[go: up one dir, main page]

WO2018179455A1 - Polymère ayant un groupe contenant du silicium réactif et son procédé de production - Google Patents

Polymère ayant un groupe contenant du silicium réactif et son procédé de production Download PDF

Info

Publication number
WO2018179455A1
WO2018179455A1 PCT/JP2017/018337 JP2017018337W WO2018179455A1 WO 2018179455 A1 WO2018179455 A1 WO 2018179455A1 JP 2017018337 W JP2017018337 W JP 2017018337W WO 2018179455 A1 WO2018179455 A1 WO 2018179455A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polymer
carbon atoms
unsubstituted
reactive silicon
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2017/018337
Other languages
English (en)
Japanese (ja)
Inventor
山田　哲郎
宗直 廣神
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical 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 Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Publication of WO2018179455A1 publication Critical patent/WO2018179455A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • 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
    • C08G18/83—Chemically modified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08L101/10—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups

Definitions

  • the present invention relates to a polymer having a reactive silicon-containing group and a method for producing the same, and more specifically, as a silicon group that can be crosslinked by forming a siloxane bond (hereinafter also referred to as “reactive silicon group”).
  • the present invention relates to a polymer containing an alkoxy group bonded to a silicon atom at a molecular chain end and a method for producing the same.
  • reactive silicon groups especially alkoxysilyl groups
  • polymers having reactive silicon groups are cured by crosslinking and curing in the presence of moisture or moisture.
  • these polymers those whose main chain is a polyoxyalkylene polymer are generally known as modified silicones, and those whose main chain is a silicon-containing compound are generally known as end-capped silicones. It has been.
  • a curable composition using a polymer having a reactive silicon group as typified by these is liquid at room temperature and has a characteristic of becoming a rubber elastic body upon curing. It is widely used for coating agents, adhesives, architectural sealants, etc.
  • the room temperature curable compositions disclosed in Patent Documents 1 and 2 have low reactivity with moisture in the air and insufficient curability, so that sufficient curability at room temperature is ensured.
  • a catalyst such as an organotin compound
  • the organotin compound is concerned about toxicity to the human body and the environment. In recent years, environmental regulations have become strict, and its use is avoided.
  • Patent Document 3 discloses an alkoxysilyl end-capped polymer obtained by reacting a polymer having a hydroxyl group at a terminal with isocyanate silane or the like in order to improve reactivity.
  • the compound of Patent Document 3 although the reactivity is improved to some extent, when it does not contain a curing catalyst, its curability is very slow, and when used as a room temperature curable composition, the curability is low. Not only is it insufficient, but when we actually confirmed the curability when using an amine compound as a curing catalyst, the curability is still not satisfactory and there is room for improvement in terms of curability. .
  • the present invention has been made in view of the above circumstances, and in both cases where no curing catalyst is contained and when an amine compound is used as a curing catalyst, fast curability is good and the reactivity is excellent in safety. It is an object of the present invention to provide a polymer having a silicon-containing group and a method for producing the same.
  • the present inventors have determined that a predetermined polymer containing a specific tertiary amino-methylene-silyl bond as a linking group between the alkoxysilyl group at the molecular chain terminal and the main chain structure And a method for producing the same, and a composition containing this polymer is suitable as a curable composition for forming a material such as a coating agent, an adhesive, and a sealant, in order to give a cured product excellent in rapid curing.
  • the headline and the present invention were completed.
  • the present invention Polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, poly Ether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and a main chain skeleton selected from these copolymers, and in one molecule
  • a polymer having one reactive silicon-containing group represented by the following structural formula (2); Wherein R 1 , R 2 , R 3 and m represent the same meaning as described above, R 5 represents the same meaning as described above independently of each other, and R 6 represents the same meaning as described above independently of each other.
  • A represents polyurethane, polyurea, polyoxyalkylene, polycarbonate, polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, Polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ether ketone, polysiloxane, polysiloxane-polyurethane copolymer and polysiloxane-polyurea copolymer, and These copolymers Represents a divalent linking group having a structure selected et.) 3.
  • the polymer having 1 or 2 reactive silicon-containing groups represented by the following formula (3): (Wherein R 6 and X each independently represent the same meaning as described above, and Y each independently represents an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted carbon, Represents an aralkylene group having 7 to 20 atoms or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, n represents an integer of 1 or more, and Z represents a polyurethane, polyurea, polyoxyalkylene, polycarbonate , Polyester, polyamide, polyimide, polyamideimide, poly (meth) acrylate, polystyrene, polyolefin, polyvinyl ester, polytetrafluoroethylene, polyacetal, polyphenylene ether, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, poly Siloxane, Polys
  • a polymer whose molecular chain ends are blocked with an isocyanate group or an isothiocyanate group, and a compound of formula (5) (In the formula, R 1 , R 2 , R 3 , R 5 and m have the same meaning as described above.)
  • A) a curable composition comprising a polymer having a reactive silicon-containing group according to any one of 1 to 5, 10. Further, (B) 9 curable composition containing a curing catalyst, 11.
  • An adhesive comprising any one of the curable compositions of 9 to 11, 14 A cured article obtained by curing any of the curable compositions of 9 to 11, 15.
  • a cured article having an adhesive layer formed by curing 13 adhesives is provided.
  • the polymer having a reactive silicon-containing group of the present invention has good fast curability even when an amine compound is used as a curing catalyst so as not to contain an organotin compound, and further the curing catalyst. Even if it does not contain, the fast curability is good.
  • the compound of the present invention having such properties can be suitably used as a main agent (base polymer) such as a coating agent, an adhesive, and a sealant.
  • the polymer having a reactive silicon-containing group according to the present invention has a polymer main chain and at least one reactive silicon-containing group represented by the following structural formula (1) in one molecule, which is bonded to the main chain. .
  • R 1 s are unsubstituted or substituted alkyl groups having 1 to 10, preferably 1 to 4 carbon atoms, or unsubstituted or substituted carbon atoms having 6 to Represents an aryl group of 10 and R 2 independently of each other is an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, or an unsubstituted or substituted carbon atom 6 Represents an aryl group of ⁇ 10.
  • the alkyl group having 1 to 10 carbon atoms may be linear, cyclic or branched, and specific examples thereof include methyl, ethyl, n-propyl, i- Linear or branched alkyl groups such as propyl, n-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl group, Examples thereof include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl group and the like. Some or all of the hydrogen atoms in these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Examples include chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like.
