300 or less.
  • An organic group, R 12 represents an organic group having a molecular weight of 200 or less,
  • the present invention provides a polyvalent aryl compound having a main chain skeleton of a poly (alkylene) -based polymer, a (meth) acrylic acid ester-based polymer or a hydrocarbon-based polymer, the terminal of which is an aryl group; — R 1 — Dithiol compound represented by SH (R 1 is as defined above), diisocyanate compound represented by formula OCN—R 2 — NCO (R 2 is as defined above), and A gist of the present invention is a method for producing a curable resin represented by the above general formula (1), which comprises reacting a compound represented by the formula HX (X has the same meaning as described above).
  • the gist of the present invention is that the curable resin of the present invention is represented by the following general formula (12).
  • R 1 , R 2 , n and X are as defined above, and R 13 is hydrogen An atom, a group represented by the above general formula (7), the general formula (8), the general formula (10), or the following general formula (13) (R 14 is an alkyl group having 1 to 20 carbon atoms;
  • 15 represents an alkyl group having 1 to 20 carbon atoms. ) Are shown.
  • the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group; R 1 - Jiisoshi represented by NCO - NHR 1 3 thioamine compounds that Ru represented by (R 1 are as defined above, R 13 represents a molecular weight 50 0 following organic groups.), wherein ⁇ CN @ - R 2 Wherein R 2 has the same meaning as described above and a compound represented by the formula HX (X has the same meaning as described above).
  • the gist is a method for producing a curable resin as shown.
  • curable resin of the present invention is represented by the following general formula (14).
  • A, R, RR 3, R 4, R 13, m and n are Ru as defined der above.
  • the present invention relates to a polyvalent alkyl compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group; - R 1 - NH R 1 3 thioamine compounds Ru indicated by (. R 1 and R 1 3 are as defined above) and compounds represented by the following general formula (1 5) (R, R 3, R 4 And m have the same meanings as above.) 4007881
  • the gist is a method for producing a curable resin.
  • the gist of the present invention is that the curable resin of the present invention is represented by the following general formula (6).
  • A, R, R 1 , R 3 , R 4 , m and n are as defined above.
  • the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group.
  • the gist is a method for producing a curable resin as shown.
  • the gist of the present invention is that the curable resin of the present invention is represented by the following general formula (17).
  • R 1 , R 2 , X and n are as defined above, and R 16 is a hydrogen atom or an organic group having a molecular weight of 500 or less.
  • the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group.
  • Jiisoshiane DOO compound represented by NCO R 2 is as defined above) as well as' the compound of formula HX to (X. is as defined above).
  • the gist of the present invention is a method for producing a curable resin represented by the general formula (17), which is characterized by reacting.
  • the gist of the present invention is that the curable resin of the present invention is represented by the following general formula (18). OR),)
  • A, R, R 1 R 3 , R 4 , R 16 , m and n are as defined above.
  • the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group.
  • Ariruamin compound represented by NHR 1 6 R 1 6 is as defined above
  • a method for producing a curable resin represented by the general formula (18) which comprises reacting the compound represented by the general formula (15).
  • the present invention provides a polyvalent alkylene compound having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, the terminal of which is an aryl group.
  • Production Method A a method for producing the curable resin of the present invention (hereinafter, referred to as Production Method A), which comprises reacting a compound represented by the following general formula (19).
  • R, R 3 , R 4 and m are as defined above.
  • the curable resin preferably has the following general formula (20) or (2)
  • the gist of the present invention is a curable resin in which the curable resin is represented by the following general formula (22) or (23).
  • the curable resin preferably has the following general formula (24) or (2) 5) A curable resin that is represented by
  • A, R, R 1 , R 3 , R 4 , R 16 , m and n are as defined above.
  • the present invention provides a reaction product of an arylglycidyl ether and a compound represented by the following general formula (27), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or Reacting a polyvalent aryl compound which is a hydrocarbon polymer and the terminal of which is an aryl group, and a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above).
  • the gist is a method for producing a curable resin represented by the general formula (20) or (21), which is characterized by the following. )
  • R, R 3 , R 4 , R 16 and m are as defined above.
  • the present invention provides a reaction product of arylglycidyl ether and a compound represented by the following general formula (28), a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or a hydrocarbon.
  • a polymer-based polymer characterized by reacting a polyvalent aryl compound whose terminal is an aryl group and a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above).
  • the gist of the present invention is a method for producing a curable resin represented by the general formula (22) or (23).
  • R, R 3 , R 4 and m are as defined above.
  • the present invention provides a compound represented by the following general formula (29) and a compound represented by the following general formula:
  • the present invention provides a compound represented by the following general formula (31), wherein the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer.
  • the gist of the present invention is a method for producing a curable resin represented by the general formula (26), wherein (31)
  • R,. R 3 , R 4 , R 16 and m are as defined above.
  • the present invention provides an adhesive composition containing the curable resin as a component.
  • the present invention provides an adhesive composition containing the curable resin and a Lewis acid and Z or a complex thereof.
  • the curable resin composition of the present invention is characterized in that the Lewis acid is boron trifluoride.
  • the present invention ′ comprises a curable resin comprising 100 parts by mass of the curable resin and 5 to 1,000 parts by mass of a vinyl polymer obtained by polymerizing a polymerizable vinyl monomer.
  • the gist is a resin composition.
  • the gist of the present invention is a method for producing the curable resin composition, characterized by polymerizing a polymerizable vinyl monomer in a curable resin.
  • the present invention has a reactive silicon group in the molecule and contains one or more nitrogen or sulfur atoms selected from a (thio) urethane bond, a urea bond, a substituted urea bond and a chemical bond from a Michael addition reaction *.
  • the present invention relates to the above-mentioned curable resin, which has a polymerizable vinyl monomer and a reactive silicon group in the molecule, and is derived from (thio) urethane bond, urea bond, substituted urea bond and Michael addition reaction. Characterized by polymerizing a compound having at least one nitrogen or sulfur atom-containing bond or a hydroxy group selected from the group consisting of:
  • the gist is a method for producing the curable resin composition.
  • the present invention provides a curable resin composition containing a Lewis acid and / or a complex thereof.
  • the curable resin composition of the present invention is characterized in that the Lewis acid is boron trifluoride.
  • the present invention provides a compound having at least one silicon atom-containing group in which at least one hydrolyzable group selected from an alkoxy group, an acetoxyl group and an oxime group is directly bonded to a silicon atom, and having (1) thioether bond And a thiol bond and / or a urea bond or a substituted urea bond, (2) a thioether bond, a hydroxyl group and a secondary or tertiary amino group, or (3) a thioether bond and a secondary or secondary bond.
  • a curable resin having a tertiary amino group and having a main chain skeleton of a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer.
  • a hydroxyl-terminated polymer produced by reacting monoepoxide with an initiator in the presence of a catalyst is preferred. Yes.
  • an initiator a hydroxy compound having one or more hydroxyl groups or the like can be used.
  • Monoepoxyds include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran, etc. Can be used.
  • the catalyst include an alkali metal catalyst such as a potassium compound and a cesium compound, a composite metal cyanide compound 'catalyst, and a metal polyphenylene catalyst.
  • an alkali metal catalyst such as a potassium compound and a cesium compound
  • a composite metal cyanide compound 'catalyst such as the composite metal cyanide compound complex catalyst
  • a complex containing zinc hexocyano cobalt as a main component, an ether and a Z or alcohol complex are preferable.
  • Ether and / or alcohol complex The composition described in JP-B-46-272500 can be essentially used.
  • ether ethylene glycol dimethyl ether (Glyme), diethyl glycol dimethyl ether (DiGlyme), and the like are preferable, and handling during the production of the complex is preferred. Glyme is particularly preferred for this reason.
  • the alcohol for example, those described in Japanese Patent Application Laid-Open No. HEI 4-145123 can be used, but tert-butanol is particularly preferred. .
  • Polyoxyalkylene polymers having two or more functional groups are preferred. Specifically, polyoxyethylene, polyoxypyrene, polyoxybutylene are preferred. And polyoxyhexylene, reoxytetramethylene and the like. Preferred polyalkylene polymers are di- to hexavalent polyoxyethylene diols, polyoxypropylene diols, or mixtures thereof. . Polyoxyethylene diol is used as polyoxyethylene diol, and polyoxypropylene diol is used as polyoxypropylene diol and polyoxypropylene diol is used as polyoxypropylene diol. Rent reals,
  • Polymethylene-based polymers are available on the market, and they can be used in the present invention.
  • the products are, for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: P—200, P—300, glass manufactured, trade names: PML—300, PML—310
  • (meth) acrylic acid ester-based polymer examples include homopolymers of acrylic acid ester or methacrylic acid ester, and those (meth) acrylic acid ester based polymers.
  • acrylates or methacrylates examples include methyl (meth) acrylate (what is referred to as (meth) acrylate). And methyl methacrylate), ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate Alkyl such as tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth) acrylate Alkoxyalkyl (meth) acrylates, such as (meth) acrylate, ethoxyxyl (meth) acrylate, butoxyshethyl (meth) acrylate, 2-methoxyethoxyxyl (meth) acrylate, 2-acrylate Alkoxyalkoxyalkyl (me
  • hydrocarbon polymer examples include monorefenes having 1 to 6 carbon atoms, such as ethylene, propylene, 1-butene, isobutene, and 1-hexene.
  • hydrocarbon polymers hydrogenated products of polymers containing isobutene as the main monomer and of butadiene polymer have a functional group introduced into the terminal and a molecular weight This is preferred because it is easy to control and the number of terminal functional groups can be increased.
  • the polymer containing isobutene as the main monomer contains not only a homopolymer of isobutene but also 50% by mass or less of a monomer copolymerizable with isobutene.
  • a copolymer containing preferably 30% by mass or less, more preferably 10% by mass or less, can also be used.
  • Examples of the monomer that can be copolymerized with isopten include an olefin having 4 to 12 carbon atoms, a vinyl ether, an aromatic vinyl compound, a vinyl silane, and an aryl silane.
  • Such monomers include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-11-pentene, 1-1pentene, 4-methyl-1-pentene, 1-1hexene, vinylcyclohexene, Examples thereof include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, polymethylstyrene, divinylstyrene, vinyltrimethoxysilane, vinyltriethoxysilane, arylaminotrimethylsilane, and aryldimethoxysilane.
  • curable resin of the present invention examples include those represented by the above general formulas (1), (12), (14), (16), (17) or (18). .
  • curable resins and a method for producing the same will be specifically described.
  • curable resin 1 has, for example, a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon having a main chain skeleton.
  • the above polyvalent aryl compound typically has a number average molecular weight in the above range, and the main chain skeleton having a hydroxyl group at the end thereof is a poly (aryl) compound.
  • Oxyalkylene-based polymers, (meth) acrylate polymers or hydrocarbon-based polymers are converted to alkali metals, alkali metal hydrides, alkali metal alkoxides or alkali metal hydroxides, etc. And by reacting it with an organic halogen compound having a terminal aryl group and having 3 to 10 carbon atoms.
