WO2018150601A1 - ポリカルボジイミド組成物、ポリカルボジイミド組成物の製造方法、水分散組成物、溶液組成物、樹脂組成物および樹脂硬化物 - Google Patents
ポリカルボジイミド組成物、ポリカルボジイミド組成物の製造方法、水分散組成物、溶液組成物、樹脂組成物および樹脂硬化物 Download PDFInfo
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- WO2018150601A1 WO2018150601A1 PCT/JP2017/022711 JP2017022711W WO2018150601A1 WO 2018150601 A1 WO2018150601 A1 WO 2018150601A1 JP 2017022711 W JP2017022711 W JP 2017022711W WO 2018150601 A1 WO2018150601 A1 WO 2018150601A1
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- oxyethylene
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
- C08G18/095—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to carbodiimide or uretone-imine groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
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- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C08G2115/00—Oligomerisation
- C08G2115/06—Oligomerisation to carbodiimide or uretone-imine groups
Definitions
- the present invention relates to a polycarbodiimide composition, a method for producing a polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition, and a cured resin product.
- resin compositions containing a main agent and a curing agent are known.
- carbodiimide curing agents are known as curing agents.
- carbodiimide-based curing agent for example, hexamethylene diisocyanate (HDI), 673 g, and 800 g of polyethylene glycol monomethyl ether having an average molecular weight of 400 are reacted at 120 ° C. for 1 hour, and a carbodiimidization catalyst ( A polycarbodiimide compound in which 13.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide) is added and further reacted at 185 ° C. for 5 hours has been proposed (for example, Patent Document 1 below (Synthesis) See Example 82).).
- HDI hexamethylene diisocyanate
- 673 g, and 800 g of polyethylene glycol monomethyl ether having an average molecular weight of 400 are reacted at 120 ° C. for 1 hour, and a carbodiimidization catalyst (A polycarbodiimide compound in which 13.5 g of 3-methyl-1-phenyl-2-phospholene-1-oxide) is added and further
- a resin composition comprising such a polycarbodiimide compound (curing agent) and a main agent, a cured resin such as a coating film can be obtained.
- the above-mentioned polycarbodiimide compound is not sufficiently stable in storage, and the fluidity may be lowered or solidified by storage.
- a resin cured product such as a coating film obtained using a polycarbodiimide compound is required to have various physical properties such as film formability, water resistance and chemical resistance.
- the present invention provides a polycarbodiimide composition capable of obtaining a resin cured product having excellent storage stability and excellent film formability, water resistance and chemical resistance, a method for producing the polycarbodiimide composition, An aqueous dispersion composition and a solution composition containing a carbodiimide composition, a resin composition containing a polycarbodiimide composition, and a cured resin obtained by curing the resin composition.
- the present invention [1] is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol, the alcohol being at least one oxyethylene-containing alcohol containing an oxyethylene group, and oxyethylene
- This invention [2] contains the polycarbodiimide composition as described in said [1] whose content rate of an oxyethylene group is 10 to 35 mass% with respect to the said polycarbodiimide composition. .
- the oxyethylene-free alcohol having a solubility parameter of 11.20 (cal / cm 3 ) 1/2 or less is a primary alcohol and / or a secondary alcohol.
- the oxyethylene-free alcohol having a solubility parameter of 11.20 (cal / cm 3 ) 1/2 or less is a monovalent alcohol containing 4 to 12 carbon atoms.
- the polycarbodiimide composition according to any one of [1] to [3] above is included.
- the oxyethylene-free alcohol having a solubility parameter of 11.20 (cal / cm 3 ) 1/2 or less, Consists of isobutanol, 2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methoxy-1-butanol, 1-octanol, 2-ethyl-1-hexanol and 1-dodecanol
- the polycarbodiimide composition according to any one of the above [1] to [4], which is at least one selected from the group.
- the present invention includes the polycarbodiimide composition according to any one of [1] to [5] above, wherein the polyisocyanate is an aliphatic polyisocyanate.
- the present invention includes the polycarbodiimide composition according to any one of [1] to [6] above, wherein the polyisocyanate is pentamethylene diisocyanate.
- a urethanation step in which a polyisocyanate having a primary isocyanate group and an alcohol are subjected to a urethanation reaction, and a reaction product in the urethanization step are heated in the presence of a carbodiimidization catalyst
- a carbodiimidization step wherein the alcohol includes at least one oxyethylene-containing alcohol containing an oxyethylene group and at least one oxyethylene-free alcohol not containing an oxyethylene group.
- a method for producing a polycarbodiimide composition wherein a solubility parameter of at least one of the oxyethylene-free alcohols is 11.20 (cal / cm 3 ) 1/2 or less.
- the manufacturing method is included.
- the present invention is an aqueous dispersion in which the polycarbodiimide composition according to any one of the above [1] to [7] is dispersed in water at a solid content concentration of 5% by mass to 90% by mass It contains an aqueous dispersion composition that is a liquid.
- the present invention [11] is a solution in which the polycarbodiimide composition according to any one of the above [1] to [7] is dissolved in an organic solvent at a solid content concentration of 5% by mass to 90% by mass.
- a solution composition is a solution in which the polycarbodiimide composition according to any one of the above [1] to [7] is dissolved in an organic solvent at a solid content concentration of 5% by mass to 90% by mass.
- the present invention [12] includes a resin composition containing a main component having a carboxyl group and a curing agent including the polycarbodiimide composition according to any one of the above [1] to [7]. .
- the present invention [13] includes a cured resin which is a cured product of the resin composition described in [12] above.
- the polycarbodiimide composition of the present invention is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing at least one oxyethylene-containing alcohol and at least one oxyethylene-free alcohol.
- the solubility parameter of the at least one oxyethylene-free alcohol is not more than the predetermined value.
- the polycarbodiimide composition of the present invention the aqueous dispersion composition of the present invention containing the polycarbodiimide composition and the solution composition of the present invention, and the resin composition of the present invention containing the polycarbodiimide composition are stable in storage.
- the polycarbodiimide composition of the present invention can be efficiently produced.
- the cured resin of the present invention is excellent in film formability, water resistance and chemical resistance.
- the polycarbodiimide composition of the present invention is a reaction product of a polyisocyanate having a primary isocyanate group (hereinafter sometimes simply referred to as polyisocyanate) and an alcohol.
- a primary isocyanate group is defined as a monovalent functional group (—CH 2 NCO) in which two hydrogen atoms (H) are bonded to a carbon atom (C) to which an isocyanate group (—NCO) is bonded.
- the polyisocyanate having a primary isocyanate group only needs to have at least one primary isocyanate group, and may have, for example, a secondary isocyanate group or a tertiary isocyanate group.
- the secondary isocyanate group is a divalent functional group (—CHR—NCO (R is substituted), wherein one hydrogen atom (H) is bonded to the carbon atom (C) to which the isocyanate group (—NCO) is bonded. Group))).
