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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • 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
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3228—Polyamines acyclic
• • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3234—Polyamines cycloaliphatic
• • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3237—Polyamines aromatic
  • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3225—Polyamines
  • C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
• • 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
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • 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
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C09D175/02—Polyureas

Definitions

• the present invention relates to a polyurea polymer, a polyurea composition, and a method for producing the same.
• Patent Document 1 proposes siloxane-modified polyurea fiber and a method for producing the same.
• Patent Document 2 proposes a method using a chlorinated solvent as the reaction solvent, but chlorinated solvents are difficult to use because various regulations are imposed on their use, disposal, etc.
• the present invention has been made in consideration of the above circumstances, and aims to provide a polyurea polymer that is soluble in a solvent that has a low boiling point and is easily volatile, and has a low distortion rate, a polyurea composition containing the same, and a method for producing the same.
• a polyurea polymer obtained from an organopolysiloxane having a specified amine equivalent, an aliphatic diisocyanate compound, and an amine compound having two or more amino groups in one molecule can solve the above problems, and also discovered that the above polyurea polymer can be produced using a secondary alcohol or tertiary alcohol as a solvent, which led to the creation of the present invention.
• the present invention provides: 1. (a) an amino group-containing organopolysiloxane represented by the following general formula (1) having an amine equivalent of more than 1,500 g/mol and not more than 7,500 g/mol; (In the above formula, R1 's are each independently a monovalent hydrocarbon group having a primary or secondary amino group and having 1 to 20 carbon atoms, and R2 's are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. n is a value that satisfies the above-mentioned amine equivalent.
• each siloxane unit shown in parentheses is arbitrary.
• a method for producing a polyurea polymer according to 1 or 2 comprising the step of reacting the components (a) to (c) in an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule to obtain a polyurea polymer; 4.
• a polyurea composition comprising (A) the polyurea polymer according to 1 or 2, and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule; 5.
• a method for producing the polyurea composition according to 5 comprising the steps of reacting the components (a) to (c) in the alcohol of the component (B) to synthesize a polyurea polymer of the component (A), and obtaining a polyurea composition as a solution in which the polyurea polymer of the component (A) is dissolved in the alcohol of the component (B).
• the polyurea polymer of the present invention is more soluble in solvents that have a low boiling point and are easily volatile than conventional polymers.
• the polyurea polymer of the present invention has a low distortion rate, making it suitable for use as a sealing material.
• polyurea Polymer The polyurea polymer of the present invention is obtained by reacting the following components (a) to (c): (a) an amino group-containing organopolysiloxane having an amine equivalent of more than 1,500 g/mol and not more than 7,500 g/mol, as represented by the following general formula (1); (b) an aliphatic diisocyanate compound having two isocyanate groups per molecule; and (c) an amine compound having two or more amino groups per molecule.
• an amino group-containing organopolysiloxane having an amine equivalent of more than 1,500 g/mol and not more than 7,500 g/mol, as represented by the following general formula (1)
• an aliphatic diisocyanate compound having two isocyanate groups per molecule
• an amine compound having two or more amino groups per molecule.
• the component (a) used in the present invention is an amino group-containing organopolysiloxane represented by the following general formula (1) having an amine equivalent of more than 1,500 g/mol and not more than 7,500 g/mol, and acts as the base agent for the polyurea polymer of the present invention.
• R 1 's are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms and containing a primary or secondary amino group.
• Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms and a primary or secondary amino group for R 1 include groups represented by the following formula (2). -R 3 NHR 4 (2)
• R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic.
• Examples of such a group include an alkylene group having 1 to 20, preferably 1 to 10, carbon atoms; a cycloalkylene group having 3 to 20, preferably 3 to 10, carbon atoms; an alkenylene group having 2 to 20, preferably 2 to 10, carbon atoms; an arylene group having 6 to 20, preferably 6 to 10, carbon atoms; and an aralkylene group having 7 to 20, preferably 7 to 10, carbon atoms.
• divalent hydrocarbon group for R3 examples include alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene, and eicosadecylene; cycloalkylene groups such as cyclopentylene and cyclohexylene; alkenylene groups such as vinylene and propenylene; arylene groups such as phenylene, methylphenylene, and naphthylene; and aralkylene groups such as benzylene and phenethylene.
• alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene,
• R3 is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, or decamethylene group, still more preferably a methylene, ethylene, trimethylene, or propylene group, and particularly preferably an ethylene or trimethylene group.