  • alkali metal sodium or potassium is preferable
  • organic halogen compound aryl chloride, aryl bromide, vinyl (chloro) is preferable.
  • examples include rometyl benzene, aryl (chloromethyl) benzene, and aryl (chloromethyl) ether.
  • commercially available products are commercially available and can be used.
  • As a commercially available product manufactured by Asahi Denka Kogyo Co., Ltd. -111, ARA-200, ARA-400, and the like.
  • the dithiol compound (hereinafter, referred to as compound (b)) used for producing the curable resin 1 is represented by the formula HS—R 1 —SH, where R 1 has a molecular weight of 10,0. It is a divalent organic group of 0 or less. Specific examples of the divalent organic group having a molecular weight of 100, 000 or less include an alkylene group having 1 or more carbon atoms which may have a side chain, and 6 or more carbon atoms which may have a side chain. CH 2 CHR 17 (G) q CHR 18 (J) r CH 2-
  • R 17 is a hydrogen atom or a hydroxy group
  • G is a sulfur atom or an oxygen atom
  • q is 0 or more
  • R 18 is a hydrogen atom or a hydrogen atom.
  • a oxy group, J is a sulfur atom or an oxygen atom, and r is 0 or 1 or more).
  • Examples of the compound (b) include 1,5-dimercapto-13-thiapentane (DMDS), eu, 8-dimercapto-3,6-dioxaoctane (DMDO), 1,3-ethanedithiol, Examples thereof include monodithiothreitol, dithioerythritol, and 3,4-dimercaptotoluene.
  • DMDS 1,5-dimercapto-13-thiapentane
  • DMDO 8-dimercapto-3,6-dioxaoctane
  • 1,3-ethanedithiol examples thereof include monodithiothreitol, dithioerythritol, and 3,4-dimercaptotoluene.
  • a compound having a spirane ring skeleton at both terminal thiols can be selected.
  • compound (c) is represented by the formula OCN—R 2 —NCO, where R 2 is a divalent organic group having a molecular weight of 10 or less.
  • R 2 is a divalent organic group having a molecular weight of 10 or less.
  • the compound (c) for example, aliphatic, alicyclic, araliphatic, aromatic diisocyanate compounds and the like can be mentioned. Hereinafter, specific examples thereof will be described.
  • Aliphatic diisocyanate compounds Trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamet Chilled sociate, 1, 2 — Propylene Residential, 1, 2 — Butylene Residual, 2, 3 — Petit Residential, 1, 3 — Petit Residential , 2,4,4-or 2,2,4-trimethylhexyl methyl isopropylate, 2,6-diisomethane dimethylproate.
  • Alicyclic di-sodium compounds 1,3—cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3—sic Hexane diisocyanate, 3 — Isolate methyl 1, 3, 5 and 5 — Trimethyl cyclohexyl isocyanate, 4 and 4 '— Bis (cyclohexylisocynate), methyl 2 and 4—cyclohexanediocyanate, methyl 1 and 2 and 6—cyclohexanediocyanate, 1, 3 — bis (isomethine methyl) cyclohexane, 1, 4 bis (isomethine methyl) cyclohexane, isophorone isothiocyanate, etc. .
  • Aroaliphatic diisocyanate compounds 1,3 or 1,4 xylylene diisocyanates or mixtures thereof, ⁇ , ⁇ '— diisocyanates — 1, 4 — Jechil Benzen, 1,
  • Aromatic diisocyanate compounds m — phenylenediocyanate, ⁇ — phenylenediocyanate, 4, 4 '— diphenyldiisocyanate, 1, 5-naphthalene socyanate, 4, 4 '-diphenylmetane ssionate, 2, 4 1 or 2, 6-triphenyl socyanate, 4, 4 'Toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, etc.
  • X in the compound represented by the formula HX (hereinafter referred to as compound (d)) used for producing the curable resin 1 is represented by the above general formula (2), (3), (4), (5) Or (6).
  • compound (e) compound (e)
  • compound (e) an ⁇ , —unsaturated carbonyl compound represented by the following general formula (33) (wherein R 6 , R 9 and ⁇ are as defined above)
  • compound (()) a maleic acid diester compound represented by the following general formula (34) (provided that R 8 and R i C have the same meanings as above).
  • a diisocyanate compound represented by the formula OCN—R 2 —NCO (where R 2 is as defined above)
  • a monool compound, a monoamine compound, A reaction product with a compound having an active hydrogen atom such as a monomeric butane compound may be used.
  • X is a compound (d) represented by the above general formula (3) or (4) is an aminosilane compound represented by the following general formula (36) (where R, R 3 , R 4 , R 5 and m are . mono represented by NC O - wherein the the same meaning) (hereinafter, compound (h) and that), the upper title compound (f), the compound (g), ⁇ Se Tonito Lil, the above formula R 1 3.
  • the compound to be reacted with the compound (h) is the compound (f), the compound (g), acetonitrile, a monoisocyanate compound represented by the above formula R 13 —NCO, or the general formula (35) )), D and E in the general formula (3) or (4) are the same as those of the compound (f), the compound (g), acetonitrile,
  • the general formula ( D and E in .3) or (4) will be different, and if three or more are used, the HX compound will consist of a different mixture of D and E in general formula (3) or (4).
  • the compound (d) in which X is represented by the above general formula (6) includes an aminosilane compound represented by the following general formula (38).
  • R, R 3, 1 4 and 111 are as defined before SL.
  • Examples of the compound (e) include a-amino-proprietary methoxysilane, ⁇ -amino-propyl triethoxylate, and a-amino-propyl Methyldimethoxysilane, D-Aminopropyl Methyljet Xilan, ⁇ -Aminore, Adimethylbutyritrimethylsilan, ⁇ —Aminor, r—Dimethylbutylmethyldimethoxysilane, ⁇ —Aminore, r—Dimethylbutyltriethoxysilane, ⁇ — Aminor, argymethyl, butylmethyl, ethyljet xylan, and the like.
  • Examples of the compound (f) include (meth) acryl compounds, vinyl ketone compounds, vinyl aldehyde compounds, and other compounds.
  • (meth) acrylic compounds methyl (meth) .acrylate, ethyl (meta) acrylate, propyl (methyl) Evening) acrylate, isopropyl (meta) acrylate, butyl (meta) acrylate, isobutyl (meta) acrylate, t-butyl (Meta) acrylate, pentyl (meta) acrylate, amimil (meta) acrylate, isoamyl (meta) acrylate, Hexyl (meta) acrylate, heptyl (meta) acrylate, octyl (meta) acrylate,
  • trimethylol property (meta) crerate, pentaerythrill (meta) crerate, pentaerythrite Tray (meta) clear rate, ethylene glycol (meta) clear rate, Tetray ethylene clear rate (meteor) clear rate , Polyethylene glycol (meta) acrylate, 1,4—butane diol (meta) acrylate, 1,6—hexan diol (Meta) acrylate, neopentyl cholesterol (meta) acrylate, trimethylol propanetrioxyl chelate (meta) acrylate, tritry (2—Hydroxy Shechil) Cryrate, tris (2-hydroxy shetil) Isonurate rate (meta) Accurate, tricyclodecane rate (meta) . ⁇ Acrylate, bisphenol A darcydil ether with epoxy (meta) acrylate added to (epoxy) (metal) acrylic, etc. Polyfunctional compound and polyfunctional compound Trade name of Taka
  • r-methacryloxypropyl methoxysilane having an alkoxysilyl group In addition to the above-mentioned compounds, r-methacryloxypropyl methoxysilane having an alkoxysilyl group, cointacryloxy propyl protry Ethoxy silane, alpha chromium oxymethyl dimethyl silane, ryoku methacryloxy meth, J reject xylan, ⁇ ⁇ Riloxypro built-in xylan, r-acryloxymethyldimethoxysilane and the like.
  • Vinyl ketone compounds include vinyl acetate, mesitylene oxide, vinyl ethyl ketone, vinyl butyl ketone, and the like, and pinyl aldehyde compounds include acrolein and metachlorine. And other compounds, such as maleic anhydride, maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, and thiochloroacetic acid.
  • compounds containing a fluorine atom, a sulfur atom, a yellow atom or a phosphorus atom therein are also included.
  • Compounds containing a fluorine atom include perfluorinated octylethyl (meta) acrylate, trifluoroethyl (meta) acrylate, and the like. Examples of such a compound include (meta) acryloxyshelfyl acid phosphate and the like.
  • Examples of the compound (g) include dimethyl methyl maleate, getyl maleate, dibutyl maleate, di-2-methyl ethylhexyl hexyl, and dioctyl maleate. These may be used alone or in combination of two or more. .
  • Examples of the monomeric amide compound represented by the above general formula (35) include N—Fenj-Ji-Ray-Mid, N—Cyclohexyi-Rem-Ay-Mid, and Hydroxif-Enil-My.
  • C N—Raw Lima Remide, Jethyl Fenil Remide, N— (2—Cross Fen) Mleimid, and the like.
  • Examples of the compound (h) include N— / 3 (aminoethyl) -aminobutyral trimethyoxysilane, N— / 3 (aminoethyl) mono-aminopropylmethyldimethoxysilane, and N— / 3 (aminoethyl) -alpha Aminobutyl pyrtriethoxysilane, N— / 3 (aminoethyl) -1-aminopropylpyrethylethoxysilane, aminopropyldimethylmethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N-1 (6-aminohexyl) -13-aminopropyl trimethoxysilane, N- (2-aminoethyl) 111 aminoundecyltrimethoxysilane and the like. These can be used alone or in combination of two or more.
  • the contact order of each compound in the reaction of the compound (a), the compound (b), the compound (c) and the compound (d) in preparing the curable resin 1 is not fixed but arbitrary. .
  • Each reaction is carried out in a temperature range of about 120 to + 150 ⁇ for about 1 to 1,000 hours.
  • the reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and cycloheptane.
  • the reaction ratio of the compound (a :), the compound (b), the compound (c) and the compound (d) is 0.5 to 1 mol of the aryl group in the compound (a). : L. 2 mol.
  • the reaction of the above compound (a) with another compound or a contact reaction product of another compound with another compound is carried out in the presence of a radical initiator.
  • a radical initiator examples include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2-methylbutyronitrile), benzoyl peroxide, and t-alkyl alcohol.
  • Peroxides such as oxyester, acetyl valoxide, and diisopropyl propyl carbonate are used.
  • ultraviolet irradiation may be used instead of using the radical initiator.
  • the above compound (e) and the above compound (f), the above compound (g), acetate nitrile or the above maleimide when preparing the compound (d) in which X is represented by the above general formula (2) The reaction with the compound is carried out in a temperature range of about ⁇ 20 to + 50 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent.
  • the reaction ratio of compound (e) with compound (f), compound (g :), acetonitrile or a maleimide compound is such that compound (f), compound (g), and acetonitrile are used per mole of compound (e).
  • the number of active hydrogens in the compound (e) is about (11) X (0.1 to 9) moles for the tolyl or maleimide compound.
  • curable resin 2 includes, for example, a polyoxyalkylene polymer having a main chain skeleton, and a (meth) acrylic polymer.
  • a Le ester polymer or hydrocarbon-based polymer, polyvalent Ariru compound thereof ends are Ariru group, the formula HS- R 1 - Chio Amin compound represented by NH R 1 3 (R 1 and R 1 3 is as defined above), wherein O CN- R 2 -..
  • Jiisoshianeto compound represented by NC O R 2 is Ru as defined der above
  • X is the same as above This is significant.
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • Thioamine compounds (. Hereinafter referred reduction compound (i)) has the formula HS- R 1 - is represented by NHR 1 3, R 1 and R 1 3 which in formula are as defined above.
  • R 1 3 has the formula HS- R 1 is a compound in the case of hydrogen atom (i) - may be used thioamine compounds of NH 2 but, R 1 3 is the general formula ( In the case of 7), the reaction product of the thioamine compound and the compound (f) or the compound (g) is used.
  • R 13 is the general formula (8)
  • the reaction product of the thioamine compound and acrylonitrile is used.
  • R 13 is the general formula (10)
  • a reaction product of the thioamine compound and the monomer compound represented by the general formula (26) may be used.
  • Specific examples of compound (i) include 2-aminobenzenethiol, 2-aminoethanethiol, 2-aminopurin-1-ol, and the like.
  • the compound (c) used in preparing the curable resin 1 can be used in the same manner.
  • the compound (d) used for preparing the curable resin 1 can be used in the same manner.
  • the order of contact of the compounds in the reaction of the polyvalent aryl compound, the thioamine compound, the diisocyanate compound, and the compound represented by HX in the preparation of the curable resin 2 is not limited and is arbitrary. You. Each reaction is carried out in a temperature range of about 20 to + 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those mentioned above.
  • the reaction ratio of the polyvalent aryl compound, the thioamine compound, the diisocyanate compound and the compound represented by the above HX is such that the ratio of the other compound is 1 mole of the aryl group in the polyvalent aryl compound. 0.5 to 1.2 mol.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from the above. Ultraviolet irradiation may be used.
  • curable resin 3 includes, for example, a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylate polymer or a hydrocarbon. a system polymer, polyhydric Ariru compound thereof ends are Ariru group, the formula HS- R 1 - NHR 1 Chio Amin compound represented by 3 (. R 1 and R 1 3 are as defined above) and It can be produced by reacting a compound represented by the above general formula (15) (R, R 3 , R 4 and m are as defined above).
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the compound (i) used in preparing the above-mentioned curable resin 2 can be used in the same manner.