  • R ⁇ 1 >, R ⁇ 2 >, a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group is more preferable from the surface of sclerosis
  • R 3 s independently of each other are unsubstituted or substituted alkyl groups having 1 to 10, preferably 1 to 6 carbon atoms, or unsubstituted or substituted carbon atoms having 6 to 6 carbon atoms. It represents a 10 aryl group, R 3 together are bonded, an unsubstituted or substituted C 1 -C 10, preferably an alkylene group having 1 to 4 carbon atoms or an unsubstituted or substituted C 6 -C, 20 arylene groups are represented, and examples of these alkyl groups and aryl groups include the same groups as those exemplified above for R 1 and R 2 .
  • alkylene group having 1 to 10 carbon atoms in R 3 include methylene, ethylene, trimethylene, propylene, tetramethylene, isobutylene, dimethylethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, heptamethylene Linear or branched alkylene groups such as octamethylene, nonamethylene, decylene (decamethylene) groups; cycloalkylene groups such as cyclopentylene groups and cyclohexylene groups.
  • Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, oxybisphenylene, sulfonebisphenylene, toluenediyl, xylenediyl, naphthalenediyl group and the like. And an arylene group. Some or all of the hydrogen atoms in these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Examples thereof include a chlorotrimethylene group, a 2,3,3-trifluorotrimethylene group, and a 2-chloro-1,4-phenylene group.
  • R 3 when R 3 is not bonded to each other and does not form a ring, R 3 is preferably a methyl, ethyl, t-butyl, or phenyl group, which is advantageous in terms of curability, availability, productivity, and cost. In consideration, methyl and t-butyl groups are more preferable.
  • R 3 when R 3 is bonded to each other to form a ring, R 3 is preferably methylene or ethylene group. In view of curability, availability, productivity, and cost, methylene group is more preferable. preferable.
  • R 5 represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkylene group for R 5 include the same groups as those exemplified for R 3 above. Among them, methylene and ethylene groups are preferable, and in consideration of curability, availability, productivity, and cost. An ethylene group is more preferable.
  • R 6 is a hydrogen atom or an unsubstituted or substituted C 1 -C 10, preferably an alkyl group having 1 to 4 carbon atoms, examples of the alkyl group, the above R 1 The thing similar to the illustrated group is mentioned.
  • R 6 a hydrogen atom, a methyl group, and a phenyl group are preferable, and a hydrogen atom is more preferable in consideration of curability, availability, productivity, and cost.
  • X represents O (oxygen atom) or S (sulfur atom), and O is preferable in consideration of curability, availability, productivity, and cost.
  • M represents an integer of 1 to 3, preferably 2 to 3, more preferably 3 from the viewpoint of reactivity.
  • the polymer of the present invention is a polymer having at least one reactive silicon group represented by the structural formula (1) in one molecule
  • the structure of the main chain skeleton to which the reactive silicon group is linked is particularly limited.
  • the main chain skeleton may have a linear structure, a branched structure, or a crosslinked structure.
  • main chain skeleton of the polymer of the present invention include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, Polyesters such as amorphous polyarylate and liquid crystal polymer; polyamide; polyimide; polyamideimide; poly (meth) acrylate; polystyrene; polyethylene, polypropylene, polyvinyl chloride, cyclic polyolefin, polybutadiene, polyisoprene, polyisobutylene, styrene-butadiene copolymer Polymer, polychloroprene, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-iso Polyethylene, such as polyole
  • polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane- Polyurethane copolymers and (dimethyl) polysiloxane-polyurea copolymers are preferred.
  • polyurethane, polyurea, polyoxyalkylene (polyether), (Dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and polyurethane, polyurea and polyoxyalkylene (polyether) are even more preferred.
  • the polymer of the present invention at least one reactive silicon group represented by the structural formula (1) is contained in one molecule at the molecular chain terminal, but the structural formula (1) contained in one molecule. If the average number of reactive silicon groups represented by is less than 1, the curability of the composition containing this as the main agent and the mechanical properties of the cured product become insufficient. On the other hand, if there are too many reactive silicon groups, the crosslink density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of reactive silicon groups contained in one molecule is preferably 1.1 to 5, more preferably 2 to 4, and even more preferably 2 (for example, one at each end of the molecular chain). Each).
  • the polymer of the present invention those represented by the following structural formula (2) are preferable.
  • the mechanical properties of the obtained cured product and the storage stability of the composition are further improved. Become.
  • R 1 , R 2 , R 3 and m represent the same meaning as described above, R 5 represents the same meaning as described above independently of each other, and R 6 represents the same as defined above independently of each other.
  • the same meaning is represented and X represents the same meaning as the above independently of each other.
  • A is not particularly limited as long as A is a divalent linking group having a structure corresponding to the above-described polymer main chain skeleton, and similarly to the above, a linear structure in the main chain skeleton, It may have a branched structure or a crosslinked structure.
  • A include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, amorphous polyarylate, liquid crystal polymer Polyamide; Polyimide; Polyamideimide; Poly (meth) acrylate; Polystyrene; Polyethylene, Polypropylene, Polyvinyl chloride, Cyclic polyolefin, Polybutadiene, Polyisoprene, Polyisobutylene, Styrene-butadiene copolymer, Polychloroprene, Acrylonitrile— Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-isoprene copolymer, ethylene Polyolefin such as propylene copolymer, ethylene-propylene (
  • A includes polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) )
  • a divalent linking group containing a polysiloxane-polyurea copolymer is preferable.
  • polyurethane, polyurea, polyoxyalkylene (polyether) Divalent linking groups containing (dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and contain polyurethane, polyurea, polyoxyalkylene (polyether) structure A divalent linking group is more preferred.
  • a in the above formula (2) is represented by the following structural formula (3).
  • R 6 and X each independently represent the same meaning as described above.
  • Y is independently of each other an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted aralkylene group having 7 to 20 carbon atoms, or an unsubstituted or substituted carbon atom having 6 to 20 carbon atoms.
  • Specific examples of the alkylene group having 1 to 20 carbon atoms include the same groups as those exemplified above for R 3 , but a chain portion and a cyclic portion represented by the following formula (A) are included. It may be a divalent group that coexists.
  • Examples of the arylene group having 6 to 20 carbon atoms include the same groups as those exemplified for R 3 above.
  • Specific examples of the aralkylene group having 7 to 20 carbon atoms include methylene bisphenylene, dimethylmethylene bisphenylene, ethylene bisphenylene, and tetramethylene bisphenylene groups.
  • some or all of hydrogen atoms of these groups may be substituted with a halogen atom such as an alkyl group, an aryl group, F, Cl, or Br, a cyano group, or the like. Specific examples thereof include difluoromethylene.
  • a bisphenylene group etc. are mentioned.
  • Y is preferably hexamethylene, methylenebisphenylene, 1,4-phenylene, toluenediyl, naphthalenediyl, or a divalent group represented by the above formula (A), and is curable or easily available.
  • hexamethylene, methylenebisphenylene, toluenediyl, and a divalent group represented by the above formula (A) are more preferable, represented by the above formula (A). Divalent groups are even more preferred.