- the tertiary isocyanate group is a trivalent functional group (—CR 1 R 2 —NCO () in which a hydrogen atom (H) is not bonded to a carbon atom (C) to which an isocyanate group (—NCO) is bonded.
- R 1 and R 2 represent the same or different substituents.)
- polyisocyanates having primary isocyanate groups examples include aliphatic polyisocyanates having primary isocyanate groups, alicyclic polyisocyanates having primary isocyanate groups, and araliphatic polyisocyanates having primary isocyanate groups. It is done.
- the aliphatic polyisocyanate having a primary isocyanate group is a linear (straight chain or branched chain: acyclic) aliphatic polyisocyanate having a primary isocyanate group, such as ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6 Hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate, heptamethylene diisocyanate, o Data diisocyanate, and aliphatic diisocyanates such as dodecamethylene diisocyanate.
- Examples of the alicyclic polyisocyanate having a primary isocyanate group include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 1,3- or 1,4-bis (isocyanate). Natomethyl) cyclohexane or a mixture thereof (hydrogenated XDI), and alicyclic diisocyanates such as norbornane diisocyanate (NBDI).
- IPDI isophorone diisocyanate
- NBDI norbornane diisocyanate
- araliphatic polyisocyanate having a primary isocyanate group examples include araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI).
- polyisocyanates having primary isocyanate groups can be used alone or in combination of two or more.
- the polyisocyanate having a primary isocyanate group is preferably an aliphatic polyisocyanate having a primary isocyanate group or an alicyclic polyisocyanate having a primary isocyanate group from the viewpoint of light resistance, handling properties and water dispersibility. From the viewpoint of chemical resistance, aliphatic polyisocyanates having primary isocyanate groups are more preferable.
- the aliphatic polyisocyanate having a primary isocyanate group is preferably 1,5-pentamethylene diisocyanate (PDI) or 1,6-hexamethylene diisocyanate (HDI), more preferably. 1,5-pentamethylene diisocyanate (PDI).
- PDI 1,5-pentamethylene diisocyanate
- HDI 1,6-hexamethylene diisocyanate
- 1,5-pentamethylene diisocyanate has a smaller number of carbon atoms and a smaller molecular weight than 1,6-hexamethylene diisocyanate. Therefore, when producing a polycarbodiimide composition having the same molecular weight, the use of 1,5-pentamethylene diisocyanate increases the concentration of carbodiimide groups in the polycarbodiimide composition compared to the use of 1,6-hexamethylene diisocyanate. be able to. As a result, a cured resin (described later) excellent in various physical properties (water resistance, chemical resistance, etc.) can be obtained.
- 1,5-pentamethylene diisocyanate having an odd number of carbon atoms is less crystalline than 1,6-hexamethylene diisocyanate having an even number of carbon atoms due to the amorphous structure derived from the odd number of carbon atoms. It is excellent in the property and the dispersibility, and the physical property of the resin cured material obtained (after-mentioned) can be improved.
- the alcohol includes an alcohol containing an oxyethylene group in the molecule (hereinafter referred to as an oxyethylene-containing alcohol) and an alcohol not containing an oxyethylene group in the molecule (hereinafter referred to as an oxyethylene-free alcohol). More specifically, it contains at least one oxyethylene-containing alcohol and at least one oxyethylene-free alcohol.
- the oxyethylene group (—CH 2 CH 2 O—) is a group composed of two carbon atoms, four hydrogen atoms, and one oxygen atom.
- an oxyethylene group (—CH 2 CH 2 O—) is obtained by replacing one or more hydrogen atoms with another atomic group (for example, an oxypropylene group (—CH (CH 3 ) CH 2 O—) Etc.).
- the oxyethylene group (—CH 2 CH 2 O—) has a terminal carbon atom bonded to a hydrogen atom or a hydrocarbon group (for example, an ethyl ether group (H—CH 2 CH 2 O—), Also distinguished from propyl ether groups (CH 3 —CH 2 CH 2 O—, etc.).
- An alcohol having such an oxyethylene group (—CH 2 CH 2 O—) structure in the molecule is defined as an oxyethylene-containing alcohol.
- An alcohol having no oxyethylene group (—CH 2 CH 2 O—) structure in the molecule is defined as an oxyethylene-free alcohol.
- Examples of the oxyethylene-containing alcohol include a polyol containing an oxyethylene group in the molecule (hereinafter referred to as an oxyethylene-containing polyol) and a monool containing an oxyethylene group in the molecule (hereinafter referred to as an oxyethylene-containing monool). Etc.
- An oxyethylene-containing polyol is an organic compound having both one or more oxyethylene groups and two or more hydroxyl groups in one molecule, such as polyoxyethylene polyol, polyoxyethylene / polyoxypropylene (random). And / or block) oxyethylene-containing polymer polyols such as copolymers.
- Polyoxyethylene polyol can be obtained, for example, by addition reaction of ethylene oxide using a low molecular weight polyol or the like as an initiator.
- the polyoxyethylene / polyoxypropylene copolymer can be obtained, for example, by addition reaction of ethylene oxide and propylene oxide using a low molecular weight polyol or the like as an initiator.
- the low molecular weight polyol is a compound having two or more hydroxyl groups and a molecular weight of 60 or more and less than 500, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol.
- 1,2-butylene glycol 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3 Dimethylol heptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A 1,4-dihydroxy-2-butene, 2,6- Dihydric alcohols such as methyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol and dipropylene glycol, for example, trihydric alcohols such as glycerin, trimethylolpropane and triisopropanolamine, such as tetra Tetrahydric alcohols such as methylolmethan
- Preferred examples of the low molecular weight polyol include dihydric alcohols.
- the number of functional groups (number of hydroxyl groups) of polyoxyethylene polyol is the same as the number of functional groups (number of hydroxyl groups) of the initiator (such as low molecular weight polyol).
- the number of functional groups (number of hydroxyl groups) of the polyoxyethylene polyol is the same as the number of functional groups (number of hydroxyl groups) of the initiator (such as low molecular weight polyol).
- a dihydric alcohol used as the initiator
- Polyoxyethylene glycol is obtained as the polyoxyethylene polyol.
- the number of functional groups (number of hydroxyl groups) of the polyoxyethylene / polyoxypropylene (random and / or block) copolymer is the same as the number of functional groups (number of hydroxyl groups) of the initiator (such as low molecular weight polyol).
- a dihydric alcohol is used as the initiator, a divalent polyoxyethylene / polyoxypropylene copolymer is obtained
- the oxyethylene-containing polyol is not limited to the above oxyethylene-containing polymer polyol as long as it has one or more oxyethylene groups and two or more hydroxyl groups in one molecule.
- Examples also include oxyethylene-containing monomer polyols such as glycol (HO—CH 2 CH 2 —OH) and diethylene glycol (HO—CH 2 CH 2 —O—CH 2 CH 2 —OH).