  • the compound represented by the above general formula (15) include f-cyanatespropyltrimethoxysilane, r-isocyanatepropylmethyldimethylmethoxysilane, f-isocyanatepropyltrimethoxysilane, and f-isocyanoatepropyltrimethoxysilane. Cyanate propyl methyl ethoxysilane and the like.
  • Each of the polyvalent aryl compounds, the thioamine compounds and the compounds represented by the general formula (15) in the reaction of the curable resin 3 is prepared.
  • the order of contact of the compounds is not fixed but arbitrary.
  • Each reaction is performed in a temperature range of about 120 to 150 ° C. for about 1 to 1,000 hours.
  • the reaction may be performed in the presence of an organic solvent medium.
  • the organic solvent is selected from the above.
  • the reaction ratio of the polyvalent aryl compound, the thioamine compound and the compound represented by the general formula (15) is such that the other compound is 1 mole of the aryl group in the polyvalent aryl compound. Each is 0.5 to 1.2 mol.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from those described above. Ultraviolet irradiation may be used.
  • curable resin 4 has, for example, a polyoxyalkylene polymer having a main chain skeleton, a (meth) acrylic acid ester polymer or A polyvalent aryl compound which is a hydrocarbon polymer and the terminal of which is an aryl group; a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above); It can be produced by reacting the compound represented by (15).
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner.
  • the compound represented by the general formula (15) used when preparing the curable resin 3 can be used in the same manner.
  • the contact order of each compound in the reaction of the polyvalent aryl compound, the dithiol compound and the compound represented by the general formula (15) when preparing the curable resin 4 is not fixed but arbitrary. .
  • Each reaction is carried out in a temperature range of about 120 to 115 ° C for about 1 to 1,000 hours.
  • Anti The reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent is selected from the above.
  • the reaction ratio of the polyvalent aryl compound, the dithiol compound and the compound represented by the general formula (15) is such that the other compound is Each is 0.5 to 1.2 mol.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from those described above. Ultraviolet irradiation may be used.
  • curable resin 5 includes, for example, a polyoxyalkylene polymer having a main chain skeleton, an Esdel polymer (meth) acrylate, or a hydrocarbon.
  • a polyvalent aryl compound whose terminal is an aryl group, a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above), a formula CH 2 CH — CH 2 — an arylamine compound represented by NHR 16 (R 16 is a hydrogen atom or an organic group having a molecular weight of less than 500;), a disocyanate compound represented by the formula 0 CN—R 2 —NC 0 It can be produced by reacting a compound (R 2 is as defined above) and a compound of the formula (X is as defined above).
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner.
  • the compound represented by diisocyanation the compound (c) used in preparing the curable resin 1 can be used in the same manner.
  • the above formula CH 2 CH- CH 2 of Ariruamin compounds - but R 1 6 that put the NHR 1 6 is a hydrogen atom or a molecular weight 5 0 0
  • the following organic groups, the organic group Specific examples include an aryl group, the above general formula (7), the above general formula (8), the above general formula (10), the above general formula (13), a group represented by the following (39) (R, R 3 , R 4 and m are the same as defined above.) And the like.
  • the reaction product of acrylonitrile with the above-mentioned general formula (10) is the reaction product of arylylamine with the above-mentioned monomaleimide compound of the general formula (35), and the general formula (13) is the arylamine.
  • the maleic acid diester compounds 13 and R 14 represented by the following general formula (41) are as defined above.
  • the reaction product with the compound to be used may be used. Further, as the compound represented by diisocyanation, the compound (c) used in preparing the curable resin 1 can be used in the same manner. .
  • the contact order of each compound in the reaction of the compound represented by the formula (I), the arylamine compound, the diisocyanate compound, and the compound represented by HX is not limited, but is arbitrary.
  • Each reaction is performed in a temperature range of about 120 to 115 ° C. for about 1 to 1,000 hours.
  • the reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent is selected from those mentioned above.
  • the reaction rate of the polyvalent aryl compound, the dithiol compound, the arylyl compound, the diisocyanate compound, and the compound represented by HX is such that the ratio of the other compound to 1 mole of the aryl group in the polyvalent aryl compound is
  • the substances are each 0.5 to 1.2 moles.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from those described above. Ultraviolet irradiation may be used.
  • curable resin 6 has, for example, a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a carbonized resin having a main chain skeleton.
  • a polyvalent aryl compound whose terminal is an aryl group; a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above); a formula CH 2 C one CH 2 - Ariruamin compound represented by NHR 1 6, wherein NC O- R 2 (R 1 6 are as defined above.) - Jiisoshianeto compound represented by NC O (R 2 is the same as above Symbol And the compound represented by the above general formula (15).
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the compound (b) used for preparing the above-mentioned curable resin 1 can be used in the same manner.
  • an arylamine compound represented by the above formula CH 2 CH— CH 2 — NH R 16
  • an arylamine compound used for preparing the curable resin 5 can be used in the same manner.
  • the compound represented by the general formula (15) used for preparing the curable resin 3 can be used similarly.
  • the contact order of the compounds in the reaction of the polyvalent aryl compound, the dithiol compound, the arylamine compound, and the compound represented by HX in preparing the curable resin 6 is not fixed but arbitrary. Each reaction is carried out in a temperature range of about 120 to + 150 ° C. for about 1 to 1,000 hours. The reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.
  • the reaction ratio of the above polyvalent aryl compound, the above dithiol compound, the above arylamine compound and the compound represented by HX is 0.5 for each mole of the aryl group in the polyvalent aryl compound. ⁇ 1.2 moles.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from those described above. Ultraviolet irradiation may be used.
  • the main chain skeleton is preferably a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, and the terminal is an aryl group.
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the dithiol compound is The compound (b) used for preparing the curable resin 1 can be used in the same manner.
  • the compound (c) used when preparing the curable resin 1 can be used in the same manner.
  • Examples of the compound represented by the above general formula (19) include ⁇ -mercaptopropyltrimethoxysilane, r-mercaptopropylmethyldimethoxysilane, 7-mercaptopropyltriethoxysilane, and ⁇ -mercaptopropylmethylethoxyethoxysilane.
  • each reaction is performed in a temperature range of about 120 to 150 ° C. for about 1 to 1,000 hours.
  • the reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent is selected from those mentioned above.
  • the reaction ratio of the polyvalent aryl compound, the dithiol compound, the arylyl compound and the compound represented by the general formula (19) is such that the ratio of the other compound to the mole of the aryl group in the polyvalent aryl compound is 1 mol. They are 0.5 to 1.2 mol respectively.
  • the reaction between the polyvalent aryl compound and another compound or a contact reaction product of another compound with another compound is performed in the presence of a radical initiator.
  • the radical initiator is selected from those described above. Ultraviolet irradiation may be used.
  • curable resin represented by the general formula (20) (hereinafter referred to as curable resin 7) or the curable resin represented by the general formula (21) (hereinafter referred to as curable resin 8) is: It can be produced by the following method (1) or (2).
  • an arylglycidyl ether is reacted with a compound represented by the above general formula (27) to obtain a reaction product (A) of both.
  • the arylidyl ether and the compound represented by the general formula (27) are The compound represented by the above general formula (27) is used in an amount of 0.8 to 1.2 mol per 1 mol of the polyester, and the reaction is performed for ⁇ ⁇ ⁇ ⁇ ,:! To 500 hours.
  • the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and a polyvalent aryl compound whose terminal is an aryl group is represented by the formula HS—R 1 —
  • a polyvalent aryl compound whose terminal is an aryl group is represented by the formula HS—R 1 —
  • SH dithiol compound represented by SH
  • an arylglycidyl ether is reacted with the compound represented by the general formula (28) to obtain a reaction product (B) of both.
  • the arylylidyl ether and the compound represented by the general formula (28) are preferably a compound represented by the general formula (28) with respect to 1 mol of the arylglycidyl ether in the presence of the amino compound. 8 to 1.2 moles used, 50 The reaction is carried out for ⁇ 100, 1 ⁇ 500 hours.
  • the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon polymer, and a polyvalent aryl compound whose terminal is an aryl group is represented by the formula HS—R 1 —SH.
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner. The reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent. The organic solvent is selected from those described above.
  • the main chain skeleton is Polyoxyalkylene polymer, (meth) acrylic ester polymer or hydrocarbon polymer, which can be produced by reacting with a polyvalent aryl compound whose terminal is an aryl group.
  • the compound (a) used when preparing the curable resin 1 can be used in the same manner.
  • the reaction conditions may be in accordance with the above method (3).
  • curable resin 11 (hereinafter referred to as curable resin 11) or the curable resin represented by the general formula (25) (hereinafter referred to as curable resin 12) is used. It can be manufactured by the following method (5) or (6).
  • the compound represented by the general formula (29) is reacted with the compound represented by the general formula (30) to obtain a reaction product (C) of both.
  • the above—the compound represented by the general formula (29) and the compound represented by the general formula (30.) are the same as the general formula (29) with respect to 1 mol of the compound represented by the general formula (29).
  • the compound represented by the formula (30) is used in an amount of 0.8 to 12 mol, and the reaction is carried out at 50 to 100 for 1 to 500 hours.
  • the main chain skeleton is a polyoxyalkylene polymer, a (meth) acrylate polymer or a hydrocarbon polymer.
  • the compound (a) used in preparing the curable resin 1 can be used in the same manner. The reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent is selected from those described above.
  • the main chain skeleton is a polyoxyalkylene-based compound. It is a polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer, and can be produced by reacting with a polyvalent aryl compound whose terminal is an aryl group.
  • the compound (a) used for preparing the curable resin 1 can be used in the same manner.
  • the reaction conditions may be in accordance with the method (5).
  • curable resin 1 The general formula (2 6) curable resin represented by (hereinafter referred to as a curable resin 1 3.) Is (I) the general formula (3 1) with a compound of formula HS- R 1 one SH represented by After reacting the dithiol compound shown below (R 1 is as defined above), the main chain skeleton is changed to a polyoxyalkylene polymer, a (meth) acrylic ester polymer or a hydrocarbon polymer.
  • a polyaryl compound whose terminal is an aryl group or (mouth) a polyoxyalkylene polymer, a (meth) acrylic acid ester polymer or a hydrocarbon After reacting a polyvalent aryl compound whose terminal is an aryl group with a dithiol compound represented by the formula HS—R 1 —SH (R 1 is as defined above), Produced by reacting the compound represented by the formula (31).
  • the compound (a) used for preparing the above-mentioned curable resin 1 can be used in the same manner as the above-mentioned compound represented by the general formula (31), the compound represented by the formula HS — R 1 — at SH
  • the reaction ratio of the dithiol compound and the polyvalent aryl compound shown in the formula is 0.8 to 1.2 moles of the compound represented by the general formula (31) and 0.1 mole of the polyvalent aryl compound per mole of the dithiol compound.
  • the reaction is carried out at 50-100 ° C. for 1-500 hours. Each reaction may be performed in the presence of a medium such as an organic solvent.
  • the organic solvent is selected from those described above.