  • N in the formula (3) is a number of 1 or more, but is preferably 1 to 1,000, more preferably 1 to 500, from the viewpoint of mechanical properties of the resulting cured product and workability of the composition. Is even more preferable.
  • Z is not particularly limited as long as Z is a divalent linking group containing a structure corresponding to the above-described polymer main chain skeleton, and as described above, the structure is linear in the main chain skeleton. It may have a structure, a branched structure, or a crosslinked structure.
  • Z include: polyurethane; polyurea; polyoxyalkylene (polyether); polycarbonate; polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, amorphous polyarylate, liquid crystal polymer Polyamide; Polyimide; Polyamideimide; Poly (meth) acrylate; Polystyrene; Polyethylene, Polypropylene, Polyvinyl chloride, Cyclic polyolefin, Polybutadiene, Polyisoprene, Polyisobutylene, Styrene-butadiene copolymer, Polychloroprene, Acrylonitrile— Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, isobutylene-isoprene copolymer, ethylene Polyolefin such as propylene copolymer, ethylene-propylene (
  • Z polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) )
  • a divalent linking group containing a polysiloxane-polyurea copolymer is preferable.
  • polyurethane, polyurea, polyoxyalkylene (polyether) Divalent linking groups containing (dimethyl) polysiloxane-polyurethane copolymer and (dimethyl) polysiloxane-polyurea copolymer are more preferred, and contain polyurethane, polyurea, polyoxyalkylene (polyether) structure And more preferably a divalent linking group From the viewpoint of the storage stability of the mechanical properties and composition of the product, a divalent linking group having a polyoxyalkylene structure are particularly preferred.
  • the polyoxyalkylene structure may have any of a linear structure, a branched structure, and a crosslinked structure. From the viewpoint of the mechanical properties of the resulting cured product and the storage stability of the composition, the polyoxyalkylene structure is linear. A polyoxyalkylene structure is preferred.
  • the polyoxyalkylene structure being “linear” means that the divalent oxyalkylene groups, which are repeating units constituting the polyoxyalkylene structure, are linearly linked. This means that each oxyalkylene group itself may be linear or branched (for example, a propyleneoxy group such as —CH 2 CH (CH 3 ) O—).
  • the polymer of the present invention preferably has a linear structure in which Z in the above formula (3) has a repeating unit represented by the following structural formula (4).
  • the mechanical properties of the resulting cured product and the storage stability of the composition are further improved.
  • R 4 is not particularly limited as long as it is a divalent hydrocarbon group, preferably a divalent aliphatic hydrocarbon group, but it is linear or branched having 1 to 14 carbon atoms.
  • a chain alkylene group is preferable, and a linear or branched alkylene group having 2 to 4 carbon atoms is more preferable.
  • Examples of the alkylene group include the same groups as those exemplified for R 3 above.
  • p is an integer of 1 or more, but is preferably 5 to 700, more preferably 10 to 500, and still more preferably 20 to 300, from the viewpoint of mechanical properties of the obtained cured product and workability of the composition. . When p is 2 or more, a plurality of R 4 may be the same or different from each other.
  • the main chain skeleton of the oxyalkylene polymer may be composed of one type of repeating units represented by the above formula (4), or may be composed of two or more types of repeating units.
  • a polymer containing propylene oxide (—CH 2 CH (CH 3 ) O—) as a main component is preferable from the viewpoint of durability.
  • the number average molecular weight of the polymer of the present invention is not particularly limited, but the workability is improved within the appropriate range of the viscosity of the curable composition containing the polymer, and sufficient curability is imparted.
  • the number average molecular weight is preferably 200 to 200,000, more preferably 1,000 to 100,000.
  • the number average molecular weight in this invention is a polystyrene conversion value in a gel permeation chromatography (GPC) analysis (hereinafter the same).
  • the viscosity of the polymer of the present invention is not particularly limited, but it is considered that the viscosity of the curable composition containing the polymer is within an appropriate range to improve workability and provide sufficient curability. Accordingly, the viscosity is preferably 10 to 200,000 mPa ⁇ s, more preferably 50 to 100,000 mPa ⁇ s, and particularly preferably 100 to 50,000 mPa ⁇ s.
  • the viscosity is a value measured at 25 ° C. by a B-type rotational viscometer.
  • the polymer of the present invention described above is a compound having a polymer having a molecular chain end blocked with an isocyanate group or an isothiocyanate group, and a secondary amino group, a tertiary amino group and an alkoxysilyl group represented by the following formula (5): (Hereinafter referred to as “secondary-tertiary diaminosilane”). More specifically, a urea bond or thiourea is formed between the isocyanate group or isothiocyanate group of the polymer whose molecular chain end is blocked with an isocyanate group or isothiocyanate group and the secondary amino group of the secondary-tertiary diaminosilane. A reaction to form a bond (urea reaction or thiourea reaction) is performed.
  • secondary-tertiary diaminosilane represented by the above formula (5) include N- (trimethoxysilylmethyl) piperazine, N- (methyldimethoxysilylmethyl) piperazine, N- (dimethylmethoxysilylmethyl).
  • Piperazine N- (triethoxysilylmethyl) piperazine, N- (methyldiethoxysilylmethyl) piperazine, N- (dimethylethoxysilylmethyl) piperazine, N- (trimethoxysilylmethyl) imidazolidine, N- (methyldimethoxysilyl) Methyl) imidazolidine, N- (dimethylmethoxysilylmethyl) imidazolidine, N- (triethoxysilylmethyl) imidazolidine, N- (methyldiethoxysilylmethyl) imidazolidine, N- (dimethylethoxysilylmethyl) imidazolidine, N, N'-dimethyl -N- (trimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (methyldimethoxysilylmethyl) ethylenediamine, N, N'-dimethyl-N- (dimethylmethoxysilylmethyl) ethylenediamine
  • the structure of the main chain skeleton to which these groups are linked is particularly limited.
  • the main chain skeleton may have a linear structure, a branched structure, or a crosslinked structure. Among these, a linear structure is preferable from the viewpoint of mechanical properties of the obtained cured product and storage stability of the composition.
  • polyurethane, polyurea, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysiloxane-poly Urea copolymers are preferred, and in view of curability, availability, productivity, and cost, polyurethane, polyurea, polyoxyalkylene (polyether), (dimethyl) polysiloxane-polyurethane copolymer, ( (Dimethyl) polysiloxane-polyurea copolymer is more preferred , Polyurethanes, polyureas, polyoxyalkylene (polyether), polyester, poly (meth) acrylate, polyolefin, (dimethyl) polysiloxane, (dimethyl) polysiloxane-polyurethane copolymer, (dimethyl) polysi
  • the polymer whose molecular chain terminal is blocked with an isocyanate group or isothiocyanate group contains at least one isocyanate group or isothiocyanate group in one molecule, but the isocyanate group contained in one molecule.
  • the number of isothiocyanate groups on average is less than 1, the curability of the composition of the present invention and the mechanical properties of the cured product become insufficient.
  • the crosslinking density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of isocyanate groups or isothiocyanate groups contained in one molecule is 1 or more, preferably 1.1 to 5, more preferably 2 to 4, and still more preferably 2 (for example, molecular chain One at each end).
  • a polymer represented by the following structural formula (6) is preferable as the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group.
  • a polymer represented by the following structural formula (6) is preferable as the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group.
  • X represents O (oxygen atom) or S (sulfur atom) independently of each other, but O is preferable from the viewpoint of curability, availability, productivity, and cost.