• R 4 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• the monovalent hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and examples thereof include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms.
• monovalent hydrocarbon groups for R4 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl, tolyl, and naphthyl; and aralkyl groups such as benzyl and phenethyl.
• alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hex
• R 4 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group, and even more preferably a hydrogen atom or a methyl group.
• Specific examples of the group represented by the above formula (2) include aminomethyl, 2-aminoeth-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, N-methylaminomethyl, N-methyl-2-aminoeth-1-yl, N-methyl-2-aminoprop-1-yl, N-methyl-3-aminoprop-1-yl, N-methyl-2-aminobut-1-yl, N-methyl-3-aminobut-1-yl, N-methyl-4-aminobut-1-yl, N-ethylaminomethyl, N-ethyl-2-aminobut-1-yl, aminoeth-1-yl, N-ethyl-2-aminoprop-1-yl, N-ethyl-3-aminoprop-1-yl, N-ethyl-2-aminobut-1-yl
• R2 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.
• Specific examples of the monovalent hydrocarbon group of R2 include the same groups as those exemplified for R4 , and among these, R2 is preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 8 carbon atoms, or a vinyl group, more preferably a methyl, ethyl, propyl, butyl, phenyl, or vinyl group, and even more preferably a methyl group or a phenyl group.
• the amine equivalent of component (a) is 1,500 to 7,500 g/mol. It is preferably more than 1,500 g/mol and not more than 7,500 g/mol, more preferably 1,600 to 7,500 g/mol, even more preferably 1,700 to 7,000 g/mol, even more preferably 1,900 to 6,500 g/mol, and particularly preferably 2,000 to 5,500 g/mol.
• This amine equivalent represents the mass of component (a) per mole of amino groups in component (a). If the amine equivalent is less than 1,500 g/mol, the balance between the hardness and distortion rate of the resulting polymer is not achieved, and if it exceeds 7,500 g/mol, it is difficult to increase the strength.
• the above amine equivalent is a value measured by the neutralization titration method described below.
• n is a value that satisfies the above-mentioned range of amine equivalent.
• the specific range of n is determined by the type of the substituents of R 1 and R 2.
• n is preferably a number from 37 to 199, more preferably a number from 42 to 186, and even more preferably a number from 48 to 172.
• the bonding order of each siloxane unit shown in parentheses is arbitrary.
• organopolysiloxanes represented by formula (1) include, but are not limited to, the following.
• Me represents a methyl group
• Ph represents a phenyl group.
• those represented by formulas (1-1) to (1-3) are preferred, and those represented by formulas (1-1) and (1-3) are more preferred.
• the arrangement of each repeating unit may be in a block or random arrangement, and is optional.
• the component (a) may be used alone or in combination of two or more kinds.
• organopolysiloxanes can be produced by conventional methods, for example, by reacting an amino group-containing disiloxane with a cyclic siloxane having any substituent under acid or alkaline conditions. Commercially available products may also be used.
• the component (b) used in the present invention is an aliphatic diisocyanate compound having two isocyanate groups in one molecule, and is a component that reacts with the component (a) to form the polyurea polymer of the present invention.
• the component (b) so long as it has two isocyanate groups in one molecule and examples include those represented by the following formula (3).
• Q is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
• the divalent hydrocarbon group having 1 to 20 carbon atoms represented by Q may be linear, branched, or cyclic, and may be the same as the groups exemplified for R3 .
• Q is preferably an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms. It may also be a group that is a combination of these groups.
• at least a portion of the hydrogen atoms of these groups may be substituted with other substituents, and examples of the other substituents include alkyl groups having 1 to 3 carbon atoms, such as methyl and ethyl groups.
• isocyanate compound represented by formula (3) examples include diisocyanate compounds such as 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.
• diisocyanate compounds such as 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexy
• 1,6-hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate are preferable, and isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate are more preferable.
• the component (b) may be used alone or in combination of two or more kinds.
• the amount of component (b) is not particularly limited, but is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of component (a).
• the component (c) used in the present invention is an amine compound having two or more amino groups in one molecule, and acts as a chain extender or crosslinking agent for the polyurea polymer of the present invention.
• the number of amino groups in the amine compound of component (c) is two or more in one molecule, preferably two to four, more preferably two to three, and even more preferably two.