  • the gist of the present invention is a curable resin composition containing the curable resin as a component (hereinafter, referred to as composition 1).
  • the gist of the present invention is also a curable resin composition (hereinafter, referred to as composition 2) containing, as a component, a polymer (D) obtained by polymerizing the curable resin with a polymerizable vinyl group-containing monomer. I do.
  • composition 2 is particularly preferred because it can improve the adhesion to various adherends.
  • Examples of the polymerizable vinyl monomer include compounds selected from acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters (hereinafter, these are referred to as (meth) acrylic compounds). Evening) A portion of the polymerizable vinyl monomer composed of an acrylic compound is converted from nitrogen atoms derived from (thio) urethane bond, urea bond, substituted urea bond, and Michael addition reaction, which have a reactive silicon group in the molecule. It is preferably used instead of a compound having a selected bond or atom (hereinafter, referred to as compound (j)).
  • the curable resin composition containing the polymerizable vinyl monomer and the compound (j) is hereinafter referred to as composition 3.
  • the above (meth) acrylic compound and compound (j) are not limited to one kind, and two or more kinds can be used.
  • a (meth) acrylic compound of an ⁇ , ⁇ -unsaturated carbonyl compound (compound (f)) used for producing the curable resin 1 is selected from the group and used. Can be.
  • Examples of the compound (j) include the following compound (j-1) and the compound (j-1 2). It can be manufactured by a synthetic method. These compounds (j-1) and (j-12) are obtained by mixing a polymer obtained by polymerizing the compound alone and a polymer obtained by polymerizing a (meth) acrylic compound. However, it is particularly preferable to use it by copolymerizing with the above (meth) acrylic compound.
  • the copolymerization method for example, the compound (j-1) is copolymerized with a (meth) acrylic compound, the (j.-2) is copolymerized with a (meth) acrylic compound, and the compound (1-1) is copolymerized. ) And the compound (j-2) and a (meth) acrylic compound are preferably copolymerized.
  • R 2Q in the above general formula ( 42 ) represents a hydrogen atom or a methyl group
  • “” in (51) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 22 represents a hydrogen atom, an alkyl group having 120 carbon atoms, an aryl group or an aralkyl group.
  • the group, Q is an integer of 1 3
  • R 24 is represented by the water atom or formula one C OO R 25 Group (R 25 is a molecule: 500 or less
  • ⁇ 27 is a phenyl group, a cyclohexyl group or a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms
  • R 28 is a 120 carbon atom.
  • An alkyl group, an aryl group or an aralkyl group, R " 9 is a hydrogen atom, a phenyl group or a carbon number
  • I 20 is a substituted or unsubstituted organic group
  • R 3Q is a compound having a molecular weight of 500 or less. It represents a substituted or unsubstituted divalent organic group.
  • Y represents a hydrogen atom, OR 31 , R ′′ 1 or NHo, and R represents a hydrogen atom, an organic group having a molecule of 500 or less, or a group represented by the following general formula (52); )
  • R 21 , R 22 and R HC 23 are as defined above, and x is an integer of 13
  • V 1 , W 1 and V 2 are groups represented by the following HC general formula (53), (54), (55) or (56), respectively, and W 2 is V " There general formula when the general formula (3) (3), (5 4), (5 5) or (5 6), V 2 is the general formula. (5 4) formula when (5 3), (5 4), (5 5) or (5 6), V 2 is the general formula (5 5) general formula when the (3), (5 4> or (5 5), V beam general formula (5 6) represents a hydrogen atom.
  • R 22 , R 24 , R 26 , R 27 , R 28 and Y in the above general formulas (53), (54), (55) and (56) are as defined above.
  • Examples of the monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate group in the molecule include m-isopropenyl-1- ⁇ , 0! -Dimethylbenzyliso- Cyanate and 2-methacryloylloxityl isocyanate. These can be used commercially.
  • the monoisocyanate compound having a group represented by the above general formula (42) or (43) and an isocyanate in a molecule is a diisocyanate compound and the following general formulas (57), (5) It can also be produced by reacting the compound represented by 8) or (59).
  • the diisocyanate compound can be appropriately selected from dizocyanate compounds (compound (c)) used in producing the curable resin 1.
  • Examples of the compound represented by the general formula (57) include a reaction product of acrylamide, arylamine and the like with the above (meth) acrylic compound. ,
  • Examples of the compound represented by the general formula (58) include full furyl mercaptan, aryl mercaptan and the like.
  • Examples of the compound represented by the above general formula (59) include 4-hydroxypropyl acrylate, 2-hydroxyshetyl acrylate, 2-hydroxypropyl acrylate, 2-acryloxypropyl acrylate, and methacrylic acid.
  • the compound represented by the general formula (44) is represented by the following general formula (60)
  • a compound represented by the following general formula (61) By reacting a compound represented by the following general formula (61) with a compound represented by the following general formula (61).
  • R 21 , R 22 , 23 and q in the following general formula (60) and R 24 , R 2o and Y in the following general formula ( 61 ) are as defined above.
  • the reaction between the compound represented by the general formula (60) and the compound represented by the general formula (61) is carried out at 20 to 100 ° C for 1 to 500 hours.
  • Examples of the compound represented by the general formula (60) include araminopropylmethyldimethoxydilan, r-aminopropylmethylethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, And aminophenyltrimethoxysilane.
  • any compound can be selected from the above-mentioned (meth) acrylic compound, pinyl ketone compound, vinyl aldehyde compound, maleic acid diester, and other compounds. They are not limited to one kind; two or more kinds can be used.
  • any one of the vinyl ketone compounds of ⁇ -unsaturated carbonyl compound ′ (compound ( ⁇ )) used in producing the curable resin 1 can be selected and used.
  • the compound represented by the general formula (45) can be produced by reacting the compound represented by the general formula (60) with acrylonitrile. The reaction between the two is carried out for 1 to 1,000 hours at 2 ⁇ to ⁇ 0 ⁇ .
  • the compound represented by the general formula (46) is obtained by reacting the compound represented by the general formula (60) with the compound represented by the following general formula (62). Can be manufactured.
  • R 27 in the following general formula (62) has the same meaning as described above. The reaction between the two is carried out at 20 to 100 ° C. for 1 to 1,000 hours.
  • Examples of the compound represented by the general formula (62) include N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmonomaleimide,
  • N-laurel maleimide getyl phenyl monomaleimide, N- (2-chlorophenyl) maleimide and the like.
  • the compound represented by the general formula (47) can be produced by reacting the compound represented by the general formula (60) with the monoisocyanate compound represented by the formula R 28 NCO.
  • the monoisocyanate compound include ethyl isocyanate, n-hexyl isocyanate, n-decyl isocyanate, ⁇ -toluenesulfonyl isocyanate, benzyl isocyanate, and 2-methoxyphenyl isocyanate.
  • Examples of the compound represented by the above general formula (48) include araminopropylmethyldimethoxysilane, r-aminopropylmethylethoxy, silane, araminopropyltrimethoxysilane, araminopropyltriethoxysilane, and N-phenyl.
  • the compounds represented by the above general formulas (49) and (50) include a compound represented by the following general formula (63), a compound represented by the above general formula (61), acrylonitrile, and a compound represented by the above general formula (6). It can be produced by reacting the compound represented by 2) or the above monoisocyanate compound. The reaction is carried out at 20-100 ° C :! Performed for ⁇ 1,000 hours.
  • R 21 , R 22 , R 23 and R 30 in the general formula (63) have the same meaning as described above, and the compound is one of the compounds (h) represented by the general formula (63) Alternatively, two or more types can be selected and used.
  • Examples of the compound represented by the general formula (51) include amercaptopropylmethyldimethylsilane, amercaptopropylmethylethoxysilane, amercaptopropylvirmethoxysilane, and amercaptopropyltriethoxysilane.
  • the reaction with the compound represented by (47), (48), (49), (50) or (51) is performed at 20 to 0.50 ° C for 1 to 200 hours. However, there is no problem even if the reaction is performed at more than 200 hours. At this time, in some cases, a polymerization inhibitor may be present.
  • a compound having a hydrolyzable silicon group-containing unsaturated double bond obtained by reacting the compound represented by (48), (49), (50) or (51).
  • A is a (meth) acrylic system having a group represented by the following general formula (65) (a) at the molecular terminal and a group represented by the following general formula (65) (b) at the other molecular terminal.
  • B represents one CO— or one C ⁇ resort—
  • R 32 is a hydrogen atom or a methyl group when B is -CO-
  • R 33 is a hydrogen atom, an alkyl group having 110 carbon atoms, an aryl group or an aralkyl group.
  • R and s each represent an integer of 13.
  • Polyvalent (meth) acrylate compounds represented by the above general formula (64) include butanediol, hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, Neopentyl glycol, trimethylol propane, pen erythritol, dipentyl erythritol, polje.
  • the polyvalent aryl compound is a polyvalent (meta) acrylate compound which has at least two terminals at both ends, such as the (meta) acryloyl compound.
  • These compounds include polyvalent (meta) acrylates.
  • a compound in which the (meth) acryloyl group at one end of the above specific example of the late compound is an aryl group.
  • the reaction with the compound represented by (48), (49), (50) or (51) is carried out at 20 to 1.00 for 1 to 1,000 hours. There is no problem if the reaction is carried out for more than 000 hours, and in this case, a polymerization inhibitor may be present in some cases, and these reactions (Michael addition reaction and nitrogen addition resulting from Michael addition reaction)
  • the compound (j) is a compound of the compound (j-11) and the compound (j-2), a compound represented by the general formula (31) or an arylglycidyl ester and the compound represented by the general formula (27)
  • a reaction product of the compound represented by the general formula (29) and the compound represented by the general formula (30) is also included.
  • the curable resin composition of the present invention preferably comprises a Pier polymer (D) as a component.
  • the vinyl polymer (D) is obtained by (co) polymerizing one or more of the above (meth) acrylic compounds, or one of the above (meth) acrylic compounds or It can be produced by copolymerizing two or more kinds and one or two or more kinds of the compound (j).
  • it is a vinyl polymer (D) obtained by copolymerizing the (meth) acrylic compound and the compound (j).
  • the proportion of the polymer of the compound (j) in the vinyl polymer (D) comprising the copolymer of the (meth) acrylic compound and the compound (a) is preferably 1 to 30% by mass. . If the proportion is less than 1% by mass or exceeds 30% by mass, the effect of adding the polymer of the above compound (j) becomes difficult to obtain.
  • the (co) polymerization of a polymerizable vinyl monomer or the copolymerization of the polymerizable biel monomer with the above compound (j) ' is usually carried out when (co) polymerizing a normal polymerizable pinyl monomer such as a (meth) acrylate compound.
  • a normal polymerizable pinyl monomer such as a (meth) acrylate compound.
  • Any of known methods such as radical polymerization, anion polymerization, and cationic polymerization can be employed.
  • the radical polymerization method is preferably carried out in the presence of a peroxide polymerization initiator such as benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, or diisopropyl propyl carbonate.
  • a peroxide polymerization initiator such as benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, or diisopropyl propyl carbonate.
  • the polymerization can be carried out in the presence of a chain transfer agent such as pill-mercaptan, tert-butyl mercaptan, arthrimethoxysilylpropyl disulfide.
  • the polymerization reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 90 ° C., for several hours to several tens of hours.
  • the polymerization can be carried out in the presence of a solvent such as xylene, toluene, acetone> methyl ethyl ketone, ethyl acetate or butyl acetate.
  • the (co) polymerization of the above (meth) acrylic compound or the copolymerization of the above (meth) acrylic compound with the above compound (j) is particularly performed in the above-mentioned curable resin. This is desirable because the effect of the present invention is further enhanced.