- oxyethylene-containing polyol when the oxyethylene-containing polyol contains two or more oxyethylene groups, these oxyethylene groups may or may not be continuous. In other words, when the oxyethylene-containing polyol contains two or more oxyethylene groups, another group (for example, an oxypropylene group) may be interposed between the oxyethylene groups, It does not have to be interposed.
- another group for example, an oxypropylene group
- oxyethylene-containing polyols can be used alone or in combination of two or more.
- oxyethylene-containing polyol examples include oxyethylene-containing polymer polyols.
- the oxyethylene-containing polyol is preferably a polyol containing two or more continuous oxyethylene groups in the molecule, more preferably a polyol containing three or more continuous oxyethylene groups in the molecule. More preferably, polyoxyethylene glycol containing three or more continuous oxyethylene groups is mentioned.
- the oxyethylene-containing monool is an organic compound having both one or more oxyethylene groups and one hydroxyl group in one molecule, and is, for example, an oxyethylene-containing polymer monolayer such as one-end-capped polyoxyethylene glycol. Examples include all.
- One-end-capped polyoxyethylene glycol is a polyethylene glycol monoalkyl ether in which one terminal hydroxyl group of polyoxyethylene glycol is substituted with an oxyalkylene group.
- the alkyl group has 1 or more carbon atoms, for example, 20 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 2 or less. It is. That is, examples of the alkyl group for sealing one end include a methyl group and an ethyl group. Specific examples of such polyethylene glycol monoalkyl ether include polyethylene glycol monomethyl ether and polyethylene glycol monoethyl ether.
- the oxyethylene-containing monool is not limited to the above-mentioned oxyethylene-containing polymer monool as long as it has one or more oxyethylene groups and one hydroxyl group in one molecule. Monomeric monools are also included. Examples of the oxyethylene-containing monomer monool include 2-methoxyethanol (CH 3 O—CH 2 CH 2 —OH), 2-ethoxyethanol (CH 3 CH 2 O—CH 2 CH 2 —OH), and diethylene glycol monoethyl. And primary alcohols such as ether (also called carbitol) (CH 3 O—CH 2 CH 2 —O—CH 2 CH 2 —OH).
- oxyethylene-containing monool contains two or more oxyethylene groups
- these oxyethylene groups may or may not be continuous.
- another group for example, an oxypropylene group
- oxyethylene-containing monools can be used alone or in combination of two or more.
- oxyethylene-containing alcohols can be used alone or in combination of two or more.
- the oxyethylene-containing alcohol is preferably an oxyethylene-containing monool, more preferably an oxyethylene-containing polymer monool, still more preferably a polyethylene glycol monoalkyl ether, and particularly preferably a polyethylene glycol monomethyl ether.
- the number of repeating units is, for example, 2 or more, preferably 3 or more, more preferably 5 or more, and further preferably 10 or more. For example, it is 60 or less, preferably 50 or less.
- the stability during synthesis and the water dispersibility of the polycarbodiimide composition can be improved.
- the molecular weight (number average molecular weight) of the oxyethylene-containing alcohol is, for example, 100 or more, preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, for example, 5000 or less, It is 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less.
- the molecular weight (number average molecular weight) of the oxyethylene-containing alcohol is within the above range, the stability during synthesis and the water dispersibility of the polycarbodiimide composition can be improved.
- the oxyethylene-free alcohol is an alcohol excluding the oxyethylene-containing alcohol described above, and specifically, an alcohol that does not contain an oxyethylene group in the molecule.
- the oxyethylene-free alcohol is an oxyethylene-free alcohol (hereinafter referred to as a low SP oxyethylene-free alcohol) having a solubility parameter (SP value) of 11.20 (cal / cm 3 ) 1/2 or less. ) At least one kind.
- SP value solubility parameter
- At least one alcohol having a solubility parameter (SP value) of 11.20 (cal / cm 3 ) 1/2 or less is selected as the oxyethylene-free alcohol.
- solubility parameter As the solubility parameter (SP value), the Fedors method (Polymer Engineering and Science, February, 1974, Vol. 14, No. 2, P. 147 to 154 (A Method for Estimating Lithium Solids The Thorbolism TheSolubleMothThroughMoletholSoMetLiS) The value calculated by the method described in) is adopted.
- a low SP oxyethylene-free alcohol specifically, an oxyethylene-free polyol containing no oxyethylene group in the molecule (hereinafter referred to as a low SP oxyethylene-free polyol), and an oxyethylene in the molecule.
- a low SP oxyethylene-free polyol an oxyethylene-free polyol containing no oxyethylene group in the molecule
- examples include monools that do not contain a group (hereinafter referred to as low SP oxyethylene-free monools), and preferably low SP oxyethylene-free monools.
- the low SP oxyethylene-free monool is an alcohol having no oxyethylene group in one molecule and one hydroxyl group in one molecule, such as isobutanol (SP value of 11.11). (Cal / cm 3 ) 1/2 ), 2-butanol (SP value 11.11 (cal / cm 3 ) 1/2 ), 2-methyl-1-butanol (SP value 10.77 (cal / cm 3 )) 1/2 ), 3-methoxy-1-butanol (SP value 10.92 (cal / cm 3 ) 1/2 ), 1-pentanol (SP value 10.96 (cal / cm 3 ) 1/2 ), 2,2-dimethyl-1-propanol (also known as neopentyl alcohol) (SP value 10.58 (cal / cm 3 ) 1/2 ), 1-hexanol (SP value 10.68 (cal / cm 3 ) 1/2 ), 1- Heptanol (SP value 10.46 (cal / cm 3 ) 1/2 ), 1-octanol (SP value 10.28 (cal
- the low SP oxyethylene-free alcohol can be used alone or in combination of two or more.
- the low SP oxyethylene-free alcohol preferably contains a low SP oxyethylene-free monool.
- the content ratio of the low SP oxyethylene-free monool is, for example, 25% by mass or more, preferably 50% by mass or more, for example, 100% by mass or less, with respect to the total amount of oxyethylene-free alcohol.
- the low SP oxyethylene-free alcohol preferably, primary alcohol and secondary alcohol are used.
- the low SP oxyethylene-free alcohol is a primary alcohol and / or a secondary alcohol (in other words, not a tertiary alcohol)
- the production efficiency of the polycarbodiimide composition is excellent, and storage stability is also achieved. Excellent in properties.
- the low SP oxyethylene-free alcohol is preferably a monohydric alcohol containing 4 to 12 carbon atoms, more preferably isobutanol, 2-butanol, 2-methyl-1-butanol. , 3-methoxy-1-butanol, 1-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 1-dodecanol .
- the reactivity in the urethanization step described later can be improved, and a polycarbodiimide composition can be obtained with excellent efficiency, and the storage stability of the obtained polycarbodiimide composition is also excellent. .