• the component (c) is not particularly limited as long as it is a compound other than the component (a) and has two or more functional groups in one molecule, but examples thereof include those represented by the following formula (4). H 2 NR-NH 2 (4)
• R is a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, which may be linear, branched, or cyclic, and includes the same groups as those exemplified for R3 . It may also be a group that is a combination of these groups.
• at least a portion of the hydrogen atoms in these groups may be substituted with other substituents, and examples of the other substituents include alkyl groups having 1 to 3 carbon atoms, such as methyl groups and ethyl groups; halogen atoms, such as chlorine atoms and bromine atoms; and groups containing heteroatoms, such as oxygen atoms and sulfur atoms.
• amine compound represented by formula (4) include, for example, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3-butanediamine, 1,2-butanediamine, 1,5-pentanediamine, 1,4-pentanediamine, 1,3-pentanediamine, 1,2-pentanediamine, 2,5-pentanediamine, 2,4-pentanediamine, and 2,3-pentanediamine.
• cyclic diamines such as piperazine
• triamines such as diethylenetriamine, bis(hexamethylene)triamine, and trisaminoethylamine
• the amount of component (c) is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass, per 100 parts by mass of component (a).
• the polyurea polymer of the present invention may contain other components as long as the effects of the present invention are not impaired.
• other components include polyols (diols), catalysts, etc.
• polyols include polyether polyols, polyester polyols, polycarbonate polyols, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,2-pentanediol, 2,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, 1,3-hexanediol, 1,2-hexanediol, 2,6-hexanediol, 2,5-hexanediol, 2,5-hexan
• trifunctional alcohols such as glycerin and trimethylolpropane
• tetrafunctional alcohols such as pentaerythritol and ⁇ -methylglycoside
• hexafunctional alcohols such as sorbitol and sucrose
• alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.
• catalysts include triethylamine, N,N-dimethylcyclohexylamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyldipropylenetriamine, triethylenediamine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N-ethylmorpholine, 1,2-dimethylimidazole, dimethylethanolamine, dimethylaminoethoxyethanol, N,N,N'-trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, Examples include amine compounds such as bis(2-dimethylaminoethyl)piperazine and bis(2-dimethylaminoethyl)
• the method for producing the polyurea polymer of the present invention (synthesis method) is not particularly limited, and any method conventionally used for producing polyurea resins can be used, for example, a prepolymer method, a one-shot method, etc.
• the component (a) and the component (b) are reacted, and then the component (c) is added and reacted.
• the component (b) may be added to the component (a) or the component (a) may be added to the component (b), but the method of adding the component (b) to the component (a) is preferred.
• the reaction can be carried out without a solvent, but it is preferable to use a solvent.
• the solvent may be added to the component (a) or the component (b).
• the solvent may be added after mixing the components (a) and (b), or the components (a) and (b) may be added to the solvent.
• the component (c) when the component (c) is added after the reaction of the components (a) and (b), the component (c) may be added simultaneously with the component (c), before the addition of the component (c), or after the addition of the component (c) and the reaction. When the components are added, they may be added dropwise or all at once.
• the reaction temperature is not particularly limited, and is preferably 10 to 150°C, more preferably 15 to 100°C, and even more preferably 20 to 60°C.
• the reaction time is also not particularly limited, and is preferably 10 minutes to 20 hours, more preferably 10 minutes to 15 hours, even more preferably 10 minutes to 10 hours, and even more preferably 0.5 to 5 hours.
• the one-shot method is a method in which components (a), (b) and (c) are reacted simultaneously.
• the reaction temperature is not particularly limited, and is preferably 10 to 150° C., more preferably 15 to 100° C., and further preferably 20 to 60° C.
• the reaction time is also not particularly limited, and is preferably 10 minutes to 10 hours, and more preferably 0.5 to 5 hours.
• the prepolymer method it is preferable to use the prepolymer method, and it is more preferable to use the prepolymer method to react components (a) to (c) in a solvent, and it is even more preferable to mix component (a) with a solvent, add component (b) to react, and then add component (c) to further react.
• the other components can be added to components (a) to (c) at any time.
• the solvent that can be used in the above reaction is not particularly limited, but is preferably an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group per molecule.
• Such an alcohol is not particularly limited as long as it has one secondary hydroxyl group or one tertiary hydroxyl group per molecule, and examples thereof include isopropyl alcohol, 2-butanol, 2-methyl-2-propanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclohexanol, 1-methoxy-2-propanol, 2-heptanol, 3-heptanol, 4-heptanol, and 1-ethoxy-2-propanol.
