Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/14—Polysulfides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
  • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
  • C07D327/04—Five-membered rings
• • 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
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/28—Polythiocarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/45—Heterocyclic compounds having sulfur in the ring
  • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups

Definitions

• the present invention relates to a dithiocarbonate composition useful for applications such as paints, adhesives, inks, building sealing agents, and semiconductor sealants. Background technology
• Reactive polymers or compounds having a functional group in the molecule are useful in various applications.
• a composition containing such a polymer or compound is used as an active ingredient such as a paint, an adhesive, an ink, an architectural sealant, or a semiconductor sealant, a crosslinking reaction or the like under specific conditions after application or printing.
• an active ingredient such as a paint, an adhesive, an ink, an architectural sealant, or a semiconductor sealant, a crosslinking reaction or the like under specific conditions after application or printing.
• Japanese Patent Application Laid-Open No. 7-145164 discloses a method for crosslinking a compound having a 5-membered dithiocarbonate group with a polymer having an active hydrogen-containing functional group. ing.
• Japanese Patent Application Laid-Open No. H5-2074707 discloses a composition comprising a compound having a 5-membered ring dithiocarbonate group and a nucleophile.
• Japanese Patent Application Laid-Open No. 7-621900 discloses an aqueous polymer composition of a 5-membered ring dithiocarbonate group-containing biel copolymer and a compound having two or more amino groups or imino groups.
• the present invention provides a compound represented by the general formula (I):
• R 1 , R 2 and R 3 are the same or different and each represents hydrogen or lower alkyl, and a polymer or compound containing at least one 5-membered dithiocarbonate group represented by the formula:
• lower alkyl is straight-chain or branched having 1 to 4 carbon atoms, for example methyl , Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, etc.
• Examples of the resin include a resin and a copolymer in which these resins are chemically bonded to each other. Of these, a butyl polymer is preferably used as a structural unit, and more preferably a general polymer (II)
• R 1 , R 2 and R 3 are as defined above, R 4 and R 5 are the same or different and represent hydrogen, methyl or ethyl, and n represents an integer of 1 to 4).
• the vinyl copolymer containing at least one 5-membered dithiocarbonate group includes a structural unit containing a 5-membered dithiocarbonate group and 1 to 10 different structural units.
• vinyl monomers copolymerized with a monomer containing a 5-membered dithiocarbonate group which is a raw material of a vinyl copolymer containing at least one 5-membered dithiocarbonate group, include (meth) acrylic.
• Acid maleic acid, fumaric acid, itaconic acid, crotonic acid, monoethyl maleate, monomethyl itaconate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid Isobutyl, t-butyl (meth) acrylate, (meth T) 2-ethylhexyl acrylate, lauryl (meth) acrylate, styrene, bininoleto / leene, ⁇ -methylstyrene, dimethyl / restyrene, divinyl / revenzen, ⁇ -methylol (meth) acrylyl amide, (Meth) acrylamide, (meta) acrylonitrile, vinyl acetate, vinyl propionate, vinyl versatate, monoethyl maleate, monobutyl maleate, getyl maleate, dibutyl maleate, gety
• Acid or lower alkyl ester thereof for example, (meth) acrylic acid, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid isobutyl ester Tert-butyl (meth) acrylate can be preferably used .
• Copolymers of a vinyl monomer and a non-vinyl monomer can also be used. These include, for example, a vinyl-modified epoxy resin (Japanese Patent Application Laid-Open No. 54-24949) and a vinyl-modified epoxy resin.
• Manufacture according to a method such as polyester resin (Japanese Patent Application Laid-Open No. 1-129702), vinyl-modified alkyd resin, and vinyl-modified urethane resin (Japanese Patent Application Laid-Open No. 11-17661). Can be.
• Polymer molecules containing at least one 5-membered dithio-carbonate group The amount is not particularly limited.
• Polymers containing at least one 5-membered dithiocarbonate group can be obtained by polymerizing and polycondensing the corresponding monomer in a known manner:
• Monomers having a 5-membered dithiocarbonate group are For example, in a known method [Japanese Patent Laid-Open Publication No. 5-257207, Journal of Organic Chemistry (J. Org. Chem.), 60 ⁇ _473 (1995)].
• it is obtained by reacting an oxysilane compound with carbon disulfide in the presence of an alkali halide such as lithium bromide.