- the solubility parameter (SP value) of the low SP oxyethylene-free alcohol is 11.20 (cal / cm 3 ) 1/2 or less, preferably 11.17 (cal / cm 3 ) as described above. ) 1/2 or less, more preferably 11.15 (cal / cm 3 ) 1/2 or less, further preferably 11.13 (cal / cm 3 ) 1/2 or less, particularly preferably 11.11 ( cal / cm 3 ) 1/2 or less, for example, 9.50 (cal / cm 3 ) 1/2 or more, preferably 9.70 (cal / cm 3 ) 1/2 or more, more preferably 10 0.000 (cal / cm 3 ) 1/2 or more, more preferably 10.10 (cal / cm 3 ) 1/2 or more, and particularly preferably 10.15 (cal / cm 3 ) 1/2 or more. .
- solubility parameter (SP value) of the low SP oxyethylene-free alcohol is within the above range, a cured resin product having excellent storage stability and excellent film forming properties, water resistance and chemical resistance can be obtained.
- the above low SP oxyethylene-free alcohol and other oxyethylene-free alcohol can be used in combination as necessary.
- other oxyethylene-free alcohols are alcohols whose solubility parameter (SP value) exceeds 11.20 (cal / cm 3 ) 1/2 (hereinafter referred to as high SP oxyethylene-free alcohols).
- high SP oxyethylene-free monool, high SP oxyethylene-free polyol, and the like are alcohols whose solubility parameter (SP value) exceeds 11.20 (cal / cm 3 ) 1/2 (hereinafter referred to as high SP oxyethylene-free alcohols).
- high SP oxyethylene-free monool, high SP oxyethylene-free polyol, and the like that is, as the oxyethylene-free alcohol, together with the above-described low SP oxyethylene-free alcohol (low SP oxyethylene-free monool and / or low SP oxyethylene-free polyol), the effects of the present invention are optionally included.
- These alcohols can be used alone or in combination of two or more.
- the content ratio of the oxyethylene-containing alcohol and the oxyethylene-free alcohol is adjusted so that the content ratio of the oxyethylene group in the obtained polycarbodiimide composition is within a predetermined range.
- the content ratio of the oxyethylene group in the polycarbodiimide composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, for example, 50% by mass or less.
- the amount is preferably 40% by mass or less, and more preferably 35% by mass or less.
- the solubility of the polycarbodiimide composition in the solvent and the water dispersibility can be improved, and a cured resin product (described later) having excellent water resistance can be obtained. be able to.
- the content ratio of oxyethylene groups can be calculated from the amount charged.
- the content ratio of the oxyethylene-containing alcohol and the oxyethylene-free alcohol in the alcohol is adjusted so that the content ratio of the oxyethylene group of the polycarbodiimide composition is in the above range.
- the content ratio of the oxyethylene-containing alcohol is, for example, 5 mol% or more, preferably 12 mol% or more, for example, 50 mol% or less, preferably, relative to the total moles of alcohols. 48 mol% or less.
- the content rate of oxyethylene free alcohol is 50 mol% or more, for example, Preferably, it is 52 mol% or more, for example, 95 mol% or less, Preferably, it is 88 mol% or less.
- the solubility of the polycarbodiimide composition in the solvent and the water dispersibility can be improved, and the water resistance can be improved.
- An excellent resin cured product (described later) can be obtained.
- the polycarbodiimide composition can be obtained by reacting the above polyisocyanate with the above alcohol under predetermined conditions, and further allowing a carbodiimidization reaction.
- urethanization step first, the polyisocyanate and the alcohols are subjected to a urethanization reaction (urethanization step).
- the reaction ratio between the polyisocyanate and the alcohol is such that the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the alcohol exceeds 2, for example, preferably 3 or more. More preferably, it is 4 or more, for example, 16 or less, preferably 14 or less, more preferably 10 or less. That is, in the urethanization step, the reaction is preferably carried out at a ratio where the isocyanate group becomes excessive with respect to the hydroxyl group.
- reaction ratio between the polyisocyanate and the alcohol is within the above range, a cured resin (explained later) having excellent storage stability and water resistance can be obtained.
- a known urethanization catalyst such as amines or organometallic compounds may be added as necessary.
- amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, And imidazoles such as 2-ethyl-4-methylimidazole.
- tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine
- quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, And imidazoles such as 2-ethyl-4-methylimidazole.
- organometallic compound examples include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dilauric acid).
- Dibutyltin (IV) dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride and the like, for example, organic lead compounds such as lead octoate and lead naphthenate, Organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octenoate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate, etc. It is below.
- examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.
- urethanization catalysts can be used alone or in combination of two or more.
- the mixing ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.
- the reaction conditions in the urethanization step are, for example, a reaction temperature of, for example, 30 ° C. or higher, preferably 60 ° C. or higher under normal pressure and an inert gas (eg, nitrogen gas) atmosphere. ° C or lower, preferably 180 ° C or lower.
- the reaction time is, for example, 1 hour or more, preferably 3 hours or more, for example, 50 hours or less, preferably 40 hours or less.
- urethane-modified product (alcohol-modified product) of polyisocyanate
- the urethane modified body (alcohol modified body) of polyisocyanate has an isocyanate group at the molecular terminal.
- the reaction solution containing the reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidization reaction (carbodiimidization step).
- the carbodiimidization catalyst is not particularly limited, and examples thereof include trialkyl phosphate compounds, phospholene oxide compounds, phospholene sulfide compounds, phosphine oxide compounds, and phosphine compounds.
- trialkyl phosphate ester examples include trialkyl phosphate ester compounds having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate, and trioctyl phosphate.
- Examples of the phospholene compound include 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholene-1-oxide (EMPO), 1 , 3-dimethyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and the like
- Examples thereof include phospholene oxide compounds having 4 to 18 carbon atoms, such as double bond isomers.
- Examples of the phospholene sulfide compound include phospholene sulfide compounds having 4 to 18 carbon atoms such as 1-phenyl-2-phospholene-1-sulfide.
- phosphine oxide compound examples include phosphine oxide compounds having 3 to 21 carbon atoms such as triphenylphosphine oxide and tolylphosphine oxide.
- phosphine compound examples include phosphine compounds having 3 to 30 carbon atoms such as bis (oxadiphenylphosphino) ethane.
- These carbodiimidization catalysts can be used alone or in combination of two or more.
- Preferred examples of the carbodiimidization catalyst include phospholene oxide compounds, more preferably 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene- 1-oxide is mentioned.
- the activity of carbodiimidization can be improved, the reaction temperature can be lowered, and side reactions such as uretonimination can be suppressed to obtain a polycarbodiimide composition with high yield.
- the content of the carbodiimide group can be improved.
- 3-methyl-1-phenyl-2-phospholene-1-oxide is particularly preferred from the viewpoint of obtaining a cured resin (explained later) excellent in water resistance.