  • the (meth) acrylic compound As the (meth) acrylic compound, the (meta) a of the 0 !, ⁇ -unsaturated calponyl compound (compound (f)) used in the production of the curable resin 1 is used.
  • One or more of the chlorinated substances can be selected and used.
  • the present invention is characterized by a curable resin composition comprising a Lewis acid and Z or a complex thereof in each of the curable resins, the composition 1 or the composition 2.
  • ⁇ C 1 3, Z n C 1 2, C u C 1 2, Z n C 1 4 or the like can be mentioned, et al are.
  • these complexes of Lewis acid include amine complexes, alcohol complexes, ether complexes and the like.
  • the amine compound used in the amine complex includes ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanol.
  • Alcohol compounds used in alcohol complexes such as methanol, triethanolamine, etc.
  • luciferic acids and complexes thereof include primary alcohols such as methanol, ethanol, propanol and n-butanol, and isopropanol.
  • ether compound used in the ether complex include secondary alcohols such as toluene and 2-butanol, and dimethyl ether, getyl ether, di-n-butyl ether, and the like.
  • BF 3 complexes are particularly preferred because they are easy to handle.
  • Lewis acid and its complex are not limited to one kind, and two or more kinds can be used.
  • the Lewis acid and Z or a complex thereof are contained in an amount of 0.001 to 10 parts by mass per 100 parts by mass of the curable resin or the curable resin in the composition 1 or the composition 2. Preferably 0.1 to 5 parts by mass is blended.
  • the curable resin and the curable resin composition of the present invention can be produced as described above, the curable resin and the curable resin composition are preferably composed of an adhesive composition, particularly an adhesive, a sealant, An adhesive composition suitable for applications such as paints, casting materials, and coating materials.
  • An adhesive composition suitable for applications such as paints, casting materials, and coating materials.
  • an organic tin compound As the curing catalyst, an organic tin compound, a metal complex, a basic substance such as an amine compound, an organic phosphoric acid compound, water (moisture in the air), or the like can be used.
  • examples of the organotin compounds include dibutyltin dilaurate, dioctyltin dimalate, dibutyltin phthalate, octylic acid primary salt, and dibutyltin.
  • examples include tin methoxide, dibutyltin diacetyl acetate, dibutyltin diversate, and reaction products of dibutyltin oxide and diethyl phthalate.
  • Nitto Kasei Co., Ltd. which is a commercial product thereof, trade names: U-700, U-700 ES, U-303 and the like can be mentioned.
  • the metal complex examples include titanate compounds such as tetrabutyl titanate, tetraisopropyl propyl titanate, and triethanolamine titanate; lead octylate, naphthenate; Metal carboxylate such as lead titanate, nickel naphthenate, cobalt naphthenate; aluminum acetyl acetonate complex, zonadium acetyl acetyl acetate Examples include metal acetyl acetonate complexes such as sodium complexes.
  • Examples of the basic substance include amino acids such as T-aminopropyl trimete xylan, aminoamine propyl triethoxysilane, and the like.
  • Quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (Registered by Sankyo Air Products) (Trademark) series, DABCOBL series, 1,8- diazabicyclo [5.4.0] pendase 7 — straight chain containing multiple nitrogen atoms, such as diene Or cyclic tertiary amines and quaternary ammonium salts.
  • ketimines, aldimines, oxazolidines and the like can also be used.
  • organic phosphoric acid compound examples include monomethyl phosphoric acid, di-n-butyl phosphoric acid, triphenyl phosphate and the like.
  • the mixing ratio of the curable catalyst is preferably from 0.02 to 10 parts by mass per 100 parts by mass of the curable resin of the present invention.
  • poly (dialkyl stanoxane) dicarboxylate represented by the following general formula (6, 6) can also be used.
  • R 3 4 and R 3 5 is rather replaced young having 1 to 2 carbon is a non-substituted hydrocarbon group, s is indicates an integer of 0 or more, respectively, R 3 4 and R 3 5 may be Tsu different but the same.
  • R 3 4 and R 3 It is in the rather substituted young 1 to 1 2 carbons which is table and unsubstituted hydrocarbon groups 5, methylmercury, Echiru, propyl, i Seo propyl, heptyl , Isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, decyl, rauryl, etc. Examples include a branched linear alkyl group, and a substituted or unsubstituted phenyl group. s may be an integer greater than or equal to 0, but is preferably an integer from 0 to 3. : R 3 4 and 3 5 may be different also the same.
  • poly (dialkylstannoxane) dicarboxylate represented by the general formula (66)
  • examples of the poly (dialkylstannoxane) dicarboxylate represented by the general formula (66) include 1,1,3,3—tetramethyl-1,3 — Bis (acetoxy) distanoxane, 1,1,3,3—tetramethyl—1,3—bis (petityloxy) distanoxane, 1,1, 3,3—Tetramethyl-1., 3—Bis (octanoyloxy) distanoxan, 1,1,3,3—Tetramethyl1 1,3— Bis (2-ethylhexanol): distanoxan, 1, 1, 3, 3 — tetramethyl 1,3 — bis (lau royoxy) Noxane, 1,1,3,3—tetrabutyl-1-1,3—bis (acetoxoxy) distanoxane, 1,1,3,3—tetrabutyl-1,3 - Screw ( (Tyroxy) dis
  • poly (dialkyl stanoxane) dicarboxylate represented by the general formula (66) is formed by the reaction with a silicate compound represented by the following general formula (67). Things can also be used.
  • R. 3 6 and R 3 7 is the number of carbon atoms:!
  • R 3 6 and R 3 7 is rather good even Tsu different also the same, R 3 6 and R 3 7 is double In the case of numbers, they may be the same or different.
  • an alkyl group having 1 to 4 carbon atoms represented by R 3 6 and R 3 7 is methylation, Echiru, propyl, i Seo propyl, butyl, I Sobutyl, s-butyl, 1; monobutyl.
  • silicate compound represented by the above general formula (67.) examples include tetramethyxilan, tetraethyxiran, tetraethyl Tetraalkoxysilan, Trietoxicilir, etc. such as Laproboxysilan, Tetraisoproboxylan, Tetrabutoxylan, etc.
  • Trial alcohols such as Lan, Trietixi Sheil Silane, Trieti Xi Provir Silane, Trieti Toxi Soprovirilane, Trieti Xipirsilan etc.
  • the hydrolyzate of these alkoxysilanes can be used in the same manner as these 0 alkoxysilanes.
  • the poly (dialkylstannoxane) disiligate compound, which is a reaction product with, is formed by reacting the two with each other at 100 to 130 for about 1 to 3 hours, and producing carbon. It is obtained by removing the acid ester under reduced pressure.
  • the reaction ratio of the two is preferably such that one equivalent of the alkoxy group is reacted with at least one equivalent of the alkoxy group to completely eliminate the epoxy group. If the carboxyl group remains, the catalytic activity decreases. This reaction can be performed in the presence or absence of a solvent.
  • the poly (dialkylstannoxane) dicarboxylate represented by the general formula (66) is a silicate compound represented by the general formula (67) and / or its hydrolysis.
  • a specific example of a poly (dialkylstannoxane) disilicate compound which is a reaction product with a compound a compound represented by the following general formula (68) can be given.
  • epoxy resins bisphenol A type epoxy resin, bisphenol F type epoxy resin, nopolox type epoxy resin, and amine Epoxy resin with silylation, epoxy resin with heterocycle, alicyclic epoxy resin, bisphenol hydride A-type epoxy resin, urethane-modified epoxy resin, An epoxy resin, etc., which can be used alone or in combination of two or more.
  • a curing agent for the epoxy resin examples include ethylenediamine, 1,3-propanediamine, hexamethylenediamine, diethylenetriamine, and triethylenetriamine.
  • modification method examples include addition of an epoxy compound, addition of ethylene oxide, addition of propylene oxide, addition of acrylonitrile, addition of Mannich with phenol and its derivatives and formalin, addition of thiourea, and ketone blockade.
  • phenol nopolak polymer butane compounds, polysulfides, ketimines, tertiary amines, organic acid hydrazides, dicyan diamides and derivatives thereof, amide imides, carboxylic esters, boron trifluoride-amine complexes , Imidazoles, acid anhydrides, halogenated acid anhydrides, aromatic diazonium salts, diaryldonium salts, triarylsulfonium salts, triarylselenium salts, polyamidoamines, polyphenols, alcohols , Acetyl acetonato metal salts, phosphines and the like, and one or more of these can be selected and used. '
  • Ketimine compounds (hereinafter referred to as compound (k)) are compounds having a group represented by the general formula: N-C (X) (Y) (where X is a hydrogen atom or an organic group, and Y is an organic group).
  • compound (k) is compounds having a group represented by the general formula: N-C (X) (Y) (where X is a hydrogen atom or an organic group, and Y is an organic group).
  • X is a hydrogen atom or an organic group
  • Y is an organic group
  • R 38 , R 39 , R 40 and R 41 are each selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a phenyl group having an alkyl group having 1 to 6 carbon atoms.
  • D 1 , D and Du are the same or different alkylene groups each having 2 to 6 carbon atoms, and X is 0 or 1.
  • Examples of the compound represented by the above general formula (69) include 2,5,8—triaza-11,8—nonagene and 2,10—dimethyl-1,3,6,9 — Trizars 2, 9 — Dendecadiene, 2,10-Diphenyl 1, 3, 5, 9 — Triazas 1, 2, 9 — Tridecane, 3, 1 1 — Dime Chill 4, 7, 10-Triaza 3, 1.0-Tride Cadien, 3, 1 1 Jethyl 4, 7, 10-Triaza 1, 3 10- Tridecadiene, 2,4,12,14—Tetramethylol 5,8,11 1 Triaza4,11 1 Bentadecadiene, 2,4,20 , 2 2 — Tetramethylo 5, 1 2, 1 9 — Triaza 1, 4, 19 Triaicogen, 2, 4, 15, 17 — Tetramethyl 1 5 , 8, 11, 14-14-year-old 14-, 14-year-old, etc. It is.
  • Examples of the compound having an epoxy group that reacts with the imiso group of the compound represented by the general formula (69) include styrene oxide, butylglycidyl ether, and arylglycidyl.
  • P-ter butyl phenylidinyl ether, p — sec — butyl phenylidyl ether, m, p — cresylglycidylether, p — cresylglycidyl ether Sidyl ether, vinylcyclohexane dioxide, glycidyl ester of persuccinic acid, modified glycidyl ether of carboxylic acid, glycidyl ester of dimer acid, 1, 6 — Hexane diol diglycidyl ether, resorcinoglycidyl ether, propylene Glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, n
  • n a number from 1 to 6.
  • X, y, and z may be the same or different.
  • a compound obtained by reacting an amine compound having at least one primary amino group in the molecule with a carbonyl compound and a primary amino group in the molecule is advantageous for the amine compound having at least one to have a primary amino group equivalent generally in the range of about 2,000 or less, preferably about 30 to 1; It generally has a number average molecular weight of about 5,000 or less, preferably in the range of about 60 to 3,000. It is preferred to do so.
  • amine compounds include ethylenediamine, propylenediamine, petylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penethyleneethylenehexamine, hexamylenediamine, trimethylhexamylenediamine, and N-aminoethylpiamine.
  • NBDA norbornane skeleton
  • meta-xylylenediamine meta-xylylenediamine.
  • Takahashi Gas Chemical Co., Ltd examples thereof include aliphatic polyamines such as MXDA, diaminodiphenylmethane, phenylenediamine, and polyamides having a primary amino group at the molecular terminal of the polyamide, aromatic polyamines, and alicyclic polyamines.
  • aliphatic polyamines such as MXDA, diaminodiphenylmethane, phenylenediamine, and polyamides having a primary amino group at the molecular terminal of the polyamide, aromatic polyamines, and alicyclic polyamines.
  • the amine compound include a silicon atom-containing amine compound such as r-aminopropyltriethoxysilane.
  • a polyamine compound having two or more primary amino groups in the molecule is particularly preferable.
  • Examples of the carbonyl compound include acetone, methyldiethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, getyl ketone, dipropyl ketone, and diisobutyl ketone.
  • Examples thereof include ketones such as ethyl propyl ketone, ethyl butyl ketone, cyclohexanone, propiophenone, and benzophenone, and aldehydes such as acetoaldehyde and benzaldehyde.
  • Ketimines can be formed by blocking the amine compound with the ketones, and aldimines can be formed by blocking with the aldehydes.
  • the compound (k) of the above (2) includes both ketiminized and aldiminated compounds.
  • the reaction between the amine compound and the carbonyl compound can be carried out by a method known per se, wherein substantially all of the primary amino groups present in the amine compound react with the carbonyl compound. The reaction is performed under such quantitative ratios and conditions. The reaction between the two is achieved by heating under reflux in the absence of a solvent, or in the presence of a non-polar solvent such as hexane, cyclohexane, toluene, and benzene, and removing water produced by azeotropic distillation. .
  • ketones which are poorly water-soluble and have little steric hindrance such as methylisobutylketone and methylethylketone can be used as the carbonyl compound.
  • the tackifier resin is not particularly limited, and any resin which is usually used at room temperature, whether solid or liquid, can be used. Specific examples include phenolic resins, modified phenolic resins (for example, cash-oil-modified phenolic resins, tol oil-modified phenolic resins, etc.).