• the polymer having a 5-membered dithiocarbonate group in the molecule has a functional group
• a polymer having a carboxyl group, a hydroxyl group, an amino group, etc. can be obtained by a known method, and then a 5-membered ring dithiocarbonate compound is subjected to a pendant bond reaction. .
• a method for producing a copolymer a method of copolymerizing a monomer having a 5-membered dithiol-carbonate group in a molecule with another copolymerizable monomer, or a method of synthesizing a homopolymer or a cobolimer and then reacting with another monomer Graft copolymerization or block copolymerization of polymer after copolymer synthesis
• a method for producing a copolymer a method of copolymerizing a monomer having a 5-membered dithiol-carbonate group in a molecule with another copolymerizable monomer, or a method of synthesizing a homopolymer or a cobolimer and then reacting with another monomer Graft copolymerization or block copolymerization of polymer after copolymer synthesis
• the law can be raised.
• a monomer is prepared in water using an emulsifier and a polymerization initiator by a known method (Japanese Patent Application Laid-Open No. 54-11048, Japanese Patent Publication No. 58-209). No. 1) may be subjected to emulsion polymerization.
• a polymer containing at least one 5-membered dithiocarbonate group can have improved storage stability by having a core shell structure.
• the core shell-type emulsion polymer in water can be prepared by a known method (JP-A-57-38050, JP-A-61-136501, JP-A-5-7703). No. 3).
• a polymer containing at least one 5-membered dithiocarbonate group can be emulsified in water by a known method.
• the polymerization solvent varies depending on the polymerization mode.For example, in radical polymerization, benzene, toluene, xylene, hexane, cyclohexane, ethyl acetate
• the polymerization initiator varies depending on the polymerization mode. For example, in radical polymerization, 2,2 ' —Azobisisobutyronitrile, 2, 2'-azobis-1-2—methinolevbutyronitrile 7, 2, 2 '—azobisnorelonitrizole, benzoinenolenoxide, acetylvaloxide, lauroyl peroxide, 1,1 —Bis (t-l-butylzoleperoxy) -1,3,3,5—trimethinolecyclohexane, t—butynorenoxy-1-2-ethizolehexanoate, cumenehyi-dro-noxoxide, t-butyl nonoxybenzoate , T-butynolepoxide, methinoleethynoleketone peroxide, m-black perbenzoic acid Are used.
• the emulsifier for aqueous emulsion polymerization examples include an anionic emulsifier such as an alkylbenzene sulfonate, a nonionic emulsifier such as polyethylene glycol alkynolepheny / reether, and Eleminol JS-2 [manufactured by Sanyo Chemical Co., Ltd.]
• a reactive emulsifier such as a polymer emulsifier obtained by introducing a hydrophilic group such as a salt of a carboxyl group or a salt of a sulfone group into various polymers such as a vinyl-based polymer and a polyester-based polymer is used.
• various protective colloids such as polyvinyl alcohol and cellulose for stabilizing emulsification can be used in combination.
• aqueous emulsified dispersion composition In order to obtain an aqueous emulsified dispersion composition by a method other than the aqueous emulsion polymerization, there are a self-emulsification method in which a tertiary amine salt of a carboxyl group is introduced into the molecule of the cobolimer, and an emulsification method using an external emulsifier.
• a vinyl resin having a functional group such as a carboxyl group, a hydroxyl group, or a glycidyl group is required.
• a method of synthesizing a polystyrene resin and a polyester resin having a glycidyl group, a hydroxyl group, a carboxyl group, etc., and bonding them by esterification Japanese Patent Application Laid-Open No.
• Examples of the compound having at least one 5-membered dithiocarbonate group of the present invention include a phenol-derived dithiocarbonate compound, an alcohol-derived dithiocarbonate compound, and a carboxylic acid-derived dithiocarbonate compound.
• Compounds obtained by reacting oxysilane compounds such as compounds, diphenyl epoxy resin, ethylene oxide, propylene oxide, butylene oxide, triglycidyl isocyanurate, epoxidized soybean oil, epoxidized soybean oil fatty acids with carbon disulfide And the like.
• phenol-derived dithiocarbonate compounds include glycidyl ether obtained by reacting a phenol compound such as phenol, resorcinol, hydroquinone, force konore, crezo-1 / lenovolac, and novolak with epichlorohydrin.
• a phenol compound such as phenol, resorcinol, hydroquinone, force konore, crezo-1 / lenovolac, and novolak with epichlorohydrin.
