WO2022009882A1 - Composition de polyisocyanate, procédé pour la production d'une composition de polyisocyanate, matière première de résine à deux composants, matériau de revêtement, agent adhésif et résine - Google Patents

Composition de polyisocyanate, procédé pour la production d'une composition de polyisocyanate, matière première de résine à deux composants, matériau de revêtement, agent adhésif et résine Download PDF

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WO2022009882A1
WO2022009882A1 PCT/JP2021/025468 JP2021025468W WO2022009882A1 WO 2022009882 A1 WO2022009882 A1 WO 2022009882A1 JP 2021025468 W JP2021025468 W JP 2021025468W WO 2022009882 A1 WO2022009882 A1 WO 2022009882A1
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polyisocyanate composition
polythiol
molecule
bis
xylylene diisocyanate
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PCT/JP2021/025468
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Japanese (ja)
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裕以智 塚田
聡 山崎
祐一 伊東
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三井化学株式会社
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Priority to JP2022535347A priority Critical patent/JP7322296B2/ja
Publication of WO2022009882A1 publication Critical patent/WO2022009882A1/fr

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    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • the present invention relates to a polyisocyanate composition, a method for producing a polyisocyanate composition, a two-component resin raw material, a coating material, an adhesive and a resin.
  • the two-component polyurethane resin raw material separately comprises a curing agent containing polyisocyanate and a main agent containing macropolyol. Then, the curing agent and the main agent are mixed immediately before use, and then applied to the object to be cured. As a result, the polyurethane resin is formed on the object.
  • a curing agent for such a two-component polyurethane resin raw material for example, a polyisocyanate composition containing an isocyanate derivative obtained by reacting xylylene diisocyanate with trimethylolalkane has been proposed (see, for example, Patent Document 1). ).
  • the polyurethane resin when the polyurethane resin is formed on the object, the polyurethane resin is required to have excellent adhesion to the object. Further, depending on the use of the polyurethane resin, it may be desired to improve the refractive index of the polyurethane resin. However, in the polyurethane resin produced from the polyisocyanate composition described in Patent Document 1, it is difficult to improve the refractive index while ensuring the adhesion.
  • the present invention has a polyisocyanate composition, a two-component resin raw material, a coating material, an adhesive, a resin, and a polyisocyanate composition, which can improve the refractive index of the resin while imparting excellent adhesion to the resin.
  • a method for manufacturing a product Provide a method for manufacturing a product.
  • the present invention is a reaction product of xylylene diisocyanate and a polythiol having two or more mercapto groups, and is a polyisocyanate composition containing an isocyanate derivative having an isocyanate group at the molecular end, wherein the isocyanate derivative is used.
  • the reaction product of the polythiol and the xylylene diisocyanate which comprises one polythiol molecule-a polythiol polymolecule having a higher molecular weight than the xylylene diisocyanate n molecule-a xylylene diisocyanate polymolecule, and the polythiol 1 It contains a polyisocyanate composition in which the mass ratio of the polythiol polymolecule-xylylene diisocyanate polymolecule to the molecule-xylylene diisocyanate n molecule is 0.50 or more and 5.2 or less.
  • the polyisocyanate composition further contains a cyclic compound having a ring structure containing two or more thiourethane bonds derived from xylylene diisocyanate, and the content ratio of the cyclic compound is one molecule of the polythiol.
  • a cyclic compound having a ring structure containing two or more thiourethane bonds derived from xylylene diisocyanate and the content ratio of the cyclic compound is one molecule of the polythiol.
  • xylylene diisocyanate and polythiol having two or more mercapto groups are reacted in the presence of a zinc-containing catalyst so that the equivalent ratio of the isocyanate group to the mercapto group is 2 or more and 12 or less.
  • a zinc-containing catalyst so that the equivalent ratio of the isocyanate group to the mercapto group is 2 or more and 12 or less.
  • the present invention [4] includes a two-component resin raw material comprising an agent A containing the polyisocyanate composition according to the above [1] or [2] and an agent B containing an active hydrogen group-containing component.
  • the present invention [5] includes a coating material made of the two-component resin raw material according to the above [4].
  • the present invention [6] includes an adhesive made of the two-component resin raw material according to the above [4].
  • the present invention [7] includes a resin containing a reaction product of the polyisocyanate composition according to the above [1] or [2] and an active hydrogen group-containing component.
  • the polyisocyanate composition of the present invention contains a polythiol 1 molecule-xylylene diisocyanate n molecule and a polythiol polymolecule-xylylene diisocyanate polymolecule, and is a polythiol polymolecule with respect to a polythiol 1 molecule-xylylene diisocyanate n molecule.
  • the mass ratio of the xylylene diisocyanate polymolecule is within the above range.
  • the two-component resin raw material of the present invention contains the above-mentioned polyisocyanate composition, it is possible to improve the refractive index of the resin while imparting excellent adhesion to the resin produced from the two-component resin raw material. can.
  • the coating material of the present invention contains the above-mentioned two-component resin raw material, it is possible to improve the refractive index of the cured film while imparting excellent adhesion to the cured film formed from the coating material.
  • the adhesive of the present invention contains the above-mentioned two-component resin raw material, it is possible to improve the refractive index of the cured product of the adhesive while imparting excellent adhesion to the cured product of the adhesive.
  • the resin of the present invention contains the reaction product of the above-mentioned polyisocyanate composition and the active hydrogen group-containing component, it is possible to improve the refractive index while improving the adhesion.
  • the method for producing a polyisocyanate composition of the present invention can smoothly produce the above-mentioned polyisocyanate composition.
  • FIG. 1 is a gel permeation chromatogram of the polyisocyanate composition of Example 1.
  • FIG. 2 is a gel permeation chromatogram of the polyisocyanate composition of Example 5.
  • the polyisocyanate composition of the present invention contains at least an isocyanate derivative.
  • the isocyanate derivative is a reaction product of xylylene diisocyanate (hereinafter referred to as XDI) and polythiol, and the molecular end is an isocyanate group.
  • XDI contains 1,2-XDI (o-XDI), 1,3-XDI (m-XDI) and 1,4-XDI (p-XDI) as structural isomers. These structural isomers of XDI may be used alone or in combination of two or more.
  • the XDI preferably comprises 1,3-XDI and / or 1,4-XDI, more preferably comprises 1,3-XDI, and even more preferably 1,3-XDI.
  • Polythiol has 2 or more, for example, 8 or less, preferably 6 or less, more preferably 4 or less mercapto groups (thiol groups).
  • polythiol examples include a bifunctional thiol having two mercapto groups, a trifunctional thiol having three mercapto groups, a tetrafunctional thiol having four mercapto groups, a pentafunctional thiol having five mercapto groups, and six mercapto groups.