  • Terpene phenolic resin Terpene phenolic resin, xylene phenolic resin, cyclopentene phenolic resin, coumarone-indene resin, rosin-based resin, b di N'esu ether resin, Mizu ⁇ Ro di emissions ester resin, key sheet Ren resins, low molecular weight Po Li styrene les down resin, scan Chi Le emissions copolymer resins, petroleum resins (e.g., C 5 hydrocarbon resins, C 9 hydrocarbon resins, C 5 ⁇ C g hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, terpene emissions resins, DCPD resins and the like et be. These may be used alone or in combination of two or more.
  • tackifying resin terpene down off error Roh Lumpur resin, ii di N'esu ether resin, hydrogenated ii di N'esu ether resin, key sheet Le emissions resins, styrene-les emission copolymer resins, C 9 hydrocarbon Hydrogen resins, hydrogenated petroleum resins, and terpene resins are preferred because of their particularly good compatibility and good adhesive properties.
  • the tackifying resin is preferably blended in an amount of 5 to 70 parts by mass per 100 parts by mass of the curable resin.
  • the one or more fine powders selected from silica fine powders and organic polymer fine powders those having a particle size of 10 nm to 300 m are suitable, but it is preferable.
  • l OO nml OO ⁇ m particularly preferably 1 to 30 fi m.
  • fine silica powder those having the above-mentioned particle diameters can be used, but hydrophobic fine silica powder is particularly preferable.
  • hydrophobic silica fine powder for example, fumed silica (aerosol) is widely used as a thixotropic agent in adhesives and others.
  • Fine silica powder such as gel or silica air gel is used to prepare organosilicon compounds, for example, dimethyldichlorosilan, hexamethyldisilazane, dimethylsiloxane, or trimethoxysiloxane.
  • Hydrophobic materials treated with tilsilane or the like can be used.
  • smoke-poor silica treated with hexame tildisilazane and silica air mouth gel can be used.
  • Those treated with methylsiloxane and / or hexamethyldisilazane are preferred.
  • the hydrophobization treatment is performed by stirring the silica fine powder and the organic silicon compound at a high speed of about 100 to 400 ° C. It is desirable to carry out the contact in a medium such as an organic solvent in order to achieve uniform contact between the two.
  • the mixing ratio of the silica fine powder and the organic silicon compound is usually 100 parts by mass of the silica fine powder, The silicon compound is 3 to 40 parts by mass.
  • organic polymer fine powder examples include urethane resin fine powder, polyster fine powder, polycarbonate fine powder, polymethylsilsesquioxane fine powder, and Fine powders of lithium resin, fine powder of styrene resin, fine powders of vinyl resin such as polyvinyl chloride, and polyolefins such as polyethylene-polypropylene Fine powder Silicone-based fine powder and the like can be mentioned. These organic polymer fine powders may be used alone or in combination of two or more.
  • amorphous high-purity fused quartz glass fine powder can be used in the same manner. Is a high purity fused silica glass la scan fine powder, with S 1 ⁇ 9 content 9 9.8 mass% or more, even the rather to prefer very little alkali metal other non neat particle size However, those having a diameter of 1 to 100 m, particularly 2 to 50 m, are preferred.
  • Amorphous high-purity fused quartz glass fine powder may be used as it is or may be surface-treated with a coupling agent.
  • the capping agent include an organic titanium compound, an organic aluminum compound, an organic zirconium compound, and an alkoxysilane.
  • organic titanate compounds include tetrapropoxy titan, tetraptoxy titan, tetrax (2-ethylhexyloxy) titan, and tetrastear.
  • organic aluminum compound acetate alcohol diisopropylate or the like
  • organic zirconium compound zirconium aluminum oxide is used.
  • alkoxysilane examples include vinyl trimethoxysilane, vinyl triethoxysilane, and pistoris ( ⁇ -methoxysilane).
  • Alkoxypolysiloxane having an alkoxy group disclosed in JP-A No. 14-No. 14 and the like can be mentioned.
  • Fillers include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica, various balloons, and aluminum hydroxide. Examples include metal hydroxides such as nickel and magnesium hydroxide, and fibrillated fibers.
  • the fibrillated fiber examples include a fibrillated aromatic polyamid fiber, a polyester fiber, a polyolefin fiber, and a polyacrylo fiber. Examples thereof include nitrile fibers, and those having an average fiber length of about 0.1 to 5 mm are preferred. Also, a low-fibrillated fiber having a lower fibrillation than the above-mentioned fibrillated fiber can be used in combination with the above-mentioned fibrillated fiber. . Low fibrillation means that there are few whisker-like branches per unit length of the trunk fiber. Examples of the low-fibrillated fiber include a fiberized or non-fibrillated polyester fiber, a polyolefin fiber, and a polyacrylonitrile. In addition to toll fiber, sepiolite, glass fiber, carbon fiber and the like can be mentioned.
  • plasticizer examples include esters of phthalic acid such as dioctyl phthalate and diptyl phthalate; fatty acid carboxylates such as dioctyl adipate and dibutyl sepate; Acid ester etc. can be used.
  • a secondary amino group, a tertiary amino group, a hydroxyl group, a carboxyl group, a mercapto group, a Z or a It is a compound having a primary amino group, and is widely used as an anti-degradation agent for various resins.
  • anti-aging agents include triaceton'diamine, poly [(6-morpholino s-triazine-1,2,4-diyl) ⁇ 2,2 , 6, 6 — Chitramethyl-4-piperidyl ⁇ imino ⁇ Hexamethylene ⁇ 2, 2, 6, 6 — Tetramethyl-1-4-Beverage ⁇ i Mino ⁇ ], bis (2,2,6,6—tetramethylyl 4—piperidyl) sepagates, bis (1,2,2,6,6—pentamethyl 4—piperri Jill) Sebasket, 4—Benzo Roxy—2, 2, 6, 6—Tetramethyl Pyridine, Poli (2, 2, 4—Domestic 1, 2 — dihide mouth quinoline), 6 — ethoxylate 2, 2, 4-1-1, 2, — dihide mouth quinoline, ⁇ , ⁇ '— diphenyl !
  • 6-Di-t-butyl One 4-methyl phenol, 2,4—dimethyl-6- (1—methyl cyclohexyl) phenol, 2— [4,6—bis (2 , 4 — dimethyl phenyl) 1, 1, 3, 5 — triazine 1 2 — yl] 1 5 — (octylokoxy) phenol, 2, 6 — ge t — Butyl — 4 — ethylenol, 2 — (2H — benzotriazole — 2 — yl) 1 4 — menthol 6 — (3, 4, 5, 6 — tetrahydrofutirimi jirumechiru) phenol, 2 — (4, 6 — di Phenol 1,3,5 — Triazine 12-yl) — 5 — [(Hexyl) oxy] phenol, 2,5-di-tert-butyl hydro Quinone, poly (2,2,4—trimethyl-1,2, -dihydroquino
  • the antioxidant is obtained by adding the above antioxidant to an aqueous solution selected from an alkoxy group and an acetate group having an organic group (I) having an isocyanate group in the group.
  • Those obtained by reacting with a silicon compound (compound (1)) having a decomposable group directly bonded to a silicon atom can also be used. The use of such a material can improve the effect of preventing aging.
  • the compound (1) has an organic group (II) having at least one group selected from a primary amino group, a secondary amino group and a (meth) acryloyl group in the group.
  • organic group (II) having at least one group selected from a primary amino group, a secondary amino group and a (meth) acryloyl group in the group.
  • One or more compounds in which a hydrolyzable group selected from an alkoxy group and an acetate group is directly bonded to 1 to 10 silicon atoms.
  • the compound is preferably a compound obtained by reacting a silicon compound bonded to up to three silicon atoms with a compound having two or more izocyanate groups in the molecule.
  • the thixotropic agent include anhydrous silica, fatty acid bisamide, hydrogenated castor oil and the like.
  • Oligomers include polyethylene oligomers, liquid polypropylene, oligostyrene, liquid polychlorinated planes, liquid polyisoprene, Liquid SBR, liquid NBR, liquid butyl rubber, liquid polyisobutylene, liquid polybutadiene, polyhydroxypolyolefin-based oligomers, methyl styrene Ligomer, styrene containing lin- ⁇ - ⁇ -methyl styrene oligomer, and oligoester acrylate.
  • process oils such as naphthene, aromatics, and paraffin can be added for the purpose of adjusting viscosity and reducing tack. it can.
  • amino silane is particularly preferred.
  • Any agent may be used as long as it is compatible with the above-mentioned curable resin and has a water content of 500 ppm or less.
  • dehydrating agents include quicklime, magnesium oxide, orthosilicate ester, anhydrous sodium sulfate, zeolite, methylsilicylate, and ethyl silicide. , Vinyl alkoxysilane, various alkyl alkoxysilanes, silane coupling agents, etc.
  • the curable resin composition of the present invention can be obtained by using a silane described in Patent Nos. 3,030,020 and 3,317,353.
  • a urethane-based resin may be blended if necessary.
  • IPDI isophorone diisocyanate
  • A—] nom 5 (trade name, manufactured by Nihon Nikka Co., N-ethylamino)
  • the mixture was reacted at 80 ° C. for 2 hours to obtain a synthesized product A.
  • DMDS (trade name, manufactured by Maruzen Chemical Co., Ltd.) was placed in a reaction vessel. , 1,5-dimercap, toe 3-thiapentane) were added thereto, and while stirring, 222 g of Compound 11A was added dropwise to obtain Compound 1-B.
  • the reaction vessel was charged with 200 g of SDX-1690 and 68 g of the compound 41C, and heated to 90 ⁇ under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.
  • KBM 5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., acryloxypropyltrimethoxysilane) and 89.5 g of KBM903 in a nitrogen atmosphere. The mixture was reacted at 23 ° C for 7 days with mixing to synthesize compound 5-A.
  • the reaction vessel was charged with 200 g of SDX-169 and 85 g of the synthesized product 5-C. The temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of A] BN and 10 g of toluene was added dropwise over 3 hours. Further, the mixture was reacted at the same temperature for 1 hour to produce a curable resin.
  • the mixture was reacted at 23 ° C. for 7 days while mixing in a nitrogen atmosphere at a rate of 203 g to synthesize a synthetic product 6-A.
  • polyether HA (trade name, manufactured by Mitsubishi Chemical Corporation, polyolefin polyol) was placed in a reaction vessel, and a 28% by mass methanol solution of sodium toxide was added to the number of hydroxyl groups in 1 mol of the above polyester ether HA.
  • the sodium atom was added in a molar amount of 1.05 times, and the mixture was stirred at 120 ° C for 30 minutes.
  • 36 g of aryl chloride was added and reacted for 1 hour. Unreacted components were distilled off under reduced pressure to remove by-product inorganic substances and the like, followed by purification to obtain an aryl-terminated hydrocarbon polymer.
  • reaction product 1 AA
  • reaction product 1 BB reaction product 1—CC
  • reaction product 1—DD reaction product 1—DD aryl alcohol 58.1
  • the compounds shown in Table 2 or the reactant 1 AA, reactant 1—BB, reactant 1 CC or reactant 1—DD obtained in Synthesis Example 3, and the reactant obtained in Synthesis Example 1 1 Use one GA or reactant 1 — GB or KBM903 in the ratio (parts by mass) shown in Table 2 and react for 1 day at 40 ° C with stirring in a nitrogen atmosphere to obtain reactant 2 — FF, Reaction product 2—GG, reaction product 2—HH, reaction product 2—II, and reaction product 2—JJ were obtained.
  • the compounds represented by the trade names in Table 2 are as follows.
  • Reactant 1 CC 248.3 Reactant 1— DD 331.4 Reactant 1— GA 263.4 263.4 Reactant 1-GB 422.6 422.6
  • reaction vessel put 114 g of allyl glycidyl ether, 196 g of KBM 803 and lg of triethylamine, and react at 50 ° C for 7 days with stirring under a nitrogen atmosphere to obtain a reaction product, 5-GA. Got.
  • Example 17 Example 18 Example 19 Example 20
  • Example 21 Example 22 Comparative Example 3
  • Example 6 1,000 1,000 1,000 500 1,000 1,000
  • KBM503 20 20 Lauryl mercaptan 10 10 10 10 10 10 10
  • a reaction vessel was charged with 300 g of a polyaryl ether having a .aryl group at both ends (number average molecular weight: 8,000) and 24 g of DMDS, and the temperature was raised to 90 ° C under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours. The mixture was further reacted at the same temperature for 1 hour to obtain a synthesized product 24-B.
  • Example 2 6 Example 2 7
  • Example 2 8 Example 2 Reaction solvent Example 2 3 1,000 1,000 1,000 1,000 1,000 1,000
  • curable resin compositions After leaving these curable resin compositions at 23 ° C for 14 days to 30 days, they were cured at a temperature of 23 ° C and a relative humidity of 60%, and the time until skin application was measured. Table 5 shows the results. Also, using these curable resin compositions, stainless steel sheets were adhered to each other as an adherend, cured at a temperature of 23 ° C and a relative humidity of 50% for 14 days, and their tensile shear adhesion strength was increased. (NZ cm 2 ) was measured according to JISK 6850. Table 5 shows the results.
  • the curable resin of the present invention When the curable resin of the present invention is compounded as an adhesive, it has the effect of increasing the adhesive strength, and therefore can be used particularly for adhesives, sealants, paints, etc. Adhesive performance can be exhibited.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