  • a polymer compound which is available as a commercially available product is a polyol compound whose molecular chain terminal is blocked with a hydroxyl group.
  • a urethanization reaction or a thiourethanization reaction between a hydroxyl group and an isocyanate group or isothiocyanate group of a polyisocyanate compound or polyisothiocyanate compound (generally known as an isocyanate prepolymer) It may be used.
  • the structure of the main chain skeleton to which the hydroxyl group is linked is not particularly limited as long as the polyol compound having the molecular chain end blocked with a hydroxyl group has a hydroxyl group at the molecular chain end. May have a linear structure, a branched structure, or a crosslinked structure. Among these, a linear structure is preferable from the viewpoint of mechanical properties of the obtained cured product and storage stability of the composition.
  • polystyrene resin examples include polyoxyalkylene polyol (polyether polyol), polyester polyol, acrylic polyol, epoxy polyol, polyolefin polyol, fluorine-containing polyol, ⁇ , ⁇ -hydroxyalkyl ( Dimethyl) polysiloxane and the like. These may be used as a single component, or may be used as a mixture or copolymer by combining two or more components.
  • polyoxyalkylene polyols polyether polyols
  • polyester polyols polyolefin polyols
  • ⁇ , ⁇ -hydroxyalkyl (dimethyl) polysiloxanes are preferred as the polyol compounds whose molecular chain ends are blocked with hydroxyl groups, and are curable.
  • polyoxyalkylene polyol (polyether polyol) and ⁇ , ⁇ -hydroxyalkyl (dimethyl) polysiloxane are more preferable, and polyoxyalkylene polyol (polyether polyol). Is even more preferable.
  • the polyol compound whose molecular chain end is blocked with a hydroxyl group contains at least one hydroxyl group in one molecule, but the average number of hydroxyl groups contained in one molecule is less than one.
  • curing material will become inadequate.
  • the number of hydroxyl groups contained in one molecule is 1 or more, preferably 1.1 to 5, more preferably 2 to 4, and even more preferably 2 (for example, at both ends of the molecular chain, respectively). One by one).
  • polyol compound whose molecular chain end is blocked with a hydroxyl group those represented by the following structural formula (7) are preferable.
  • the mechanical properties of the resulting cured product and the composition Storage stability is further improved.
  • polyol compound in which the molecular chain terminal is blocked with a hydroxyl group include those represented by the following structural formulas, but are not limited thereto, and the molecular chain terminal is blocked with a hydroxyl group. Any polyol compound can be used.
  • the number average molecular weight of the polyol compound in which the molecular chain terminal is blocked with a hydroxyl group is not particularly limited, but it is sufficient to improve workability by setting the viscosity of the curable composition of the present invention within an appropriate range.
  • the number average molecular weight is preferably 200 to 50,000, more preferably 1,000 to 20,000.
  • the polyisocyanate compound or polyisothiocyanate compound is not particularly limited as long as it contains at least two isocyanate groups or isothiocyanate groups in one molecule at the molecular chain end, and is not limited in the main chain skeleton. May have a linear structure, a branched structure, or a crosslinked structure. Among these, those containing a linear structure and / or a branched structure are preferred from the viewpoint of the mechanical properties of the resulting cured product and the storage stability of the composition.
  • the polyisocyanate compound or polyisothiocyanate compound contains at least two isocyanate groups or isothiocyanate groups in one molecule, but the number of isocyanate groups or isothiocyanate groups contained in one molecule. If the average number is less than 2, the curability of the composition containing the polymer of the present invention prepared using this as a main ingredient and the mechanical properties of the cured product become insufficient. On the other hand, if there are too many isocyanate groups or isothiocyanate groups, the crosslinking density becomes too high, and the resulting cured product may not exhibit good mechanical properties, or the storage stability of the composition may deteriorate. Therefore, the number of isocyanate groups or isothiocyanate groups contained in one molecule is 2 or more, preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 (for example, both molecular chains One at each end).
  • polyisocyanate compound or polyisothiocyanate compound those represented by the following structural formula (8) are preferable.
  • the mechanical properties of the resulting cured product and the storage stability of the composition are obtained. Is even better.
  • polyisocyanate compound or polyisothiocyanate compound examples include hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, 4,4'-bis- (isocyanatemethyl) -diphenylmethane, polymethylene polyphenyl polyisocyanate, and phenylene.
  • hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate are preferred, and hexamethylene diisocyanate and isophorone diisocyanate are more preferred.
  • the production method is not particularly limited. What is necessary is just to select suitably from the well-known manufacturing method currently used by the urethanation reaction.
  • the reaction ratio of the polyol compound whose molecular chain end is blocked with a hydroxyl group and the polyisocyanate compound or polyisothiocyanate compound suppresses by-products during the urethanization reaction or thiourethanization reaction
  • the isocyanate group or isothiocyanate group of the polyisocyanate compound or polyisothiocyanate compound is 1 mol of the hydroxyl group in the polyol compound whose molecular chain end is blocked with a hydroxyl group.
  • a ratio of greater than 1 mol to 100 mol or less is preferred, a ratio of 1.1 to 50 mol is more preferred, and a ratio of 1.2 to 10 mol is even more preferred.
  • a catalyst may not be used, but a catalyst may be used for improving the reaction rate.
  • the catalyst may be appropriately selected from those generally used in the urethanization reaction or thiourethanation reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethyl). Hexanoate), dibutyltin dilaurate, dioctyltin dilaurate and the like.
  • the amount of the catalyst used may be a catalytic amount, but is usually 0.001 to 1% by mass based on the total of the polyol compound and the polyisocyanate compound or polyisothiocyanate compound whose molecular chain ends are blocked with a hydroxyl group.
  • a solvent that does not adversely influence the reaction can be used in the urethanization reaction or thiourethanation reaction.
  • hydrocarbon solvents such as pentane, hexane, heptane, octane, decane and cyclohexane
  • aromatic solvents such as benzene, toluene and xylene
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • formamide Amide solvents such as N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ester solvents such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, propylene glycol-1-monomethyl ether-2-acetate; diethyl ether
  • examples include ether solvents such as dibutyl ether, cyclopentyl methyl ether, tetrahydrofur
  • the reaction temperature during the urethanization reaction or thiourethanization reaction is not particularly limited, but is preferably 25 to 90 ° C. in consideration of suppressing side reactions such as allophanatization while making the reaction rate appropriate. 40 to 80 ° C. is more preferable.
  • the reaction time is not particularly limited, but is usually 10 minutes to 24 hours.
  • the polymer having a reactive silicon-containing group of the present invention is obtained by reacting a polymer whose molecular chain end is blocked with an isocyanate group or an isothiocyanate group and a secondary-tertiary diaminosilane represented by the above formula (5).
  • the specific method is not particularly limited, and may be appropriately selected from known production methods generally used in the urea reaction or thiourea reaction. More specifically, the reaction ratio between the secondary / tertiary diaminosilane represented by the above formula (5) and the polymer whose molecular chain terminal is blocked with an isocyanate group or an isothiocyanate group is represented by urea reaction or thiourea.