• the power of the compound obtained by reacting with carbon sulfide S especially the general formula (III)
• R 6 , R 8 , R 9 and R 11 are the same or different, and 1 to 4 hydrogen atoms may be substituted with Br, or phenylene or cyclohexylene, R 7 and R 10 are the same or different and represent methylene, C (CH 3 ), or S And m represents an integer of 1 to 40), and a hydroxy compound having a thiocarbonate group represented by the following formula (II): R 6 , R 8 , R 9 And R 11 are the same, and compounds wherein R 7 and R 1 Q are the same can be more preferably used. Further, R 6 , R 8 , R 9 and R 11 are phenylene, and R 7 and R 1 .
• R 6 , R 8 , R 9 and R 11 are cyclohexylene, and R 10 is C (CH 3 ) 2 , or R 6 , R s , R 9 and Compounds in which R 11 is cyclohexylene and R 7 and R 10 are methylene can be more preferably used.
• alcohol-derived dithiocarbonate compounds examples include methanol, ethanol, propanol / butane, butanore, octanore, nonanozore, isodecanol, ethylene glycolone, propylene glycolone, neobennole glycolone, and glycerine.
• alcohol such as trimethylonolepronone, ventaeris litonore, diventaeris litonore, butylethinolepropanediol, 2,4-getinolene 3-methinolene 1,5-1-pentanediol with epichlorohydrin.
• Compounds obtained by further reacting the obtained glycidyl ether with carbon disulfide are exemplified.
• a daricidyl compound obtained by reacting a carboxylic acid such as acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, and phthalic acid with epichlorohydrin is further reacted with carbon disulfide. And the compounds obtained by the above method.
• Compounds having at least one 5-membered dithio-carbonate group can be prepared by a known method [JP-A-5-247027; Journal of Organics, Chemistry (J. Org. Chem.), 60 ⁇ 473 (1995)], and can be obtained by reacting an oxysilane compound corresponding to the desired product with carbon disulfide in the presence of an alkali halide such as lithium bromide.
• the hydroxy compound represented by the general formula (III) can be obtained by preparing a corresponding commercially available epoxy resin (E-1001-1001, manufactured by Yuka Shell Co., Ltd.) in the same manner as described above. It can be obtained by reacting carbon sulfide in the presence of an alkali halide such as lithium bromide.Also, the oxysilane compound may be a commercially available compound, but if it is not available commercially, a compound having a hydroxyl group And epichlorohydrin in the presence of a base by a known method.
• an alkali halide such as lithium bromide.Also
• the oxysilane compound may be a commercially available compound, but if it is not available commercially, a compound having a hydroxyl group And epichlorohydrin in the presence of a base by a known method.
• the ketimine derivative, enamine derivative or aldimine derivative which is a component of the composition of the present invention is synthesized by a known method from an amino compound having a primary or secondary amino group and a low molecular weight luponyl compound or a low molecular weight aldehyde compound.
• a commercially available product, for example, H-2 manufactured by Yuka Shell Epoxy Co., Ltd. may be used.
• amino compound primary and secondary amine compounds can be used.
• the amino compound include monoamines such as methylamine, ethylamine, propylamine, butyramine, hexylamine, octylamine, monoethanolamine, diethanolamine, dimethylamine, getylamine, diisopropylamine, dibutylamine, and 2-amino-2-methylpropanol.
• Amines or ethylenediamine 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,8 diaminooctane, 1,2-diaminocyclo Hexane, dimermonoamide, N, N'-bis (2-aminoethyl) ethylenediamine, N, N'-bis (3-aminopropyl) ethylenediamine, N, N'-diamines such as dimethyldiaminopropane, Or, Dicyandi Mid, 1,2,3-triaminopronone, 1,2,3-triamino-12-methylpropane, 1,3-diamino-12-aminomethylpropane, 1,2-diamino_2-aminomethyl Butane, 1,3-diamino-12-methyl-1-aminomethylpropane, tris (2-aminoethy
• high molecular weight amino compound examples include vinyl polymerizable monomers having an amino group in a molecule such as (meth) acrylic acid monohydrazide, 2-aminoethyl (meth) atalylate, arylamine, N-methylarylamine, and diarylamine. Copolymers with other vinyl monomers or hydrolysates of copolymers of N-vinylformamide, N-vinylacetamide, etc.
• ketone compounds such as acetone, methylethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
• Examples of low-molecular-weight carbonyl compounds for synthesizing aldimine derivatives include acetoaldehyde, propion aldehyde, isoptyl aldehyde, and octyl aldehyde.