  • bifunctional thiol examples include an aliphatic bifunctional thiol, an aromatic bifunctional thiol, a heterocyclic-containing bifunctional thiol, and a bifunctional thiol containing a sulfur atom in addition to the mercapto group in one molecule.
  • aliphatic bifunctional thiol for example, methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4 -Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3- Dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, 1,2-dimercaptopropylmethyl ether, 2,3 -Dimercaptopropylmethyl ether, bis (2-mercapto
  • aromatic bifunctional thiols for example, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis ( Mercaptomethyl) Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1 , 2-bis (mercaptomethyleneoxy) benzene, 1,3-bis (mercaptomethyleneoxy) benzene, 1,4-bis (mercaptomethyleneoxy) benzene, 1,2-bis (mercaptoethyleneoxy) benzene, 1,3 -Bis (mercaptoethyleneoxy) benzene, 1,4-bis (mercaptoethyleneoxy) benzene, 2,5-toluenedithio
  • heterocyclic-containing bifunctional thiol for example, 2-methylamino-4,6-dithiol-sim-triazine, 2-ethylamino-4,6-dithiol-sim-triazine, 2-amino-4,6-dithiol- sym-triazine, 2-morpholino-4,6-dithiol-sim-triazine, 2-cyclohexylamino-4,6-dithiol-sim-triazine, 2-methoxy-4,6-dithiol-sim-triazine, 2-phenoxy Included are -4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sim-triazine, and 2-thiobutyloxy-4,6-dithiol-sym-triazine.
  • Bifunctional thiols containing sulfur atoms in addition to the mercapto group include, for example, bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, and bis (mercaptopropyl) sulfide.
  • trifunctional thiol examples include an aliphatic trifunctional thiol, an aromatic trifunctional thiol, and a trifunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.
  • Examples of the aliphatic trifunctional thiol include 1,2,3-propanetrithiol, 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), thioapple acid bis (2-mercaptoethyl ester), and 2,3-.
  • aromatic trifunctional thiols for example, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) Benzene, 1,2,4-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) benzene, 1,2,4-tris (mercapto) Ethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 1,2,3-tris (mercaptomethyleneoxy) benzene, 1,2,4-tris (mercaptomethyleneoxy) benzene, 1,3,5 -Tris (mercaptoethyleneoxy) benzene, 1,2,3-tris (mercaptoethyleneoxy) benzene, 1,2,4-tris (mercaptoethyleneoxy) benzene, and
  • trifunctional thiols containing a sulfur atom in addition to the mercapto group examples include 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3.
  • tetrafunctional thiol examples include an aliphatic tetrafunctional thiol, an aromatic tetrafunctional thiol, and a tetrafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.
  • aliphatic tetrafunctional thiols for example, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), and Tetrakis (mercaptomethyl) methane can be mentioned.
  • aromatic tetrafunctional thiols for example, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3 , 4-Tetrax (mercaptomethyl) benzene, 1,2,3,5-tetrakis (mercaptomethyl) benzene, 1,2,4,5-tetrakis (mercaptomethyl) benzene, 1,2,3,4-tetrakis ( Mercaptoethyl) Benzene, 1,2,3,5-tetrakis (mercaptoethyl) benzene, 1,2,4,5-tetrakis (mercaptoethyl) benzene, 1,2,3,4-tetrakis (mercaptomethyleneoxy) benzene , 1,2,3,5-tetrakis (mercaptoethyleneoxy) benzene, 1,2,4,5-tetrakis (mercaptomethyleneoxy)
  • a tetrafunctional thiol containing a sulfur atom in addition to the mercapto group for example, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane, 4,7-dimercaptomethyl-1, 11-Dimercapto-3,6,9-Trithiandecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiandecane, Tetrakiss (mercaptomethylthiomethyl) methane, Tetrakiss (2- Mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bisthiodipropionic acid (2,3-dimercaptopropyl ester), dithiodiglycolic acid Bis (2,3-dimercaptopropyl ester), thio
  • pentafunctional thiol examples include a pentafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.
  • a pentafunctional thiol containing a sulfur atom in addition to the mercapto group for example, 1- [4- (6-mercaptomethylthio) -1,3-dithianylthio] -3- [2,2-bis (mercaptomethylthio) ethyl]- 7,9-bis (mercaptomethylthio) -2,4,6,10-tetrathiaundecane and bis [4,4-bis (mercaptomethylthio) -1,3-dithiabutyl]-(mercaptomethylthio) methane are mentioned. Be done.
  • hexafunctional thiol examples include a hexafunctional thiol containing a sulfur atom in addition to the mercapto group in one molecule.
  • a hexafunctional thiol containing a sulfur atom in addition to the mercapto group for example, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3,3-bis (mercaptomethylthio) -1-thiapropyl) 3,7 -Dithiolane, Tris (2,2-bis (mercaptomethylthio) ethyl) methane, Tris (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11-tetrakis (mercaptomethylthio)- 1,13-Dimercapto-2,6,8,12-tetrathiatridecane, 3,4,8,9-tetrakis (mercaptomethylthio) -1,11-dimercapto-2,5,7,10-tetrathiaundecan , 4,6-bis [3,5-bis (mercaptomethylthio) -7-mercapto-2,6-d
  • octafunctional thiol examples include an octafunctional thiol containing a sulfur atom in addition to a mercapto group in one molecule.
  • octafunctional thiols containing sulfur atoms in addition to the mercapto group for example, tetrakis (4,4-bis (mercaptomethylthio) -2-thiabutyl) methane, 3,5,9,11,15,17-hexakis (mercaptomethylthio) )-1,19-Dimercapto-2,6,8,12,14,18-Hexadecane decane, 9- (2,2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis ( Mercaptomethylthio) -1,17-dimercapto-2,6,8,10,12,16-hexadecaneheptadecane, tetrakis (2,2-bis (mercaptomethylthio) ethyl) methane, 3,4,8,9, 13,14-Hexadecane (Mercaptomethylthio) -1,16-Dimercapto-2,5,7,
  • the above-mentioned halogen substituted product of polythiol can also be used.
  • the halogen-substituted product of the above-mentioned polythiol include the chlorine-substituted product of the above-mentioned polythiol and the bromine-substituted product of the above-mentioned polythiol.
  • polythiol is not limited to the above-mentioned exemplified compounds.
  • Polythiol can be used alone or in combination of two or more.
  • the polythiol preferably contains a trifunctional thiol and / or a tetrafunctional thiol, and more preferably contains a trifunctional thiol or a tetrafunctional thiol.
  • the trifunctional thiol preferably includes a trifunctional thiol containing a sulfur atom in addition to the mercapto group, and more preferably 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane (hereinafter referred to as GST). .) Can be mentioned.