- the blending ratio of the carbodiimidization catalyst is, for example, 0.01 parts by mass or more, preferably 0.05 parts by mass or more with respect to 100 parts by mass of polyisocyanate (polyisocyanate used in the urethanization step). 20 parts by mass or less, preferably 10 parts by mass or less.
- the reaction conditions in the carbodiimidization step are set so that the content ratio of the carbodiimide group of the obtained polycarbodiimide composition falls within a specific range described later.
- the reaction temperature is, for example, 125 ° C. or higher, under atmospheric pressure and an inert gas (such as nitrogen gas) atmosphere, 130 degreeC or more, More preferably, it is 135 degreeC or more, for example, 160 degrees C or less, Preferably, it is 155 degrees C or less, More preferably, it is less than 155 degreeC.
- the reaction time is, for example, 1 hour or more, preferably 3 hours or more, for example, 50 hours or less, preferably 40 hours or less.
- reaction product (urethane modified polyisocyanate) obtained in the urethanization step can be decarboxylated and condensed through an isocyanate group, and a carbodiimide group can be efficiently generated. .
- the reaction temperature is equal to or higher than the lower limit
- the carbodiimidization reaction can proceed while promoting the reaction of the generated uretonimine to decompose into carbodiimide and isocyanate groups.
- the temperature is lower than the lower limit, this thermal decomposition reaction hardly occurs, the content of uretonimine increases, and the content of carbodiimide groups decreases.
- the molecular weight increases due to the increase in uretonimine, and the reaction solution may solidify.
- the reaction temperature is not more than the above upper limit, the polymerization loss can be reduced.
- the reaction solution is preferably refluxed in the presence of an organic solvent from the viewpoint of smoothly causing a carbodiimidization reaction and promoting decarboxylation condensation. That is, a carbodiimidization reaction is performed under reflux.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, such as nitriles such as acetonitrile, alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and amyl acetate.
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
- nitriles such as acetonitrile
- alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and amyl acetate.
- Aliphatic hydrocarbons such as n-hexane, n-heptane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, for example Methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene Glycol ether esters such as recall methyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol Ethers such
- the organic solvent is preferably an organic solvent having a reflux temperature within the above reaction temperature range.
- organic solvent examples include xylene, ethylene glycol methyl ether acetate, and propylene glycol methyl ether acetate.
- the blending ratio of the organic solvent is not particularly limited, but is, for example, 50 parts by mass or more, preferably 100 parts by mass or more with respect to 100 parts by mass of polyisocyanate (polyisocyanate used in the urethanization step). , 2000 parts by mass or less, preferably 500 parts by mass or less.
- the uretonimine decomposition reaction By refluxing the reaction solution in the presence of an organic solvent, the uretonimine decomposition reaction can be promoted and the carbodiimidization reaction can be carried out smoothly, and the carbon dioxide gas generated by the carbodiimidization of the isocyanate group can be eliminated. Therefore, carbodiimidization can be promoted.
- a polycarbodiimide composition containing a urethane group and a carbodiimide group and optionally containing a uretonimine group can be obtained.
- a urethane group derived from an isocyanate group of a polyisocyanate is generated in the urethanization step.
- reaction product (urethane modified polyisocyanate) obtained in the urethanization step is heated in the carbodiimidization step, a carbodiimide group derived from the isocyanate group at the molecular end is generated, and in some cases, A part of the generated carbodiimide group reacts with an isocyanate group at the molecular end to generate a uretonimine group.
- the uretonimine group is thermally decomposed by continued heating in the carbodiimidization step, and the carbodiimide group and the isocyanate group at the molecular end are regenerated, and further, a carbodiimide group derived from the isocyanate group at the molecular end is generated. .
- the isocyanate group of the polyisocyanate is converted into a urethane group and a carbodiimide group (and possibly a uretonimine group).
- the polycarbodiimide composition obtained in the above-described carbodiimidization step can be further reacted with an alcohol as necessary.
- the urethanization step before the carbodiimidization step may be referred to as a first urethanization step
- the urethanization step after the carbodiimidization step may be referred to as a second urethanization step.
- the polycarbodiimide composition obtained in the carbodiimidization process further has an isocyanate group at the molecular end
- the polycarbodiimide composition is reacted with an alcohol to thereby react the isocyanate at the molecular end.
- the group can be urethanized.
- examples of the alcohol include the oxyethylene-free alcohol described above.
- the blending ratio of the alcohols in the second urethanization step is the polyisocyanate used in the first urethanization step, where the total amount of alcohols used in the first urethanization step and alcohols used in the second urethanization step is Is adjusted to a predetermined ratio.
- Exceeds 2 for example, preferably 3 or more, more preferably 4 or more, for example, 16 or less, preferably 14 or less, more preferably 10 or less.
- the above urethanization catalyst may be added as necessary.
- the compounding ratio of a urethanization catalyst is not restrict
- reaction temperature is preferably in the same range as the reaction temperature in the carbodiimidization step under normal pressure and an inert gas (for example, nitrogen gas) atmosphere.
- reaction time is 15 minutes or more, for example, Preferably, it is 30 minutes or more, for example, is 5 hours or less, Preferably, it is 1 hour or less.
- the second urethanization step when the second urethanization step is carried out, the amount of by-products derived from alcohols increases, the molecular weight increases rapidly, the fluidity decreases, and the workability decreases. Dispersibility in the product may be reduced. Therefore, preferably, the second urethanization step is not performed, and only the first urethanization step and the carbodiimidization step are performed.
- polycarbodiimide composition is not limited to the above,
- polyisocyanate, a carbodiimidization catalyst, and alcohol can be mix
- polycarbodiimide composition for example, unreacted polyisocyanate, unreacted alcohols, low molecular weight compounds (by-products), organic solvents, carbodiimidization catalysts, urethanization catalysts, etc. are distilled. It can also be removed by known methods such as extraction and filtration.
- the polycarbodiimide composition may further contain known additives, for example, storage stabilizers (eg, o-toluenesulfonamide, p-toluenesulfonamide), plasticizers, antiblocking agents, heat-resistant stability, if necessary.
- storage stabilizers eg, o-toluenesulfonamide, p-toluenesulfonamide
- plasticizers eg., o-toluenesulfonamide, p-toluenesulfonamide
- antiblocking agents heat-resistant stability
- heat-resistant stability if necessary.
- An agent, a light resistance stabilizer, an antioxidant, a release agent, a catalyst, a pigment, a dye, a lubricant, a filler, a hydrolysis inhibitor, and the like can be added at an appropriate timing.
- the addition ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.
- polycarbodiimide composition can be used alone or in combination of two or more.
- the content ratio of the oxyethylene group in the polycarbodiimide composition thus obtained is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, as described above. For example, it is 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.
- Such a polycarbodiimide composition is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing an oxyethylene-containing alcohol and an oxyethylene-free alcohol, the oxyethylene-free alcohol.
- the solubility parameter is less than or equal to the predetermined value.