Cette invention concerne une résine durcissable, laquelle résine durcit à l'humidité et comprend un groupe silyle au niveau d'une extrémité et présente une excellente propriété d'adhérence lorsqu'elle est utilisée dans des adhésifs, des agents d'étanchéité, des composés de revêtement ou analogue. La résine durcissable renferme un groupe contenant un atome de silicium au niveau de l'extrémité de la molécule, un ou plusieurs groupes hydrolysables, tels que des groupes alkoxy, des groupes acétoxy ou des groupes oxime, étant directement liés à un atome de silicium. En outre, la résine durcissable comprend au moins une liaison thiouréthane dans la molécule, et le squelette de chaîne principale de la résine durcissable est composé d'un polymère de polyoxyalkylène, d'un polymère de (méth)acrylate ou d'un polymère d'hydrocarbures.
PCT/JP2004/007881 2003-06-03 2004-06-01 Resine durcissable, son procede de production et composition contenant cette resine durcissable WO2004108774A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2005506803A JPWO2004108774A1 (ja) 2003-06-03 2004-06-01 硬化性樹脂、その製造方法及び該硬化性樹脂を含む組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003-157812 2003-06-03
JP2003157812 2003-06-03

Publications (1)

Publication Number Publication Date
WO2004108774A1 true WO2004108774A1 (fr) 2004-12-16