  • the tetrafunctional thiol preferably includes a tetrafunctional thiol containing a sulfur atom in addition to the mercapto group, and more preferably 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithia.
  • Undecane hereinafter referred to as FSH
  • FSH Undecane
  • the polythiol contains a bifunctional thiol
  • the bifunctional thiol is preferably used in combination with a trifunctional thiol and / or a tetrafunctional thiol.
  • bifunctional thiol examples include bifunctional thiols containing a sulfur atom in addition to the mercapto group, and more preferably bis (mercaptoethyl) sulfide.
  • the content ratio of the bifunctional thiol is, for example, 1 part by mass with respect to 100 parts by mass of the total of the trifunctional thiol and the tetrafunctional thiol.
  • the above is preferably 5 parts by mass or more, for example, 30 parts by mass or less, preferably 20 parts by mass or less.
  • polythiol is particularly preferably composed of a trifunctional thiol or a tetrafunctional thiol, and particularly preferably composed of a trifunctional thiol.
  • Polythiol can also be used in combination with at least one polyol.
  • XDI and the above-mentioned polythiol have an equivalent ratio of isocyanate groups to mercapto groups ([NCO] / [SH]) in the range described later.
  • the thiourethaneization reaction is carried out so as to be.
  • the equivalent ratio of isocyanate groups to mercapto groups ([NCO] / [SH]) is 2.0 or more, preferably 2.2 or more and 12.0 or less, preferably 8.0 or less, more preferably 6. It is less than or equal to 0.0.
  • the equivalent ratio of isocyanate groups to mercapto groups is at least the above lower limit, gelation of the polyisocyanate composition can be suppressed.
  • the equivalent ratio of the isocyanate group to the mercapto group is not more than the above upper limit, the refractive index of the polyisocyanate composition can be improved, and by extension, the refractive index of the resin produced from the polyisocyanate composition can be surely improved. Can be planned.
  • Examples of the zinc-containing catalyst include the zinc compounds described in International Publication No. 2010/001550, preferably zinc dithiocarbamate and zinc fatty acid.
  • Examples of zinc dithiocarbamate include bis (N, N-dimethyldithiocarbamate) zinc, bis (N, N-diethyldithiocarbamate) zinc, bis (N, N-dipropyldithiocarbamate) zinc, and bis (N, N).
  • -Dibutyldithiocarbamic acid) Zinc, bis (N-ethyl-N-phenyldithiocarbamic acid) zinc, and bis (N, N-dibenzyldithiocarbamic acid) zinc can be mentioned.
  • Examples of the fatty acid zinc include zinc 2-ethylhexanate, zinc stearate, zinc tartrate, and zinc oxalate.
  • the zinc-containing catalyst can be used alone or in combination of two or more.
  • the zinc-containing catalyst preferably contains zinc dithiocarbamate and / or zinc fatty acid, more preferably zinc dithiocarbamate, and even more preferably zinc bis (N, N-dibutyldithiocarbamate).
  • the zinc-containing catalyst is preferably composed of zinc dithiocarbamate and / or the fatty acid zinc.
  • the addition ratio of the zinc-containing catalyst is, for example, 0.0001 parts by mass or more, preferably 0.0005 parts by mass or more, and for example, 0.01 parts by mass or less, preferably 0. It is 005 parts by mass or less.
  • the zinc-containing catalyst is dissolved in an organic solvent (described later) in advance to prepare a zinc-containing catalyst solution, and the zinc-containing catalyst solution is added to XDI. Then, the above-mentioned polythiol is added to the zinc-containing catalyst solution and the mixed solution of XDI so that the equivalent ratio of the isocyanate group to the mercapto group ([NCO] / [SH]) is in the above range.
  • the thiourethanization reaction is carried out under an atmosphere of an inert gas such as nitrogen gas and normal pressure (atmospheric pressure).
  • the reaction temperature is, for example, 50 ° C. or higher, preferably 70 ° C. or higher, and for example, 100 ° C. or lower, preferably 90 ° C. or lower.
  • the reaction time is, for example, 2 hours or more, preferably 4 hours or more, and for example, 72 hours or less, preferably 24 hours or less.
  • the thiourethanization reaction is terminated when the desired isocyanate group content (theoretical amount of the unreacted isocyanate group concentration calculated from the charged amount) is reached in the reaction system.
  • isocyanate group of XDI and the mercapto group of polythiol undergo a thiourethanization reaction.
  • isocyanate derivatives (mononuclear and polynuclear bodies described later) are produced, and cyclic compounds described later are by-produced.
  • the isocyanate derivative contains a polythiol single molecule-xylylene diisocyanate n molecule (hereinafter referred to as a mononuclear body) and a polythiol polymolecule-xylylene diisocyanate polymolecule (hereinafter referred to as a polynuclear body).
  • the mononuclear body is a reaction product of one polythiol molecule having n (n represents an integer of 2 or more) mercapto groups and an XDIn molecule.
  • n represents an integer of 2 or more, and for example, 8 or less, preferably 6 or less, more preferably 4 or less (the same applies hereinafter).
  • the mononuclear structure corresponds to the type of polythiol used in the production of the polyisocyanate composition.
  • mononuclear bodies polythiol 1 molecule-xylylene diisocyanate n molecule
  • bifunctional thiol 1 molecule-XDI dichotome trifunctional thiol 1 molecule-XDI trisection
  • the mononuclear body can be contained alone or in two or more types depending on the type of polythiol.
  • the mononuclear body preferably comprises a trifunctional thiol 1 molecule-XDI trisection and / or a tetrafunctional thiol 1 molecule-XDI quaternary, and more preferably a trifunctional thiol 1 molecule-XDI trisection or a tetrafunctional thiol 1. Includes molecule-XDI quartet.
  • the mononuclear body when the mononuclear body contains a bifunctional thiol 1 molecule-XDI dichotome, the mononuclear body is preferably a bifunctional thiol 1 molecule-XDI dichotome and a trifunctional thiol 1 molecule-XDI trisection and / or. Contains 1 molecule of tetrafunctional thiol-XDI quaternate.
  • the mononuclear body is particularly preferably composed of one trifunctional thiol molecule-XDI trisection or one tetrafunctional thiol molecule-XDI quaternary, and particularly preferably composed of one trifunctional thiol molecule-XDI trisection.
  • a polynuclear cell is a reaction product of two or more polythiol molecules having n (n indicates an integer of two or more) mercapto groups and three or more XDI molecules.
  • the structure of the polynuclear body corresponds to the type of polythiol used in the production of the polyisocyanate composition as well as the mononuclear body.
  • the molecular weight of a polynuclear body is greater than that of a mononuclear body produced from the same polythiol.
  • Polynuclear cells are distinguished based on the number of polythiol-derived units (hereinafter referred to as thiol-derived units).