  • the ratio of the isocyanate group or isothiocyanate group in the polymer whose molecular chain end is blocked with an isocyanate group or isothiocyanate group is preferably 0.1 to 2.0 mol, and the ratio of 0.4 to 1.5 mol is preferable. More preferably, the ratio of 0.8 to 1.2 mol is even more preferable.
  • a catalyst may be used to improve the reaction rate.
  • the catalyst may be appropriately selected from those generally used in urea reaction or thiourea reaction, and specific examples thereof include dibutyltin oxide, dioctyltin oxide, tin (II) bis (2-ethylhexa). Noate), dibutyltin dilaurate, dioctyltin dilaurate and the like.
  • the catalyst may be used in any catalytic amount, but is usually the sum of the secondary and tertiary diaminosilane represented by the above formula (5) and the polymer whose molecular chain ends are blocked with isocyanate groups or isothiocyanate groups.
  • the content is 0.001 to 1% by mass.
  • a solvent that does not adversely influence the reaction can be used for the urea reaction or thiourea reaction.
  • hydrocarbon solvents such as pentane, hexane, heptane, octane, decane and cyclohexane
  • aromatic solvents such as benzene, toluene and xylene
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • formamide Amide solvents such as N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ester solvents such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, propylene glycol-1-monomethyl ether-2-acetate; diethyl ether
  • examples include ether solvents such as dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran,
  • the reaction temperature at the time of urea reaction or thiourea reaction is not particularly limited, but it is preferably 0 to 90 ° C. in consideration of suppressing side reactions such as allophanatization while making the reaction rate appropriate. 25 to 80 ° C. is more preferable.
  • the reaction time is not particularly limited, but is usually 10 minutes to 24 hours.
  • the first curable composition, the coating agent composition and the adhesive composition of the present invention are (A) at least one in one molecule. It contains a polymer containing a reactive silicon group represented by the structural formula (1) at the molecular chain terminal, and (B) a curing catalyst.
  • the polymer of the above component (A) is derived from the structure of the polymer, and a cured product obtained by coating or adhering using a composition containing this polymer has excellent curability compared to conventional compositions. give.
  • the curing catalyst (B) used in the first composition of the present invention promotes a reaction in which a hydrolyzable group contained in a polymer having a reactive silicon-containing group (A) is hydrolytically condensed with moisture in the air. It is a component that accelerates the curing of the composition and is added for efficient curing.
  • the curing catalyst is not particularly limited as long as it is a curing catalyst used for curing a general moisture condensation curable composition.
  • alkyltin compounds such as dibutyltin oxide and dioctyltin oxide.
  • Alkyltriester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, dioctyltin dioctoate, dioctyltin diversate; tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium , Titanate esters such as dipropoxybis (acetylacetonato) titanium, titanium diisopropoxybis (ethylacetoacetate), titanium isopropoxyoctylene glycol, and titanium chelate compounds Partially hydrolyzed products thereof: zinc naphthen
  • 3-aminopropyltrimethoxysilane and tetramethylguanidylpropyltrimethoxysilane are more preferred because they contain no organotin compound and are less toxic. From the viewpoint of curability of the composition, tetraaminosilane is preferred. Methylguanidylpropyltrimethoxysilane is particularly preferred.
  • the addition amount of the curing catalyst is not particularly limited, but considering that the workability is improved by adjusting the curing rate to an appropriate range, 0.01 to 15 parts by mass is preferable, and 0.1 to 5 parts by mass is more preferable.
  • the second curable composition, coating agent composition and adhesive composition of the present invention (hereinafter sometimes collectively referred to as the second composition) contain (A) component, but (B) cure. It does not contain a catalyst.
  • the polymer having a reactive silicon-containing group (A) of the present invention is derived from the structure of the polymer, and (B) a coating treatment using a composition containing a polymer without containing a curing catalyst.
  • the cured product obtained by the adhesion treatment gives a cured product that is superior to the conventional composition in terms of curability.
  • the first and second compositions of the present invention may contain a solvent.
  • the solvent is not particularly limited as long as it has the ability to dissolve the component (A). Specific examples thereof include hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, and cyclohexane; benzene , Aromatic solvents such as toluene and xylene; amide solvents such as formamide, N, N-dimethylformamide, pyrrolidone and N-methylpyrrolidone, ethyl acetate, butyl acetate, ⁇ -butyrolactone, propylene glycol-1-monomethyl ether Ester solvents such as 2-acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl
  • aromatic solvents such as toluene and xylene are preferable from the viewpoints of solubility and volatility.
  • the amount of the solvent added is preferably 10 to 20,000 parts by mass, more preferably 100 to 10,000 parts by mass with respect to 100 parts by mass of component (A).
  • the first and second compositions of the present invention include an adhesion improver, an inorganic and organic ultraviolet absorber, a storage stability improver, a plasticizer, a filler, a pigment, and a fragrance depending on the purpose of use.
  • Various additives such as can be added.
  • the coating composition of the present invention described above is applied to the surface of a solid substrate and cured to form a coating layer, whereby a coated solid substrate is obtained, and the adhesive composition of the present invention is applied to the solid substrate. After applying another solid base material on the surface, and then curing the composition to form an adhesive layer, an adhesive laminate can be obtained.
  • the application method of each composition is not particularly limited, and specific examples thereof are appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating. Can do.
  • the solid substrate is not particularly limited, and specific examples thereof include epoxy resins, phenol resins, polyimide resins, polycarbonate resins such as polycarbonates and polycarbonate blends, acrylic resins such as poly (methyl methacrylate), poly (ethylene Terephthalate), poly (butylene terephthalate), polyester resins such as unsaturated polyester resin, polyamide resin, acrylonitrile-styrene copolymer resin, styrene-acrylonitrile-butadiene copolymer resin, polyvinyl chloride resin, polystyrene resin, polystyrene and polyphenylene Organic resin base materials such as ether blends, cellulose acetate butyrate, polyethylene resin; metal base materials such as iron plate, copper plate, steel plate; paint application surface; glass; ceramic; concrete; Sheet; textile; wood, stone, tile, inorganic filler such as (hollow) silica, titania, zirconia, alumina; glass fiber including glass fiber, glass tape, glass
  • the hydrolysis and condensation reaction of the polymer having a reactive silicon-containing group proceeds.
  • any humidity of 10 to 100% RH may be used. In general, the higher the humidity, the faster the hydrolysis proceeds. Therefore, moisture may be added to the atmosphere as desired.
  • the curing reaction temperature and time can be appropriately changed according to factors such as the substrate used, the moisture concentration, the catalyst concentration, and the type of hydrolyzable group.
  • the curing reaction temperature is preferably about 25 ° C. from the viewpoint of workability, etc., but in order to accelerate the curing reaction, it is cured by heating within a range not exceeding the heat resistance temperature of the substrate to be used. May be.