• the boiling point of the solvent is preferably 200°C or lower, more preferably 50 to 180°C, further preferably 60 to 150°C, and particularly preferably 70 to 120°C.
• the amount added is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more, per 100 parts by mass of the total of components (a) to (c) and other components.
• the polyurea polymer of the present invention can be obtained by drying preferably at 20 to 200° C., more preferably at 20 to 150° C., preferably for 1 to 30 hours, more preferably for 5 to 20 hours.
• the drying step is preferably carried out in an inert gas atmosphere such as nitrogen or under reduced pressure of 700 Pa or less, since this can prevent deterioration of the product.
• the weight average molecular weight of the polyurea polymer of the present invention is not particularly limited, but is preferably 4,000 to 800,000, more preferably 50,000 to 800,000, and even more preferably 50,000 to 600,000.
• the weight average molecular weight is a standard polymethyl methacrylate equivalent value measured by gel permeation chromatography (GPC).
• the hardness measured under the following conditions is preferably 85 or less, more preferably 80 or less, and even more preferably 75 or less, in Shore A.
• the distortion rate at 100° C. determined under the following conditions is preferably 55% or less, more preferably 50% or less, and further preferably 45% or less.
• the polyurea polymer of the present invention has the above-mentioned Shore A hardness and distortion rate, and is therefore particularly suitable for use as a sealing material.
• Hardness measurement method The polyurea polymer of the present invention is pressed at a predetermined temperature to prepare a sheet having a thickness of 2 mm by melt molding, and then the sheet is left for 2 days or more at 25° C.
• the polyurea polymer of the present invention is press-molded in a mold of 50 mm x 50 mm x 6 mm (thickness), cut into a piece of 10 mm x 10 mm, and annealed at 100°C for 16 hours.
• the polymer annealed in (1) is compressed to a thickness of 3.9 mm and heated at 100° C. for 22 hours.
• the polyurea composition of the present invention contains (A) the above-mentioned polyurea polymer and (B) an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group in each molecule.
• the component (A) is the above-mentioned polyurea polymer, and its content in the composition is preferably 10 to 50 mass %, and more preferably 20 to 40 mass %.
• the component (B) used in the present invention is an alcohol having one secondary hydroxyl group or one tertiary hydroxyl group in each molecule, and is used as a dilution solvent in the polyurea composition of the present invention.
• the (B) component is not particularly limited as long as it has one secondary hydroxyl group or one tertiary hydroxyl group per molecule, and examples thereof include the same solvents as those used in the production of the polyurea polymer of the present invention described above.
• the amount of component (B) is preferably 10 parts by mass or more, more preferably 40 parts by mass or more, even more preferably 100 parts by mass or more, and particularly preferably 200 parts by mass or more, per 100 parts by mass of the polyurea polymer (A). If the amount is too small, the polyurea polymer may not be compatible. There is no particular upper limit, but the amount is preferably 300 parts by mass or less, and more preferably 250 parts by mass or less.
• composition of the present invention may be added to the composition of the present invention within the range that does not impair the effects of the present invention.
• other components include antioxidants, ultraviolet absorbers, light stabilizers, and solvents other than component (B).
• antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
• ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and benzoate-based ultraviolet absorbers.
• light stabilizers include hindered amine light stabilizers.
• solvents are those other than component (B), such as toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, and butyl acetate.
• solvents are those other than component (B), such as toluene, xylene, benzene, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, tetrahydrofuran (THF), diethyl ether, acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, and butyl acetate.
• THF tetrahydro
• the method for producing the polyurea composition of the present invention is not particularly limited, and the polyurea composition can be obtained by mixing the above-mentioned components (A) and (B) and, if necessary, other components according to a conventional method.
• the other components can be added to the components (A) and (B) at any time.
• the above-mentioned (a) to (c) components are reacted in the alcohol of the (B) component to synthesize the polyurea polymer of the (A) component, and the solution after the reaction in which the polyurea polymer of the (A) component is dissolved in the alcohol of the (B) component can be obtained as it is as the polyurea composition of the present invention.
• the polyurea composition of the present invention forms a resin or elastomer having thermoplasticity depending on its composition, but can also be made into a thermosetting composition by using an alcohol having three or more functional groups.
• the molding method of the polyurea composition of the present invention is not particularly limited, and any conventionally known method can be adopted.
• the composition may be cut into pellets using a twin-screw extruder, and then processed into a molded product using various commonly used molding machines, i.e., an extrusion molding machine, an injection molding machine, a calendar molding machine, a press molding machine, or the like.