  • examples of the polynuclear body include a dinuclear body, a trinuclear body, a tetranuclear body, a pentanuclear body, and a polynuclear body having six or more nuclei (hereinafter, referred to as m nuclei (m ⁇ 6)).
  • the dinuclear body is a reaction product of two polythiol molecules having n mercapto groups and an XDI (2n-1) molecule, and has two thiol-derived units.
  • Examples of the binuclear body include a bifunctional thiol 2 molecule-XDI trisection, a trifunctional thiol 2 molecule-XDI quintuple, and a tetrafunctional thiol 2 molecule-XDI 7 fraction.
  • the trinuclear body is a reaction product of three polythiol molecules having n mercapto groups and an XDI (3n-2) molecule, and has three thiol-derived units.
  • Examples of the trinuclear body include a bifunctional thiol 3 molecule-XDI quaternary body, a trifunctional thiol 3 molecule-XDI 7 shard, and a tetrafunctional thiol 3 molecule-XDI 10 shard.
  • the tetranuclear body is a reaction product of four polythiol molecules having n mercapto groups and an XDI (4n-3) molecule, and has four thiol-derived units.
  • Examples of the tetranuclear body include a bifunctional thiol 4 molecule-XDI 5 molecule, a trifunctional thiol 4 molecule-XDI 9 fraction, and a tetrafunctional thiol 4 molecule-XDI 13 fraction.
  • the pentanucleus is a reaction product of 5 polythiol molecules having n mercapto groups and XDI (5n-4) molecules, and has 5 thiol-derived units.
  • Examples of the pentanuclear body include a bifunctional thiol 5 molecule-XDI hexadecimal body, a trifunctional thiol 5 molecule-XDI 11 dichotome, and a tetrafunctional thiol 5 molecule-XDI 16 dichotome.
  • the m-nucleus includes polynuclear bodies having six or more nuclei.
  • the hexanucleus is a reaction product of 6 polythiol molecules with n mercapto groups and XDI (6n-5) molecules, and has 6 thiol-derived units.
  • Examples of the hexanuclear body include a bifunctional thiol 6 molecule-XDI 7 molecule, a trifunctional thiol 6 molecule-XDI 13 molecule, and a tetrafunctional thiol 6 molecule-XDI 19 fraction.
  • the polynuclear cell can be contained alone or in combination of two or more, depending on the type of polythiol.
  • Polynuclear bodies preferably include dinuclear bodies and trinuclear bodies.
  • the content ratio of the polyisocyanate derivative in the polyisocyanate composition is, for example, 30% by mass or more, preferably 40% by mass or more, and for example, 99% by mass or less, preferably 95% by mass or less.
  • the content ratio of the polyisocyanate derivative can be calculated according to the method described in Examples described later.
  • the content ratio of the mononuclear body in the polyisocyanate composition is, for example, 5% by mass or more, preferably 10% by mass or more, and for example, 80% by mass or less, preferably 60% by mass or less.
  • the content ratio of the mononuclear body can be calculated according to the method described in Examples described later.
  • the content ratio of the mononuclear body is at least the above lower limit, a polyisocyanate composition having excellent solubility in a solvent and compatibility with an active hydrogen group-containing component (described later) can be obtained.
  • the content ratio of the mononuclear body is not more than the above upper limit, the adhesiveness can be surely imparted to the resin produced from the polyisocyanate composition.
  • the content of the polynuclear body in the polyisocyanate composition is, for example, 3% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and for example, 80% by mass or less, preferably 70% by mass. % Or less.
  • the content ratio of the polynuclear body can be measured according to the method described in Examples described later.
  • the mass ratio of the polynuclear body (polythiol polymolecule-xylylene diisocyanate polymolecule) to the mononuclear compound (polythiol 1 molecule-xylylene diisocyanate n molecule) is 0.50 or more, preferably 0.70 or more. It is more preferably 1.00 or more, still more preferably 1.10 or more, and 5.2 or less, preferably 3.0 or less.
  • the mass ratio of the polynuclear body to the mononuclear body can be calculated from the content ratio of the mononuclear body and the polynuclear body calculated according to the method described in Examples described later.
  • the mass ratio of the polynuclear body is within the above range, the adhesiveness can be imparted to the resin, the refractive index of the polyisocyanate composition can be improved, and the refractive index of the resin can be improved.
  • the mass ratio of the binuclear body to the mononuclear body is, for example, 0.3 or more, preferably 0.35 or more, more preferably 0.40 or more, and for example, 1.5 or less, preferably 1.5 or less. It is 1.0 or less, more preferably 0.70 or less.
  • the mass ratio of the binuclear body to the mononuclear body can be calculated from the content ratio of the mononuclear body and the binuclear body calculated according to the method described in Examples described later.
  • the mass ratio of the binuclear body is not less than the above lower limit, the adhesiveness can be surely imparted to the resin and the refractive index of the polyisocyanate composition can be surely improved.
  • the mass ratio of the trinuclear body to the mononuclear body is, for example, 0.05 or more, preferably 0.10 or more, more preferably 0.20 or more, and for example, 1.0 or less, preferably 0. It is 70 or less.
  • the mass ratio of the trinuclear body to the mononuclear body can be calculated from the content ratio of the mononuclear body and the trinuclear body calculated according to the method described in Examples described later.
  • the mass ratio of the trinuclear body is at least the above lower limit, the refractive index of the polyisocyanate composition can be improved more reliably.
  • the content ratio of the trinuclear body is not more than the above upper limit, a polyisocyanate composition having excellent solubility in a solvent and compatibility with an active hydrogen group-containing component (described later) can be obtained.
  • the cyclic compound is a thiourethane compound produced as a by-product in the production of the above-mentioned polyisocyanate composition.
  • the cyclic compound has a ring structure containing two or more thiourethane bonds derived from XDI.
  • the structure of the cyclic compound corresponds to the type of polythiol used in the production of the polyisocyanate composition.
  • Examples of the cyclic compound include a first cyclic compound corresponding to a bifunctional thiol, a second cyclic compound corresponding to a trifunctional thiol, and a third cyclic compound corresponding to a tetrafunctional thiol.
  • Examples of the first cyclic compound include a thiourethane bond-containing cyclic compound represented by the following formula (1).
  • the thiourethane bond-containing cyclic compound represented by the following formula (1) corresponds to bis (mercaptoethyl) sulfide.
  • Examples of the second cyclic compound include thiourethane bond-containing cyclic compounds represented by the following formulas (2) to (4).
  • the thiourethane bond-containing cyclic compound represented by the following formula (2) corresponds to 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (3) corresponds to 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (4) corresponds to 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane.
  • Examples of the third cyclic compound include thiourethane bond-containing cyclic compounds represented by the following formulas (5) to (9).