- such a polycarbodiimide composition can obtain a cured resin (described later) excellent in film formability, water resistance and chemical resistance, and is excellent in storage stability.
- a cured resin (described later) excellent in film formability, water resistance and chemical resistance can be obtained. Moreover, the fall of handling property in the case of storing the polycarbodiimide composition can be suppressed. Furthermore, also when the polycarbodiimide composition after storage is used, a cured resin (described later) having excellent film forming properties, water resistance and chemical resistance can be obtained.
- the polycarbodiimide composition can be produced efficiently.
- a polycarbodiimide composition is excellent in storage stability and can obtain the resin hardened
- the resin composition contains a curing agent including a polycarbodiimide composition and a main component having a carboxyl group.
- the curing agent is not particularly limited as long as it contains a polycarbodiimide composition.
- a polycarbodiimide composition for example, an aqueous dispersion in which the polycarbodiimide composition is dispersed in water (hereinafter referred to as an aqueous dispersion composition) or a polycarbodiimide composition. It is prepared as a solution in which the product is dissolved in an organic solvent (hereinafter referred to as a solution composition).
- the water dispersion composition contains a polycarbodiimide composition and water.
- the method for dispersing the polycarbodiimide composition in water is not particularly limited, and examples thereof include a method of adding water to the polycarbodiimide composition and stirring, a method of adding the polycarbodiimide composition to water, and a method of stirring. .
- water is added to the polycarbodiimide composition.
- the ratio of the polycarbodiimide composition and water is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the aqueous dispersion composition (that is, the solid content concentration) is, for example, 5% by mass or more, preferably It is 10 mass% or more, for example, 90 mass% or less, Preferably, it is 80 mass% or less.
- the curing agent is a water-dispersed composition
- compatibility with the aqueous resin (main agent) can be improved, and a cured product excellent in film formability, water resistance and chemical resistance can be obtained.
- a solution composition contains the said polycarbodiimide composition, it is excellent in storage stability.
- the solution composition contains a polycarbodiimide composition and an organic solvent.
- organic solvent examples include the organic solvents described above, and preferably methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.
- the method for dissolving the polycarbodiimide composition in the organic solvent is not particularly limited, and a method of adding and stirring the organic solvent to the polycarbodiimide composition, a method of adding and stirring the polycarbodiimide composition to the organic solvent, etc. Is mentioned.
- an organic solvent is added to the polycarbodiimide composition.
- the ratio between the polycarbodiimide composition and the organic solvent is not particularly limited, but the concentration of the polycarbodiimide composition (resin component) in the solution composition (that is, the solid content concentration) is, for example, 5% by mass or more, preferably It is 10 mass% or more, for example, 90 mass% or less, Preferably, it is 80 mass% or less.
- the curing agent is a solution composition
- compatibility with the oil-based resin (main agent) can be improved, and a cured product excellent in film formability, water resistance, and chemical resistance can be obtained.
- a solution composition contains the said polycarbodiimide composition, it is excellent in storage stability.
- Examples of the main agent having a carboxyl group include a water-based resin having a carboxyl group and an oil-based resin having a carboxyl group.
- water-based resin having a carboxyl group examples include a hydrophilic polymer having a carboxyl group, and specifically, a hydrophilic polyester resin having a carboxyl group, a hydrophilic polyamide resin having a carboxyl group, and a carboxyl group.
- These aqueous resins having a carboxyl group can be used alone or in combination of two or more.
- aqueous resin having a carboxyl group examples include a hydrophilic polyurethane resin having a carboxyl group and a hydrophilic acrylic resin having a carboxyl group.
- oil-based resin having a carboxyl group examples include a hydrophobic polymer having a carboxyl group, and specifically, a hydrophobic polyester resin having a carboxyl group, a hydrophobic polyamide resin having a carboxyl group, and a carboxyl group.
- the above polyolefin) resin etc. are mentioned.
- These oil-based resins having a carboxyl group can be used alone or in combination of two or more.
- oil-based resin having a carboxyl group examples include a hydrophobic polyurethane resin having a carboxyl group and a hydrophobic acrylic resin having a carboxyl group.
- the main agent and the curing agent a combination in which the main agent is an aqueous resin and the curing agent is an aqueous dispersion composition is preferable.
- a combination in which the main agent is an oil-based resin and the curing agent is a solution composition is also preferable.
- the resin composition is preferably a combination of an aqueous main component and an aqueous dispersion composition.
- the resin composition is not particularly limited as long as it contains the above-described main agent and the above-described curing agent, and the two-component type in which the main agent and the curing agent are separately prepared and mixed at the time of use.
- it may be a one-component type in which a main agent and a curing agent are premixed.
- the resin composition is preferably a two-component resin composition.
- the content ratio of the main agent and the curing agent is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, for example, 99.5 parts by mass or less, preferably 100 parts by mass with respect to their total amount 95.0 parts by mass or less.
- curing agent is 0.5 mass part or more, for example, Preferably, it is 5 mass parts or more, for example, is 90 mass parts or less, Preferably, it is 70 mass parts or less.
- the molar ratio of the carbodiimide group in the curing agent to the carboxyl group in the main agent is, for example, 0.1 or more, preferably 0.2 or more, for example, 2.0 or less, preferably 1.5. It is as follows.
- the main agent and the curing agent if necessary, either or both of them, for example, epoxy resin, catalyst, coating improver, leveling agent, antifoaming agent, antioxidant, ultraviolet absorber, etc.
- Additives such as stabilizers, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, antifungal agents, and silane coupling agents may be added. The amount of these additives is appropriately determined depending on the purpose and application.
- the above-described aqueous resin having a carboxyl group, and / or the above-described oil-based resin having a carboxyl group, and other resins can be used in combination.
- a hydroxyl group-containing polyurethane resin, a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, Melamine resin etc. can be used in combination.
- the curing agent the above-described polycarbodiimide composition and other curing agents (for example, polyisocyanate resin, epoxy resin, etc.) can be used in combination.
- the method for producing the cured resin product is not particularly limited.
- the resin composition is a one-component type
- the resin composition is directly applied to an object to be coated or an adherend.
- the main agent and the curing agent are mixed, and the obtained mixture is applied to an object to be coated or an adherend.
- a resin hardened material is obtained by carrying out heat hardening of a resin composition.
- the curing temperature is relatively low, and specifically, for example, 100 ° C. or lower, preferably 80 ° C. or lower.
- it is 20 degreeC or more, Preferably, it is 30 degreeC or more.
- the curing time is relatively short, specifically, for example, 1 hour or less, preferably 30 minutes or less. For example, it is 1 minute or more, preferably 5 minutes or more.
- the cured resin cured by heating can be further dried.
- the drying temperature may be room temperature, for example, 10 ° C. or higher, preferably 15 ° C. or higher, for example, 40 ° C. or lower, preferably 30 ° C. or lower.
- drying time is, for example, 1 minute or more, preferably 5 minutes or more, for example, 2 hours or less, preferably 1 hour or less.