  • the curing reaction time is usually about 1 minute to 1 week from the viewpoint of workability and the like.
  • the composition of the present invention cures well even at room temperature, and therefore, even when room temperature curing is indispensable for on-site construction or the like, there is no stickiness (tack) on the surface of the coating film in several minutes to several hours, and curability. Although it is excellent in workability, the heat treatment may be performed within a range not exceeding the heat-resistant temperature of the substrate.
  • the viscosity is a value measured at 25 ° C. using a B-type rotational viscometer
  • the molecular weight and the degree of polymerization are measured by GPC (gel permeation chromatograph). These are the number average molecular weight and number average degree of polymerization calculated in terms of polystyrene.
  • Example 1-2 Synthesis of polymer 2
  • a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 100 g of both end hydroxyl groups-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl groups).
  • 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour.
  • reaction product was a pale yellow transparent liquid having a number average molecular weight of 9,000 and a viscosity of 5,100 mPa ⁇ s.
  • Example 1-3 Synthesis of polymer 3
  • 100 g of both ends hydroxyl group-containing polypropylene glycol having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C.
  • 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour.
  • Example 1-4 Synthesis of polymer 4 In a 200 mL separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 100 g of polypropylene glycol containing hydroxyl groups at both ends having a number average molecular weight of 5,100 and a polymerization degree of 50 (terminal hydroxyl groups) Of 0.070 mol in terms of functional group) and heated to 90 ° C. Into this, 24.3 g of toluene diisocyanate (the amount of functional group of isocyanate group was 0.14 mol) was added and stirred with heating at 90 ° C. for 1 hour.
  • reaction product was a pale yellow transparent liquid having a number average molecular weight of 17,400 and a viscosity of 32,000 mPa ⁇ s.
  • Example 1-6 Synthesis of polymer 6 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both hydroxyl groups at a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour.
  • Example 1-7 Synthesis of polymer 7 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of polypropylene glycol containing both end hydroxyl groups having a number average molecular weight of 7,800 and a polymerization degree of 130 (terminal hydroxyl group) was converted to a functional group equivalent of 0.039 mol) and heated to 90 ° C. Into this, 17.3 g of isophorone diisocyanate (functional amount of isocyanate group 0.078 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour.
  • Example 1-9 Synthesis of polymer 9
  • a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer was mixed with a hydroxyl group-containing polypropylene glycol / polyethylene glycol having a number average molecular weight of 5,200 and a polymerization degree of 65.
  • a polymer 100 g (polypropylene glycol structural unit / polyethylene glycol structural unit molar ratio 25/75, terminal hydroxyl group equivalent 0.068 mol) was charged and heated to 90 ° C.
  • 30.2 g of isophorone diisocyanate (the amount of functional group of isocyanate group was 0.14 mol) was added and heated and stirred at 90 ° C.
  • reaction product was a pale yellow transparent liquid having a number average molecular weight of 6,400 and a viscosity of 1,260 mPa ⁇ s.
  • Example 1-10 Synthesis of polymer 10 In a 200 mL separable flask equipped with a stirrer, a reflux condenser and a thermometer, ⁇ , ⁇ -hydroxypropyl (dimethyl) poly having a number average molecular weight of 15,000 and a polymerization degree of 200 was added. 100 g of siloxane (0.013 mol in terms of functional group of terminal hydroxyl group) was charged and heated to 90 ° C. Into this, 5.8 g of isophorone diisocyanate (functional amount of isocyanate group: 0.026 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour.
  • reaction product was a colorless and transparent liquid, and had a number average molecular weight of 16,800 and a viscosity of 16,000 mPa ⁇ s.
  • reaction product was a pale yellow transparent liquid having a number average molecular weight of 8,000, a degree of polymerization of 130, and a viscosity of 3,700 mPa ⁇ s.
  • N-phenylaminomethyltrimethoxysilane (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. It was confirmed that the absorption peak derived from the isocyanate group of the raw material disappeared completely by IR measurement, and that an absorption peak derived from a urea bond and a urethane bond was generated instead, and the reaction was completed.
  • the obtained reaction product was a pale yellow transparent liquid having a number average molecular weight of 8,700 and a viscosity of 5,000 mPa ⁇ s.
  • reaction product was a colorless and transparent liquid, and had a number average molecular weight of 11,300 and a viscosity of 7,500 mm 2 / s.
  • N-2- (aminoethyl) -aminomethyltrimethoxysilane (secondary amino group functional group amount: 0.039 mol) was added, and the mixture was heated and stirred at 90 ° C. for 1 hour. Gelled and a reaction product could not be obtained.
  • composition and cured film [Example 2-1] 100 parts by mass of the polymer 1 obtained in Example 1-1 above and 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane as a curing catalyst were uniformly mixed using a stirrer while blocking moisture. A composition was prepared. The obtained composition was subjected to bar coater No. 5 under air at 25 ° C. and 50% RH. 14 was applied to a glass plate and dried and cured for 1 day in air at 25 ° C. and 50% RH to prepare a cured film.
  • Example 2-2 to 2-10 and Comparative Examples 2-1 to 2-5 Except for changing the polymer 1 of Example 2-1 to the polymers 2 to 10 obtained in Examples 1-2 to 1-10 and the polymers 11 to 15 obtained in Comparative Examples 1-1 to 1-5, respectively. Produced a composition and a cured film in the same manner as in Example 2-1.
  • Example 2-11 The composition and curing were carried out in the same manner as in Example 2-1, except that 5 parts by mass of 3-aminopropyltrimethoxysilane was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. A coating was prepared.
  • Example 2-12 A composition and a cured film were prepared in the same manner as in Example 2-1, except that 5 parts by mass of dioctyltin diversate was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. .
  • Example 2-13 The composition was the same as in Example 2-1, except that 2 parts by mass of titanium diisopropoxybis (ethylacetoacetate) was used as a curing catalyst instead of 0.5 parts by mass of tetramethylguanidylpropyltrimethoxysilane. And cured coatings were prepared.
  • Example 2-14 A composition and a cured film were produced in the same manner as in Example 2-1, except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • Example 2-15 A composition and a cured film were produced in the same manner as in Example 2-7, except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • Comparative Example 2-6 A composition and a cured film were prepared in the same manner as in Comparative Example 2-1, except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • Comparative Example 2-7 A composition and a cured film were prepared in the same manner as in Comparative Example 2-2 except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • Comparative Example 2-8 A composition and a cured film were produced in the same manner as in Comparative Example 2-4 except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • Comparative Example 2-9 A composition and a cured film were produced in the same manner as in Comparative Example 2-5 except that tetramethylguanidylpropyltrimethoxysilane was not used.
  • a cured film having excellent curability can be obtained by using the polymer having a reactive silicon-containing group of the present invention. Moreover, even when an amine compound is used as a curing catalyst so as not to contain a highly toxic organotin compound, a curable composition having good curability, which was difficult with the prior art, can be obtained. Furthermore, even if it does not contain a curing catalyst, a curable composition having good curability can be obtained.