  • the thiourethane bond-containing cyclic compound represented by the following formula (5) corresponds to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (6) corresponds to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (7) corresponds to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (8) corresponds to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane.
  • the thiourethane bond-containing cyclic compound represented by the following formula (9) corresponds to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trichiaundecane.
  • R represents a hydrogen atom or an atomic group represented by the following formula (10).
  • the cyclic compound can be contained alone or in combination of two or more, corresponding to polythiol.
  • the content of the cyclic compound in the polyisocyanate composition is, for example, 0% by mass or more, preferably 1% by mass or more, or, for example, 15% by mass or less, preferably 10% by mass or less, more preferably 7% by mass. % Or less, more preferably 5% by mass or less.
  • the content ratio of the cyclic compound can be measured according to the method described in Examples described later.
  • the content ratio of the cyclic compound is not more than the above upper limit, the curability with the active hydrogen group-containing component (described later) is excellent, and the adhesion of the resin can be surely improved.
  • the mass ratio of the cyclic compound to the mononuclear body is, for example, 0.05 or more, preferably 0.10 or more, or, for example, 0.40 or less, preferably 0.35 or less.
  • the mass ratio of the cyclic compound to the mononuclear compound can be calculated from the content ratio of the mononuclear compound and the cyclic compound calculated according to the method described in Examples described later.
  • polyisocyanate composition may contain unreacted XDI as a residual monomer remaining in the production of the above-mentioned polyisocyanate composition.
  • the content of XDI in the polyisocyanate composition is, for example, 0% by mass or more, preferably 0.1% by mass or more, or, for example, 85% by mass or less, preferably 80% by mass or less, more preferably 60. It is less than mass%.
  • the content ratio of XDI can be calculated according to the method described in Examples described later.
  • Examples of the method for removing unreacted XDI include a distillation method such as thin film distillation and an extraction purification method such as liquid-liquid extraction.
  • the polyisocyanate composition in which XDI remains is distilled by a thin film distiller.
  • an extraction solvent for example, an organic solvent described later
  • XDI an organic solvent described later
  • a liquid-liquid extraction method is preferable as a method for removing unreacted XDI.
  • a part of the extraction solvent may be used as it is for diluting the polyisocyanate composition.
  • the isocyanate group concentration of such a polyisocyanate composition is, for example, 5.0% by mass or more, preferably 10.0% by mass or more, and for example, 50.0% by mass or less, preferably 30.0% by mass. % Or less.
  • the isocyanate group concentration can be measured by the n-dibutylamine method based on JIS K-1556 using a potentiometric titrator (the same applies hereinafter).
  • the average number of functional groups in the polyisocyanate composition is, for example, 2.0 or more, preferably 2.5 or more, and for example, 30 or less, preferably 20 or less.
  • the average number of functional groups can be calculated from the amount of raw materials charged in the production of the polyisocyanate composition.
  • the refractive index of the polyisocyanate composition is, for example, 1.50 or more, preferably 1.57 or more, more preferably 1.59 or more, and for example, 1.80 or less, preferably 1.70. It is as follows.
  • the refractive index of the polyisocyanate composition can be measured according to the method described in Examples described later.
  • the refractive index of the resin produced from the polyisocyanate composition is proportional to the refractive index of the polyisocyanate composition. Therefore, if the refractive index of the polyisocyanate composition is at least the above lower limit, an excellent refractive index can be imparted to the resin produced from the polyisocyanate composition.
  • polyisocyanate composition may be diluted with an organic solvent if necessary.
  • the solid content concentration in the polyisocyanate composition before dilution is 100% by mass.
  • organic solvent examples include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, ethers, esters, glycol ether esters, halogenated aliphatic hydrocarbons, and nitrogen-containing compounds.
  • aliphatic hydrocarbons examples include n-hexane, n-heptane, and octane.
  • aromatic hydrocarbons examples include benzene, toluene, and xylene.
  • ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • ethers examples include dityl ether, tetrahydrofuran, dioxane, and propylene glycol dimethyl ether.
  • esters examples include ethyl acetate and butyl acetate.
  • glycol ether esters examples include methyl cellosolve acetate and ethyl cellosolve acetate.
  • halogenated aliphatic hydrocarbons examples include dichloromethane, dichloroethane, chloroform, and carbon tetrachloride.
  • nitrogen-containing compounds examples include N-methylpyrrolidone, dimethylimidazolidinone, and dimethylformaldehyde.
  • the organic solvent can be used alone or in combination of two or more.
  • esters and ketones are preferable, and ethyl acetate and methyl ethyl ketone are more preferable.
  • the solid concentration of the polyisocyanate composition in the diluted solution is, for example, 30% by mass or more, preferably 50% by mass or more, and for example, 90% by mass or less, preferably 80% by mass or less.
  • the viscosity of the polyisocyanate composition at 25 ° C. is, for example, 30 mPa ⁇ s or more, and for example, 10,000 mPa ⁇ s or less.
  • the viscosity of the polyisocyanate composition at 25 ° C. is equal to or higher than the above lower limit, the scattering of the liquid can be suppressed and the workability can be improved. Further, when the viscosity of the polyisocyanate composition at 25 ° C. is not more than the above upper limit, fluidity can be ensured and miscibility with the main agent can be sufficiently performed.
  • the above-mentioned polyisocyanate composition contains a polythiol 1 molecule-xylylene diisocyanate n molecule and a polythiol polymolecule-xylylene diisocyanate polymolecule, and has a polythiol polymorphism with respect to a polythiol 1 molecule-xylylene diisocyanate n molecule.
  • the mass ratio of the molecule-xylylene diisocyanate polymolecule is within the above range.
  • the content ratio of the cyclic compound is not more than the above upper limit with respect to 100 parts by mass of the total of the mononuclear body and the polynuclear body. Therefore, it is possible to surely improve the adhesion of the resin.
  • the above-mentioned polyisocyanate composition can be smoothly produced.
  • the above-mentioned polyisocyanate composition can be used as a raw material for resin in various industrial products. Specifically, the polyisocyanate composition can be suitably used as an agent A (curing agent) as a two-component resin raw material.
  • agent A curing agent
  • the two-component resin raw material includes, for example, coating materials (for example, plastic paints, automobile paints, and film coating agents), adhesives, two-component curable sealing raw materials, and potting agents.
  • coating materials for example, plastic paints, automobile paints, and film coating agents
  • adhesives two-component curable sealing raw materials
  • potting agents preferably, a coating material and an adhesive are mentioned, and more preferably, an optical coating material and an optical adhesive which require an excellent refractive index are mentioned.
  • the two-component resin raw material separately comprises an agent A (curing agent) containing a polyisocyanate composition and an agent B (main agent) containing an active hydrogen group-containing component, and the agent A and the agent B are immediately before use. It is to be mixed.