• the polyurea composition of the present invention in a liquid state in which the polyurea polymer (A) is dissolved in the component (B), or in a two-liquid or three-liquid state in which the prepolymer and the chain extender are separated, can also be suitably used as a primer coating agent or top coating agent for various plastics such as polyester, nylon, polyvinyl chloride, ABS, OPP, CPP, etc. Furthermore, it can be used as a paint, surface coating material, sealant, office automation roll, shoes, ski boots, adhesive, sealing material, wood binder, thermoplastic elastomer, thermosetting elastomer, etc. for various fibers such as elastic fibers, various woven and woven fibers, nonwoven fabrics, paper, natural leather, artificial leather, synthetic leather, wood, etc.
• component (a-5) is an organopolysiloxane represented by the following formula:
• siloxane units may be bonded in a block or random manner.
• the method for measuring the amine equivalent is as follows. [Method for measuring amine equivalent] The measurement was performed under the following conditions using an automatic titrator COM1750 (manufactured by HIRANUMA Co., Ltd.) and a glass composite electrode GR-511B. The sample was weighed into a beaker, 25 mL each of toluene and IPA were added thereto, and the mixture was stirred, followed by neutralization titration with 0.1 N hydrochloric acid.
• Component (b) H-MDI 4,4'-dicyclohexylmethane diisocyanate (mixture of isomers)
• IPDI Isophorone diisocyanate (mixture of isomers)
• IPDA isophoronediamine (cis-, trans-mixture) MDA 4,4'-methylenedianiline DDDA 1,12-dodecanediamine DDA 1,10-decanediamine TMHMDA Trimethylhexamethylenediamine (2,2,4- and 2, 4,4-mixture) ODA 1,8-Octanediamine H-MDA 4,4'-Diaminodicyclohexylmethane (mixture of isomers) PRZ Piperazine HDA 1,6-Hexanediamine
• Example 1-1 Production of polyurea polymer and evaluation of physical properties
• 85 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and then 11.34 parts by mass of H-MDI was added at 20° C. and reacted for 1 hour.
• 8.65 parts by mass of IPDA was added at 20° C. and reacted for 12 hours.
• the reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours, and then dried in a vacuum dryer at 120° C. and 1 mmHg for 5 hours to obtain a lump.
• Examples 1-2 to 1-14 The same operation as in Example 1-1 was carried out to obtain lumps of Examples 1-2 to 1-14. The physical properties of the obtained lumps were evaluated in the same manner as in Example 1-1. The amount of IPA used was the same as in Example 1-1. The blended compositions are shown in Table 1, and the evaluation results are shown in Table 2.
• Comparative Examples 1-1 and 1-2 The same procedure as in Example 1 was carried out to obtain lumps of Comparative Examples 1-1 and 1-2. The amount of IPA used was the same as in Example 1-1. The blended compositions are shown in Table 1, and the evaluation results are shown in Table 2.
• the polyurea polymers of Examples 1-1 to 1-14 have a Shore A of 75 or less and a distortion rate at 100°C of 50% or less.
• Examples 2-2 to 2-14 The same operation as in Example 2-1 was carried out to obtain polyurea compositions of Examples 2-2 to 2-14 as solutions in which the polyurea polymer was dissolved in IPA.
• the blending compositions were the same as in Examples 1-2 to 1-14, respectively.
• the amount of IPA used was the same as in Example 2-1.
• Example 2-1 and 2-2 The same operation as in Example 2-1 was carried out to obtain polyurea compositions of Comparative Examples 2-1 and 2-2 as solutions in which a polyurea polymer was dissolved in IPA.
• the blending compositions were the same as those of Comparative Examples 1-1 and 1-2, respectively.
• the amount of IPA used was the same as that of Example 2-1.
• Example 2-15 85 parts by mass of (a-1) and 233.33 parts by mass of IPA were mixed, and then 11.34 parts by mass of H-MDI was added at 20° C. and reacted for 1 hour. Then, 8.65 parts by mass of IPDA was added at 20° C. and reacted for 12 hours. The reaction product was transferred to a polytetrafluoroethylene tray and dried at room temperature for 12 hours, and then dried in a vacuum dryer at 120° C. and 1 mmHg for 5 hours to obtain a lump. When 70 parts by mass of IPA was added to 30 parts by mass of the obtained lump, it was dissolved again, and a polyurea composition was obtained.

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