• the low-molecular-weight carbonyl compound is usually used in an amount of 0.5 to 5 equivalents, preferably 0.8 to 1.5 equivalents, based on the amino compound, but it may be used in a large excess in combination with the solvent. Absent.
• the constituent ketimine derivative, enamine derivative or aldimine derivative has an amino group or an imino group or a group in which hydrogen of the amino group or the amino group is substituted with an alkyl group or the like.
• the composition of the c the present invention is being used to be 2 give good coating properties, especially, the even less di Chio carbonate group It is characterized by containing a polymer or compound containing one and a ketimine derivative, an enamine derivative or an aldimine derivative, and can be obtained by uniformly dispersing and mixing the two, but containing various solvents as necessary. You may go out.
• the solvent in this case, for example, the above-mentioned polymerization solvent alone or a mixture of 2 to 4 kinds thereof is used in an amount of 0.2 to 100 times (weight ratio) with respect to the copolymer of the present invention:
• composition of the present invention is useful for applications such as paints, adhesives, inks, sealing agents, sealants, and the like, and in particular, a polymer or compound containing at least one dithiocarbonate group and a ketimine derivative
• Solvent-type paints comprising an enamine derivative or an aldimine derivative and a solvent other than water are preferred uses in terms of storage stability.
• the solvent other than water for example, a solvent other than water of the above-mentioned polymerization solvent can be used.
• composition of the present invention has excellent storage stability, it can be used as a one-pack type when used for applications such as paints.
• the solution or suspension of the composition of the present invention itself can be used as a clear paint or clear ink, but it can be used as a colored paint or colored ink by further adding a pigment or a dispersed pigment. Can also.
• the way the pigment dispersion, conventional vane tosylate acre, ball mill or the like can be used
• the compositions of the present invention if necessary, various ultraviolet absorbers, antioxidants, hindered one Doamin based light stabilizer Ingredients, pigment dispersants, and the like can be blended. Further, the composition of the present invention can be used, if necessary, with various kinds of commonly used alkyd resins, acrylic resins, cellulose resins, petroleum resins. , An epoxy resin, a plasticizer, a film-forming aid, a water-absorbing agent, and the like.
• composition of the present invention When the composition of the present invention is used for coatings, a common brushing method, a spraying method, etc. can be adopted as a coating method, and a wide range of curing conditions from room temperature drying to heat drying can be selected. is there. Also, as the type of object to be coated, it can be applied to metals, woods, plastics, inorganic materials, concrete, asphalt, etc., and is useful for undercoating, overcoating, as a one-coat finishing agent for protecting the material, improving the appearance, etc.
• Example 3 resin obtained in Reference Example 1 (A- 1) 20 g was added 'stirring ketimine derivative conductor 0. 3 2 g obtained in Reference Example 6, was prepared clear one varnish
• the clear varnish obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was applied to an iron phosphate treated plate (manufactured by Nippon Test Panel Co., Ltd.) using a paint coater to dry the film. After painting to 0 microns, dry at room temperature for 1 week to make a test piece
• Gel fraction About 0.5 g of a film was collected from the test piece, and washed with an Soxhlet extractor under reflux of acedone for 8 hours. After that, drying under reduced pressure was carried out for 1 ⁇ , and the residual weight ratio was determined to be a gel fraction.
• Pencil hardness Performed according to the handwriting method of JISK 5400 (paint general test method).
• Adhesion According to the cross-cut test method of JISK 5400 (General paint test method), Given c
• JISK540 General Paint Test Method
• composition of the present invention is superior to the composition of Comparative Example in terms of film coating performance and storage stability.
• dithio-carbonate composition useful for applications such as paints, adhesives, inks, sealing agents, and sealants.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Epoxy Resins (AREA)
• Paints Or Removers (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 1997
  • 1997-11-21 EP EP97913426A patent/EP0943660A1/en not_active Withdrawn
  • 1997-11-21 US US09/319,449 patent/US6372871B1/en not_active Expired - Fee Related
  • 1997-11-21 CN CN97180285A patent/CN1239492A/zh active Pending
  • 1997-11-21 WO PCT/JP1997/004258 patent/WO1998024849A1/ja not_active Ceased
  • 1997-11-21 AU AU50665/98A patent/AU5066598A/en not_active Abandoned
  • 1997-11-21 KR KR1019990704220A patent/KR20000053242A/ko not_active Ceased

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