  • the two-component resin raw material is a coating material or an adhesive
  • each of the coating material and the adhesive comprises a two-component resin raw material, specifically, an agent A containing a polyisocyanate composition.
  • a B agent containing an active hydrogen group-containing component is an agent A containing a polyisocyanate composition.
  • Agent A contains the above-mentioned polyisocyanate composition as an essential component.
  • agent A can contain other polyisocyanates (polyisocyanates excluding the above-mentioned polyisocyanate composition), if necessary.
  • polyisocyanates examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified products modified from these polyisocyanates.
  • aliphatic polyisocyanate examples include 1,5-pentamethylene diisocyanate (PDI) and 1,6-hexamethylene diisocyanate (HDI).
  • PDI 1,5-pentamethylene diisocyanate
  • HDI 1,6-hexamethylene diisocyanate
  • alicyclic polyisocyanates for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (IPDI), 1,3- and / or 1,4-bis (isocyanatomethyl) cyclohexane (H 6 XDI). ) (Trans-form, Cis-form, or a mixture thereof), and methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, Trans, Transs thereof). -Body, Trans, Cis-body, Cis, Cis-body, or a mixture thereof)) (H 12 MDI).
  • aromatic polyisocyanate examples include diphenylmethane diisocyanate (MDI) and tolylene diisocyanate (TDI).
  • modified product modified from polyisocyanate examples include a multimer, an isocyanurate modified product, a biuret modified product, an allophanate modified product, and a triol adduct.
  • the content ratio of the other polyisocyanate is, for example, 0 parts by mass or more, and for example, 40 parts by mass or less, preferably 20 parts by mass or less, based on 100 parts by mass of the polyisocyanate composition.
  • Agent A particularly preferably does not contain other polyisocyanates, but contains only the above-mentioned polyisocyanate composition as an isocyanate component.
  • Agent B contains an active hydrogen group-containing component as an essential component.
  • the active hydrogen group-containing component examples include a polyol component (a component mainly containing a polyol having two or more hydroxyl groups), a polythiol component (a component mainly containing polythiol having two or more mercapto groups), and a polyamine component (amino).
  • a polyol component a component mainly containing a polyol having two or more hydroxyl groups
  • a polythiol component a component mainly containing polythiol having two or more mercapto groups
  • a polyamine component amino
  • the active hydrogen group-containing component can be used alone or in combination of two or more.
  • a polyol component and a polythiol component are preferable.
  • polyol component examples include low molecular weight polyols and high molecular weight polyols.
  • the low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more and less than 400, preferably 300 or less.
  • Examples of the low molecular weight polyol include dihydric alcohols, trihydric alcohols, tetrahydric alcohols, pentahydric alcohols, hexahydric alcohols, heptavalent alcohols, and octahydric alcohols.
  • dihydric alcohols and trihydric alcohols are preferable.
  • dihydric alcohol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol and neopentyl.
  • Isosorbide 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl- Examples thereof include 1-octene-3,8-diol and bisphenol A.
  • trihydric alcohol examples include glycerin and trimethylolpropane.
  • examples of the low molecular weight polyol include polyalkylene oxides having a number average molecular weight of 60 or more and less than 400.
  • Polyalkylene oxides include random and / or block copolymers of two or more alkylene oxides.
  • the polyalkylene oxide is obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, etc.) using the above alcohol as an initiator.
  • the high molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, preferably 500 or more, and for example, 10,000 or less, preferably 5000 or less.
  • high molecular weight polyols examples include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, and vinyl monomer-modified polyols.
  • polystyrene resin a high molecular weight polyol is preferable, and a polyester polyol is more preferable.
  • polyester polyol examples include an adipate-based polyester polyol, a phthalic acid-based polyester polyol, and a lactone-based polyester polyol.
  • Such polyol components can be used alone or in combination of two or more.
  • the hydroxyl value of the polyol component is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, 300 mgKOH / g or less, preferably 250 mgKOH / g or less.
  • the hydroxyl value can be measured by the acetylation method or the phthalation method based on the A method or the B method of JISK1557-1.
  • the number average molecular weight of the polyol component is, for example, 2000 or more, preferably 5000 or more, and for example, 100,000 or less, preferably 50,000 or less in terms of standard polystyrene measured by gel permeation chromatography (GPC). ..
  • polythiol component examples include the above-mentioned polythiol, preferably the above-mentioned tetrafunctional thiol, and more preferably the above-mentioned tetrafunctional thiol containing an ion atom in addition to the above-mentioned mercapto group.
  • the polythiol component can be used alone or in combination of two or more.
  • the resin contains a reaction product of the above-mentioned polyisocyanate composition and the above-mentioned active hydrogen group-containing component.
  • the resin include polyurethane resin, polythiourethane resin, and polyurea resin.
  • the equivalent ratio of the isocyanate group in the agent A to the active hydrogen group in the agent B is, for example, 0.5 or more, preferably 0. It is 8.8 or more, for example, 1.5 or less, preferably 1.2 or less.
  • the two-component resin raw material may contain known additives (for example, color pigments, dyes, ultraviolet absorbers, curing accelerators, light stabilizers, matting agents, phosphorus oxygen acids or derivatives thereof, and the like, if necessary. , Silane coupling agent) can be contained in an appropriate ratio.
  • known additives for example, color pigments, dyes, ultraviolet absorbers, curing accelerators, light stabilizers, matting agents, phosphorus oxygen acids or derivatives thereof, and the like, if necessary.
  • Silane coupling agent can be contained in an appropriate ratio.
  • the additive may be added to the agent A and / or the agent B in advance, or the agent A and the agent B may be mixed and then added to the mixed solution.
  • the two-component resin raw material is a coating material
  • a known coating method for example, spray coating, brush coating, and coating
  • spray coating, brush coating, and coating can be applied to the object to be coated with the above-mentioned mixture of agents A and B. , Roll coater to paint and cure.
  • a cured film containing the resin is formed on the object to be coated.
  • Such a coating material can impart excellent adhesion to the cured film and can improve the refractive index of the cured film.
  • Examples of the object to be coated include inorganic substances (for example, concrete, natural stone, glass, and metal) and organic substances (for example, plastic, rubber, adhesive, and wood), and organic substances are preferable. And more preferably plastic.
  • plastic examples include polyolefins (eg, polyethylene and polypropylene), polyesters (eg, polyethylene terephthalates), polyamides, polycarbonates, and polystyrenes, preferably polyolefins and polyesters.
  • the two-component resin raw material is an adhesive
  • a known coating method for example, a dry laminating method and a wet laminating method
  • a dry laminating method and a wet laminating method is applied to a predetermined position for adhering an adherend by applying the above-mentioned mixture of agents A and B to an adhesive.