Family

ID=33508405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/007881 WO2004108774A1 (fr) 2003-06-03 2004-06-01 Resine durcissable, son procede de production et composition contenant cette resine durcissable

Country Status (3)

Country Link
JP (1) JPWO2004108774A1 (fr)
TW (1) TW200504154A (fr)
WO (1) WO2004108774A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005054174A (ja) * 2003-07-18 2005-03-03 Konishi Co Ltd 硬化性樹脂組成物及びそれを含有する湿気硬化型接着剤組成物
JP2006199905A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199906A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199725A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199730A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物及び湿気硬化型接着剤
WO2011005614A1 (fr) * 2009-07-09 2011-01-13 Prc-Desoto International, Inc. Mastic à un composant durcissable à l’humidité et procédé de fabrication associé
JP2011178906A (ja) * 2010-03-02 2011-09-15 Konishi Co Ltd 硬化性樹脂組成物
KR20190047136A (ko) * 2012-01-25 2019-05-07 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
US11760841B2 (en) 2018-12-21 2023-09-19 Dow Silicones Corporation Silicone-polycarbonate copolymer, sealants comprising same, and related methods
US11807775B2 (en) 2018-12-21 2023-11-07 Dow Silicones Corporation Silicone-organic copolymer, sealants comprising same, and related methods

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007162001A (ja) * 2005-11-21 2007-06-28 Shin Etsu Chem Co Ltd 液状エポキシ樹脂組成物
US10246607B2 (en) * 2017-07-20 2019-04-02 Chang Chun Plastics Co., Ltd. Resin composition, coating composition and article by using the same
CN114437314B (zh) * 2022-03-10 2024-01-23 韦尔通科技股份有限公司 一种聚硫醇固化剂和单组份环氧胶黏剂及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS636003A (ja) * 1986-06-26 1988-01-12 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH11322917A (ja) * 1998-05-11 1999-11-26 Kazunori Kataoka 有機シリルスルフイド基を片末端に有するポリオキシエチレン誘導体
JP2001072854A (ja) * 1999-09-01 2001-03-21 Asahi Glass Co Ltd 室温硬化性組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS636003A (ja) * 1986-06-26 1988-01-12 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JPH11322917A (ja) * 1998-05-11 1999-11-26 Kazunori Kataoka 有機シリルスルフイド基を片末端に有するポリオキシエチレン誘導体
JP2001072854A (ja) * 1999-09-01 2001-03-21 Asahi Glass Co Ltd 室温硬化性組成物

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4578166B2 (ja) * 2003-07-18 2010-11-10 コニシ株式会社 硬化性樹脂組成物及びそれを含有する湿気硬化型接着剤組成物
JP2005054174A (ja) * 2003-07-18 2005-03-03 Konishi Co Ltd 硬化性樹脂組成物及びそれを含有する湿気硬化型接着剤組成物
JP4685470B2 (ja) * 2005-01-18 2011-05-18 コニシ株式会社 硬化性樹脂組成物の製造方法
JP2006199905A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199906A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199725A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物
JP2006199730A (ja) * 2005-01-18 2006-08-03 Konishi Co Ltd 硬化性樹脂組成物及び湿気硬化型接着剤
KR101397808B1 (ko) * 2009-07-09 2014-05-20 피알시-데소토 인터내쇼날, 인코포레이티드 1-파트 수분 경화성 실란트 및 이의 제조 방법
US8143370B2 (en) 2009-07-09 2012-03-27 Prc-Desoto International, Inc. One-part moisture curable sealant and method of making the same
CN102471662A (zh) * 2009-07-09 2012-05-23 Prc-迪索托国际公司 单组分可湿固化密封剂及其制备方法
JP2012532955A (ja) * 2009-07-09 2012-12-20 ピーアールシー−デソト インターナショナル，インコーポレイティド １成分の水分硬化性シーラントおよびその作製方法
WO2011005614A1 (fr) * 2009-07-09 2011-01-13 Prc-Desoto International, Inc. Mastic à un composant durcissable à l’humidité et procédé de fabrication associé
JP2011178906A (ja) * 2010-03-02 2011-09-15 Konishi Co Ltd 硬化性樹脂組成物
US10618267B2 (en) 2012-01-25 2020-04-14 Dexerials Corporation Method of manufacturing image display device
KR102097383B1 (ko) * 2012-01-25 2020-04-06 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
KR20200037443A (ko) * 2012-01-25 2020-04-08 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
KR20190047136A (ko) * 2012-01-25 2019-05-07 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
KR20200090950A (ko) * 2012-01-25 2020-07-29 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
KR102137449B1 (ko) 2012-01-25 2020-08-13 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
US10759156B2 (en) 2012-01-25 2020-09-01 Dexerials Corporation Method of manufacturing image display device
US10843448B2 (en) 2012-01-25 2020-11-24 Dexerials Corporation Method of manufacturing image display device
KR102277736B1 (ko) 2012-01-25 2021-07-16 데쿠세리아루즈 가부시키가이샤 화상 표시 장치의 제조 방법
US11738548B2 (en) 2012-01-25 2023-08-29 Dexerials Corporation Method of manufacturing image display device
US11760841B2 (en) 2018-12-21 2023-09-19 Dow Silicones Corporation Silicone-polycarbonate copolymer, sealants comprising same, and related methods
US11807775B2 (en) 2018-12-21 2023-11-07 Dow Silicones Corporation Silicone-organic copolymer, sealants comprising same, and related methods

Also Published As

Publication number Publication date
JPWO2004108774A1 (ja) 2006-07-20
TW200504154A (en) 2005-02-01

Similar Documents

Publication Publication Date Title
WO2004074330A1 (fr) Resine durcissable, son procede de production et composition de resine durcissable
KR100720816B1 (ko) 경화성 수지 조성물 및 상온 경화 접착제
JP3313360B1 (ja) 硬化性樹脂組成物とその製造方法並びにそれを用いた接着方法
JP4213259B2 (ja) ウレタン系樹脂組成物
WO2004108774A1 (fr) Resine durcissable, son procede de production et composition contenant cette resine durcissable
JP2006052168A (ja) 新規メルカプトシラン化合物、それを用いた硬化性樹脂、及び、それを用いた硬化性樹脂組成物
WO2007023669A1 (fr) Compositions de résine durcissable
EP4011978A1 (fr) Composition durcissable
CN116997610A (zh) 固化性组合物及其固化物
EP0604851A1 (fr) Composition de polymère acrylique fonctionnalisé par un alkoxysilane
JP4445584B2 (ja) 硬化性樹脂組成物
JP2004323660A (ja) 反応性ホットメルト接着剤組成物
JPWO2020170908A1 (ja) 硬化性組成物
CN111201295A (zh) 光固化性粘着剂组合物以及粘接方法
JP3725095B2 (ja) 硬化性組成物及びシーリング材組成物
WO2003099929A1 (fr) Composition en resine polymerisable
WO2019073979A1 (fr) Composition d'adhésif photodurcissable, et procédé de collage
JP2005179387A (ja) 硬化性組成物及びシーリング材組成物
JP3990608B2 (ja) 硬化性組成物及びシーリング材組成物
JP2018162387A (ja) 硬化性組成物
JP5924536B2 (ja) 金属用表面処理剤及び該表面処理剤で処理された金属材
JP2021134276A (ja) 硬化性組成物
JP3464972B2 (ja) 硬化性樹脂組成物
JP2004035591A (ja) 硬化性樹脂組成物とその製造方法並びにそれを用いた接着方法
JP2006052321A (ja) 新規ビニルシラン化合物、それを用いた硬化性樹脂、及び、それを用いた硬化性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005506803

Country of ref document: JP

122 Ep: pct application non-entry in european phase