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)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un polymère qui a un squelette de chaîne principale comprenant un polymère donné, par exemple un polyuréthane, une polyurée ou un polyoxyalkylène, et qui a, dans la molécule, au moins un groupe contenant du silicium réactif représenté par la formule développée (1). Le polymère présente des propriétés de durcissement rapide satisfaisantes indépendamment du fait qu'aucun catalyseur de durcissement n'est contenu ou qu'un composé à base d'amine est utilisé comme catalyseur de durcissement. Le polymère est très sûr. (R1 et R2 représentent chacun indépendamment un alkyle en C1-10, etc.; deux R3 représentent chacun indépendamment un alkyle en C1-10, etc. ou sont liés l'un à l'autre pour représenter un alkylène en C1-10, etc.; R5 représente un alkylène en C1-10; R6 représente un atome d'hydrogène, etc.; X représente O, S, etc.; m est un nombre entier de 1 à 3; et * indique une liaison de liaison.)
PCT/JP2017/018337 2017-03-30 2017-05-16 Polymère ayant un groupe contenant du silicium réactif et son procédé de production Ceased WO2018179455A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-067557 2017-03-30
JP2017067557A JP2017141467A (ja) 2017-03-30 2017-03-30 反応性ケイ素含有基を有するポリマーおよびその製造方法