  • the adherend as an object is brought into contact with the adhesive to cure the adhesive.
  • the adhesive cures and adheres the adherend in place.
  • Such an adhesive can impart excellent adhesion to the cured product of the adhesive, and can improve the refractive index of the cured product of the adhesive.
  • Examples of the adherend include various building materials and various laminated films, specifically, packaging materials (for example, plastic films, metal foils, and metal vapor deposition films), and civil engineering materials (for example, FRP and steel materials).
  • packaging materials for example, plastic films, metal foils, and metal vapor deposition films
  • civil engineering materials for example, FRP and steel materials.
  • a packaging material is preferable, and a plastic film is more preferable.
  • plastic film examples include a plastic film formed from the above-mentioned plastic, preferably a polyolefin film and a polyester film.
  • the compounding ratio (content ratio), the physical property value, and the specific numerical values of the parameters used in the following description are the compounding ratios (containing) corresponding to those described in the above-mentioned “Mode for carrying out the invention”.
  • Substitute for the upper limit (value defined as “less than or equal to” or “less than”) or the lower limit value (value defined as “greater than or equal to” or “excess”) of the corresponding description of the parameter), physical property value, and parameter. can do.
  • “part” and “%” are based on mass unless otherwise specified.
  • the sample was then analyzed by gel permeation chromatography (GPC) under the following conditions.
  • Equipment Alliance (manufactured by WATERS), Column; 3 Plgel 5 ⁇ M Mixed-C (measured molecular weight range; 100-1000000, manufactured by Polymerlab) connected in series, Detector; Differential Refractometer Detector, Free liquid; tetrahydrofuran, Flow rate; 1.0 mL / min, Column temperature; 40 ° C, Detector temperature; 40 ° C, Injection volume; 10 ⁇ L.
  • GPC gel permeation chromatography
  • the content ratios of mononuclear bodies, polynuclear bodies, cyclic compounds and residual monomers in the polyisocyanate composition were calculated from the area values of the gas chromatogram (GPC chart). ..
  • the ratio (area%) of the sum of the peak areas of the peaks a) to e) to the total peak area is calculated, and the polynuclear body (polythiol polymolecule-xylylene diisocyanate polymolecule) in the polyisocyanate composition is calculated. ) was used as the content ratio.
  • the ratio (area%) of the total peak area of the peak f) to the total peak area is calculated to be the content ratio of the mononuclear body (polythiol 1 molecule-xylylene diisocyanate n molecule) in the polyisocyanate composition. did.
  • the ratio (area%) of the total peak area of the peak g) to the total peak area was calculated and used as the content ratio of the cyclic compound in the polyisocyanate composition.
  • the ratio (area%) of the total peak area of peak h) to the total peak area was calculated and used as the content ratio of the residual monomer (XDI) in the polyisocyanate composition.
  • the polyisocyanate composition is based on the solid content concentration and the value of the refractive index of the diluted solution of the polyisocyanate composition and the value of the refractive index of the organic solvent. The refractive index of the object was calculated.
  • Example 1 In the presence of bis (dibutyldithiocarbamic acid) zinc (ZnBTC) as a zinc-containing catalyst, 4-mercaptomethyl-1,8-dimercapto-3,6-diaoctane (GST) and m-XDI as polythiols were added. It was reacted with thiourethaneization. The equivalent ratio of the isocyanate group of XDI to the mercapto group of GST ([NCO] / [SH]) was set to 2.2.
  • Example 1 shows the type of polythiol, the type of catalyst, the equivalent ratio of isocyanate groups to mercapto groups ([NCO] / [SH]), the solid content concentration of the polyisocyanate composition, and the GPC chart.
  • Table 1 shows the area value of each peak in the above, the mass ratio of the polynuclear body to the mononuclear body, and the refractive index of the polyisocyanate composition.
  • the GPC chart (gel permeation chromatogram) of Example 1 is shown in FIG.
  • Example 2 The polyisocyanate composition of Example 2 was obtained in the same manner as in Example 1 except that [NCO] / [SH] was changed to 3.0.
  • Example 3 The polyisocyanate composition of Example 3 was obtained in the same manner as in Example 1 except that [NCO] / [SH] was changed to 6.0.
  • Example 4 The polyisocyanate composition of Example 4 was obtained in the same manner as in Example 3 except that the zinc-containing catalyst was changed to bis (2-ethylhexanoic acid) zinc (2EHA-Zn).
  • Example 5 The residual monomer (unreacted XDI) was removed from the polyisocyanate composition obtained in the same manner as in Example 3.
  • Example 5 The GPC chart (gel permeation chromatogram) of Example 5 is shown in FIG.
  • Example 6 Polyisocyanate of Example 6 in the same manner as in Example 5, except that the polythiol was changed to 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (FSH). A diluted solution of the composition was obtained.
  • FSH 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane
  • Example 7 A diluted solution of the polyisocyanate composition of Example 7 was obtained in the same manner as in Example 5 except that the polythiol was changed to a mixture of GST and bis (mercaptoethyl) sulfide (MES). The mass ratio of GST to MES (GST: MES) was 90:10.
  • Example 8 A diluted solution of the polyisocyanate composition of Example 8 was obtained in the same manner as in Example 5 except that [NCO] / [SH] was changed to 12.0.
  • Comparative Example 1 Takenate D-110N (XDI trimethylolpropane (TMP) adduct, isocyanate group content 11.5% by mass, solid content 75% by mass, solvent: ethyl acetate, manufactured by Mitsui Chemicals, Inc.) was used as the polyisocyanate of Comparative Example 1. Prepared as a diluent for the composition.
  • the retention time of the peak corresponding to the tetranuclear body is 26.1 minutes, and the retention time of the peak corresponding to the trinuclear body is 26.5. Minutes, the retention time of the peak corresponding to the binuclear body is 27.1 minutes, the retention time of the peak corresponding to the mononuclear body is 28.0 minutes, and the retention time of the peak corresponding to the residual monomer (XDI). The retention time was 30.3 minutes.
  • Comparative Example 2 A diluted solution of the polyisocyanate composition of Comparative Example 2 was obtained in the same manner as in Example 5 except that a zinc-containing catalyst was not used.
  • Comparative Example 3 A diluted solution of the polyisocyanate composition of Comparative Example 3 was obtained in the same manner as in Example 5 except that the zinc-containing catalyst was changed to tin octylate (SnOct).
  • Comparative Example 4 The polyisocyanate composition of Comparative Example 4 was obtained in the same manner as in Example 1 except that [NCO] / [SH] was changed to 1.5. The polyisocyanate composition of Comparative Example 4 was gelled and could not be analyzed by GPC.
  • dibutyltin dichloride manufactured by Tokyo Chemical Industry Co., Ltd.
  • methyl ethyl ketone a concentration of 100 ppm with respect to the solid content
  • the mixture was added to the surface of the polyethylene terephthalate (PET) substrate to a thickness.
  • PET polyethylene terephthalate
  • the PET substrate coated with the mixed solution was heated at 60 ° C. for 2 hours and further cured at 25 ° C. for 7 days. As a result, a cured film was formed on the PET substrate.
  • the adhesion (curability) of the obtained cured film was evaluated according to the following criteria. ⁇ : No peeling of the cured film. X: At least a part of the cured film is peeled off.
  • a polyester polyol (trade name: Olestar Q202, manufactured by Mitsui Chemicals, Inc., hydroxyl value (OHV): 225 mgKOH / g) was prepared as a main agent (agent B). Further, the diluted solution of the polyisocyanate composition of Example 5 was used as a curing agent (agent A).
  • dibutyltin dichloride manufactured by Tokyo Chemical Industry Co., Ltd.
  • a curing catalyst was diluted with methyl ethyl ketone so as to have a concentration of 100 ppm with respect to the solid content, and the mixture was added to the surface of the polypropylene (PP) substrate to increase the thickness. It was applied so as to be 40 ⁇ m.
  • the PP base material coated with the mixed solution was heated at 60 ° C. for 2 hours and further cured at 25 ° C. for 7 days. As a result, a cured film was formed on the PP substrate.
  • the cured film was peeled off from the PP substrate, and the refractive index of the cured film was measured using an Abbe refractive index meter (DR-M4, manufactured by Atago, D line, 25 ° C.).
  • the refractive index of the cured film was 1.593.
  • the Tg and storage elastic modulus of the cured film were measured using a rheometer (RSA-III, manufactured by TS Instruments).
  • the Tg of the cured film was 52 ° C.
  • the storage elastic modulus of the cured film at 25 ° C. was 1347 MPa.
  • a cured film was prepared in the same manner as above except that the main agent (agent B) was changed as shown in Table 2, and the refractive index, Tg, and storage elastic modulus of the cured film at 25 ° C. were measured.
  • the main agent and the curing agent are used so that the equivalent ratio ([NCO] / [SH]) of the isocyanate group of the polyisocyanate composition to the thiol group of FSH is 1.05. Was mixed. The results are shown in Table 2.
  • the polyisocyanate composition of the present invention the method for producing a polyisocyanate composition, a two-component resin raw material, a coating material, an adhesive and a resin can be suitably used in the fields of coating materials and adhesives.

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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)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une composition de polyisocyanate qui contient un dérivé d'isocyanate. Le dérivé d'isocyanate est un produit d'une réaction entre le xylylène diisocyanate et un polythiol ayant au moins deux groupes mercapto. Une extrémité terminale moléculaire du dérivé est un groupe isocyanate. Le dérivé d'isocyanate contient : un adduit d'une molécule d'un polythiol et de n molécules de xylylène diisocyanate ; et un adduit de plusieurs molécules d'un polythiol et de plusieurs molécules de xylylène diisocyanate. De plus, le rapport massique de l'adduit de plusieurs molécules d'un polythiol et de plusieurs molécules de xylylène diisocyanate à l'adduit d'une molécule d'un polythiol et de n molécules de xylylène diisocyanate est ajusté à 0,50 - 5,2.
PCT/JP2021/025468 2020-07-10 2021-07-06 Composition de polyisocyanate, procédé pour la production d'une composition de polyisocyanate, matière première de résine à deux composants, matériau de revêtement, agent adhésif et résine WO2022009882A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023176153A1 (fr) * 2022-03-18 2023-09-21 三井化学株式会社 Film de polythiouréthane, matériau pour verre de lunettes, verre de lunettes et procédé de production pour verre de lunettes
WO2024080384A1 (fr) * 2022-10-14 2024-04-18 三井化学株式会社 Composition de polythiol, composition polymérisable, résine, corps moulé, matériau optique et lentille

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208794A (ja) * 1995-02-03 1996-08-13 Mitsui Toatsu Chem Inc 含硫ウレタン系プラスチックレンズの製造方法
JPH0912663A (ja) * 1995-06-30 1997-01-14 Mitsui Toatsu Chem Inc 光重合含硫ウレタン系プラスチックレンズ
JPH0971625A (ja) * 1995-06-30 1997-03-18 Mitsui Toatsu Chem Inc 含硫ウレタン系樹脂組成物、該樹脂その樹脂よりなる光学素子及びレンズ
JPH09110983A (ja) * 1995-05-12 1997-04-28 Mitsui Toatsu Chem Inc ポリスルフィド系樹脂組成物、該樹脂及びその樹脂よりなる光学材料
JPH1081726A (ja) * 1996-09-09 1998-03-31 Mitsui Petrochem Ind Ltd ウレタン系プラスチックレンズ用組成物、それよりなるプラスチックレンズおよびその製造方法
JP2005508417A (ja) * 2001-11-05 2005-03-31 エシロール　アテルナジオナール　カンパニー　ジェネラーレ　デ　オプティック 透過性ポリチオウレタン基材とりわけ光学基材の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208794A (ja) * 1995-02-03 1996-08-13 Mitsui Toatsu Chem Inc 含硫ウレタン系プラスチックレンズの製造方法
JPH09110983A (ja) * 1995-05-12 1997-04-28 Mitsui Toatsu Chem Inc ポリスルフィド系樹脂組成物、該樹脂及びその樹脂よりなる光学材料
JPH0912663A (ja) * 1995-06-30 1997-01-14 Mitsui Toatsu Chem Inc 光重合含硫ウレタン系プラスチックレンズ
JPH0971625A (ja) * 1995-06-30 1997-03-18 Mitsui Toatsu Chem Inc 含硫ウレタン系樹脂組成物、該樹脂その樹脂よりなる光学素子及びレンズ
JPH1081726A (ja) * 1996-09-09 1998-03-31 Mitsui Petrochem Ind Ltd ウレタン系プラスチックレンズ用組成物、それよりなるプラスチックレンズおよびその製造方法
JP2005508417A (ja) * 2001-11-05 2005-03-31 エシロール　アテルナジオナール　カンパニー　ジェネラーレ　デ　オプティック 透過性ポリチオウレタン基材とりわけ光学基材の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023176153A1 (fr) * 2022-03-18 2023-09-21 三井化学株式会社 Film de polythiouréthane, matériau pour verre de lunettes, verre de lunettes et procédé de production pour verre de lunettes
WO2024080384A1 (fr) * 2022-10-14 2024-04-18 三井化学株式会社 Composition de polythiol, composition polymérisable, résine, corps moulé, matériau optique et lentille

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