Publications (1)

Publication Number Publication Date
WO2018179455A1 true WO2018179455A1 (fr) 2018-10-04

Family

ID=59628913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/018337 Ceased WO2018179455A1 (fr) 2017-03-30 2017-05-16 Polymère ayant un groupe contenant du silicium réactif et son procédé de production

Country Status (2)

Country Link
JP (1) JP2017141467A (fr)
WO (1) WO2018179455A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020026731A1 (fr) * 2018-08-03 2020-02-06 信越化学工業株式会社 Composition de résine de polybutadiène durcissable à la température ambiante, procédé pour la produire, et carte de circuit encapsulée

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168302A (ja) * 1996-12-11 1998-06-23 Sunstar Eng Inc 一液型湿気硬化性組成物
JPH10176028A (ja) * 1996-12-19 1998-06-30 Asahi Chem Ind Co Ltd 室温硬化性樹脂組成物及びシーリング材
JP2008523177A (ja) * 2004-12-09 2008-07-03 ワッカー ケミー アクチエンゲゼルシャフト アルコキシシラン末端プレポリマー

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10168302A (ja) * 1996-12-11 1998-06-23 Sunstar Eng Inc 一液型湿気硬化性組成物
JPH10176028A (ja) * 1996-12-19 1998-06-30 Asahi Chem Ind Co Ltd 室温硬化性樹脂組成物及びシーリング材
JP2008523177A (ja) * 2004-12-09 2008-07-03 ワッカー ケミー アクチエンゲゼルシャフト アルコキシシラン末端プレポリマー

Also Published As

Publication number Publication date
JP2017141467A (ja) 2017-08-17

Similar Documents

Publication Publication Date Title
KR101519459B1 (ko) 오르가닐 옥시실란 말단을 가진 폴리머를 기반으로 하는 가교성 물질
JP4221301B2 (ja) アルコキシシランを末端基とするポリマーを含有している架橋性ポリマーブレンド
ES2349850T3 (es) Composición que contiene silicona.
US7871675B2 (en) Silane-crosslinkable coating formulations
US9493691B2 (en) Moisture curable organopolysiloxane compositions
EP3783003B1 (fr) Composé de silicium organique et procédé de production associé
JP7276214B2 (ja) オルガノポリシロキサンおよびそれを含有する硬化性組成物
JP6269875B2 (ja) 有機ケイ素化合物およびその製造方法
EP4059991A1 (fr) Organopolysiloxane et composition de revêtement le contenant
JP6642324B2 (ja) オルガノポリシロキサン化合物およびそれを含有するコーティング用組成物
KR20140081869A (ko) 다성분 실온-경화성 실리콘 탄성중합체 조성물
EP3594261B1 (fr) Composé silicium organique comprenant un groupe polyoxyalkylène, et procédé de fabrication de celui-ci
WO2018179455A1 (fr) Polymère ayant un groupe contenant du silicium réactif et son procédé de production
JP7139995B2 (ja) 有機ケイ素化合物、その製造方法および硬化性組成物
WO2023199747A1 (fr) Copolymère modifié par silane, son procédé de production et composition le contenant
JP2024539682A (ja) アルファ－シラン末端有機ポリマーに基づく反応性ホットメルト接着剤組成物
CN118382664A (zh) 缩合固化性组合物
EP3428197A1 (fr) Composé organosilicié et procédé pour sa production

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17903055

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17903055

Country of ref document: EP

Kind code of ref document: A1