- the obtained cured resin is a cured product of the resin composition having excellent storage stability, it is excellent in productivity and excellent in film formability, water resistance and chemical resistance.
- the cured resin obtained using the polycarbodiimide composition is also excellent in light resistance (weather resistance).
- the resin composition and the cured resin are made of a coating material, an adhesive material (adhesive), an adhesive material (adhesive material), an ink, a sealant, a molding material, a foam and an optical material, polyester, polylactic acid, polyamide, It is suitably used in various fields such as resin modifiers for modifying resins such as polyimide and polyvinyl alcohol, textile printing treatment agents, and fiber treatment agents.
- coating material for example, plastic coatings, automotive exterior coatings, automotive interior coatings, electrical and electronic material coatings, optical material (lens, etc.) coatings, building material coatings, glass coat coatings, woodworking Examples thereof include paints, film coating paints, ink paints, artificial and synthetic leather paints (coat agents), can paints (coat agents), paper coat paints, and thermal paper coat paints.
- paints for plastics include, for example, paints for molded articles in which plastic materials (for example, various polymer materials such as polyolefins, ABS, polycarbonates, polyamides, polyesters, and composites thereof) are used. Paints for casings (mobile phones, smartphones, PCs, tablets, etc.), paints for automobile parts (automobile interior materials, headlamps, etc.), paints for household appliances, paints for robot materials, paints for furniture, stationery Examples thereof include paints for flexible materials such as paints, rubbers, elastomers and gels, paints for eyewear materials (lenses, etc.), paints for optical lenses of electronic devices (surface coating agents), and the like.
- plastic materials for example, various polymer materials such as polyolefins, ABS, polycarbonates, polyamides, polyesters, and composites thereof
- Paints for casings mobile phones, smartphones, PCs, tablets, etc.
- paints for automobile parts automobile interior materials, headlamps, etc.
- paints for household appliances paint
- examples of the above-mentioned automotive exterior paint include paints for new cars (intermediate coating, base, top, etc.), automotive repairs (intermediate coating, base, top, etc.), and paints for exterior parts (aluminum wheels, bumpers, etc.). Etc.
- the above-mentioned water-based resin having a carboxyl group and the above-described oil-based resin having a carboxyl group can be used as the main agent.
- an aqueous resin having a carboxyl group is used.
- the water-based resin having a carboxyl group examples include a hydrophilic acrylic resin having a carboxyl group, a hydrophilic polyurethane resin having a carboxyl group, and a hydrophilic polyester resin having a carboxyl group, and more preferably, a hydrophilic resin having a carboxyl group. And a hydrophilic acrylic resin having a carboxyl group.
- two or more types of aqueous resins having a carboxyl group as described above can be used in combination.
- the above-described aqueous resin having a carboxyl group, and / or the above-described oil-based resin having a carboxyl group, and other resins can be used in combination.
- a hydroxyl group-containing polyurethane resin, a hydroxyl group-containing acrylic resin, a hydroxyl group-containing polyester resin, Melamine resin etc. can be used in combination.
- the solid content concentration of the main agent is usually 5% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more. 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.
- the acid value in terms of solid content of the main agent is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, for example, 200 mgKOH / g or less, preferably 100 mgKOH / g or less.
- curing agent examples include the polycarbodiimide composition described above, and the polycarbodiimide composition and other curing agents (for example, polyisocyanate resin, epoxy resin, etc.) can be used in combination.
- film coating paint examples include, for example, paints for optical members (optical films, optical sheets, etc.), optical coating materials, textile paints, electronic electrical material paints, food packaging paints, medical film paints, Examples include cosmetic package paints, decorative film paints, and release film paints.
- adhesives examples include adhesives for packaging materials, adhesives for electrical equipment, adhesives for liquid crystal displays (LCD), adhesives for organic EL displays, adhesives for organic EL lighting, and display devices (electronic paper and plasma displays) Etc.) Adhesive for LED, Adhesive for LED, Adhesive for automobile interior and exterior, Adhesive for home appliance, Adhesive for building material, Adhesive for solar battery back sheet, Adhesive for various batteries (lithium ion battery, etc.) Is mentioned.
- examples of the resin for ink include vehicles of various inks (plate ink, screen ink, flexo ink, gravure ink, jet ink, textile printing ink, etc.).
- polycarbodiimide composition is not limited to the above.
- a hydrolysis-resistant inhibitor such as polyester polyol, acid modification, for example, Compounding with maleic acid-modified polyolefin, or polyolefin emulsion in which acid-modified polyolefin is dispersed in water, compounding with acrylic emulsion containing acid sites, curing agent, converging material for various fibers such as carbon fiber and glass fiber, CFRP, It can be suitably used as a reinforcing material for fiber reinforced plastic such as FRP, a sizing agent or a curing agent.
- Production Example 1 (Production of pentamethylene diisocyanate) 99.9% by mass of 1,5-pentamethylene diisocyanate (hereinafter sometimes abbreviated as PDI) was obtained by the same operation as in Example 1 in the specification of International Publication Pamphlet WO2012 / 121291.
- PDI 1,5-pentamethylene diisocyanate
- Example 1 Provide of polycarbodiimide composition
- 100.0 parts by mass of the pentamethylene diisocyanate obtained in Production Example 1 at room temperature 100.0 parts by mass of the pentamethylene diisocyanate obtained in Production Example 1 at room temperature, 34.6 parts by mass of UNIOX M400 (manufactured by NOF Corporation, polyethylene glycol monomethyl ether molecular weight 400) and 9.6 parts by mass of isobutanol were charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 6 hours (urethanization step).
- the reaction mixture was cooled to 80 ° C., and PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.
- a polycarbodiimide composition As a result of taking out a part of the obtained polycarbodiimide composition and measuring the E-type viscosity at 25 ° C., it was 1100 mPa ⁇ s.
- the E-type viscosity at 25 ° C. was measured and found to be 2500 mPa ⁇ s.
- aqueous dispersion composition aqueous dispersion composition
- the polycarbodiimide composition was placed in a flask, heated to 80 ° C, and distilled water was gradually added so that the resin solid content was 40%. . After stirring for 5 minutes, it was cooled to room temperature. This obtained the water dispersion of the polycarbodiimide composition. Further, an aqueous dispersion was similarly prepared for a polycarbodiimide composition stored at 25 ° C. for 2 months in a nitrogen atmosphere.
- polycarbodiimide composition solution solution composition
- the polycarbodiimide composition was placed in a flask, heated to 80 ° C, and butyl acetate was gradually added so that the resin solid content was 40%. After stirring for 5 minutes, it was cooled to room temperature. This obtained the solution of the polycarbodiimide composition. Further, an aqueous dispersion was similarly prepared for a polycarbodiimide composition stored at 25 ° C. for 2 months in a nitrogen atmosphere.
- aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. And 1.5 mass parts of hardening
- Example 2 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 9.6 parts by mass of 2-butanol was used instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 3 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 11.4 parts by mass of 2-methyl-1-butanol and 306.5 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 4 A polycarbodiimide composition was obtained in the same manner as in Example 1, except that 11.4 parts by mass of 2,2-dimethyl-1-propanol and 306.5 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 5 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 13.5 parts by mass of 3-methoxy-1-butanol and 310.8 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 6 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 16.9 parts by mass of 1-octanol and 317.8 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 7 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 16.9 parts by mass of 2-ethyl-1-hexanol and 317.8 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 8 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 24.2 parts by mass of 1-dodecanol and 332.9 parts by mass of PMA were charged instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 9 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 35.1 parts by mass of 1-octadecanol and 355.5 parts by mass of PMA were used instead of isobutanol.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- the polycarbodiimide composition stored in a nitrogen atmosphere for 2 months at 25 ° C. solidified (the solidified product was waxy), and an aqueous dispersion could not be obtained.
- Example 10 Example 1 except that 43.2 parts by mass of UNIOX M400, 24.0 parts by mass of isobutanol and 350.6 parts by mass of PMA were charged, and the reaction time of the carbodiimidization step was changed to 6.5 hours. A polycarbodiimide composition was obtained in the same manner.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 11 The same method as in Example 1 except that 23.1 parts by mass of UNIOX M400, 6.4 parts by mass of isobutanol and 272.2 parts by mass of PMA were charged, and the reaction time of the carbodiimidization step was changed to 8 hours. A polycarbodiimide composition was obtained.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 12 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 12.4 parts by mass of UNIOX M400, 13.7 parts by mass of isobutanol, and 265.2 parts by mass of PMA were charged.
- Example 1 An aqueous dispersion and solution of the polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared. Thereafter, a resin composition was prepared in the same manner as in Example 1.
- Example 13 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 74.1 parts by mass of UNIOX M400, 2.3 parts by mass of isobutanol, and 369.5 parts by mass of PMA were charged.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 14 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 9.6 parts by mass of tert-butanol was used instead of isobutanol and the reaction time of the urethanization step was changed to 12 hours.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 15 To a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of 1,3-xylylene diisocyanate and 28.3 parts by mass of UNIOX M400 at room temperature, 7.9 parts by mass of isobutanol was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 2 hours (urethanization step).
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 16 In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane and 27. UNIOX M400 at room temperature. 5 parts by mass and 7.6 parts by mass of isobutanol were charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 7 hours (urethanization step).
- reaction mixture was cooled to 80 ° C., and PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 17 In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of isophorone diisocyanate, 33.0 parts by mass of UNIOX M400, and 8. 1 part by mass was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 7 hours (urethanization step).
- reaction mixture was cooled to 80 ° C., and PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Example 18 Example 1 except that 100 parts by mass of hexamethylene diisocyanate, 31.7 parts by mass of UNIOX M400, 8.8 parts by mass of isobutanol, and 295.1 parts by mass of PMA were charged instead of pentamethylene diisocyanate. A polycarbodiimide composition was obtained by this method.
- Example 2 an aqueous dispersion and solution of the polycarbodiimide composition were prepared to prepare a resin composition.
- Comparative Example 1 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 4.2 parts by mass of methanol and 291.5 parts by mass of PMA were charged instead of isobutanol.
- an aqueous dispersion and solution of a polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared.
- the polycarbodiimide composition stored in a nitrogen atmosphere at 25 ° C. for 2 months was It solidified (the solidified product was rubbery), and an aqueous dispersion and solution could not be obtained.
- Comparative Example 2 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 9.6 parts by mass of 1-butanol was used instead of isobutanol.
- an aqueous dispersion and solution of a polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared.
- the polycarbodiimide composition stored in a nitrogen atmosphere at 25 ° C. for 2 months was It solidified (the solidified product was rubbery), and an aqueous dispersion and solution could not be obtained.
- Comparative Example 3 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 11.7 parts by mass of 1-methoxy-2-propanol and 307.1 parts by mass of PMA were charged instead of isobutanol.
- an aqueous dispersion and solution of a polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared.
- the polycarbodiimide composition stored in a nitrogen atmosphere at 25 ° C. for 2 months was It solidified (the solidified product was rubbery), and an aqueous dispersion and solution could not be obtained.
- Comparative Example 4 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 13.0 parts by mass of cyclohexanol and 309.8 parts by mass of PMA were charged instead of isobutanol.
- an aqueous dispersion and solution of a polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared.
- the polycarbodiimide composition stored in a nitrogen atmosphere at 25 ° C. for 2 months was It solidified (the solidified product was rubbery), and an aqueous dispersion and solution could not be obtained.
- Comparative Example 5 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 14.0 parts by mass of benzyl alcohol and 311.9 parts by mass of PMA were charged instead of isobutanol.
- an aqueous dispersion and solution of a polycarbodiimide composition were prepared in the same manner as in Example 1, and a resin composition was prepared.
- the polycarbodiimide composition stored in a nitrogen atmosphere at 25 ° C. for 2 months was It solidified (the solidified product was rubbery), and an aqueous dispersion and solution could not be obtained.
- Comparative Example 6 A polycarbodiimide composition was obtained in the same manner as in Example 1 except that 16.1 parts by mass of 4-methoxyphenol and 316.2 parts by mass of PMA were used instead of isobutanol, but the PMA was distilled under reduced pressure. While leaving, it gradually thickened and solidified (the solidified product was rubbery), so an aqueous dispersion and solution of polycarbodiimide could not be obtained.
- Comparative Example 7 A polycarbodiimide composition was synthesized with reference to the method described in Synthesis Example 83 of JP-A-10-316930.
- ⁇ Film forming properties> The appearance of the coating film (80 ° C. for 10 minutes) was visually evaluated. The criteria for evaluation are as follows. Good A clear and smooth coating was confirmed. Defects were confirmed.
- the polycarbodiimide composition of the present invention the method for producing the polycarbodiimide composition, the water dispersion composition, the solution composition, the resin composition and the cured resin are a coating material, an adhesive material (adhesive), and an adhesive material (adhesive material). , Inks, sealants, molding materials, foams and optical materials, resin modifiers, textile processing agents, fiber processing agents and the like.
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Abstract
Description
イソブタノール、2-ブタノール、2-メチル-1-ブタノール、2,2-ジメチル-1-プロパノール、3-メトキシ-1-ブタノール、1-オクタノール、2-エチル-1-ヘキサノールおよび1-ドデカノールからなる群から選択される少なくとも1種である、上記[1]~[4]のいずれか一項に記載のポリカルボジイミド組成物を含んでいる。
ポリカルボジイミド組成物に対するオキシエチレン基の含有割合は、仕込み量および化学構造式から算出した。
国際公開パンフレットWO2012/121291号の明細書における実施例1と同じ操作にて、99.9質量%の1,5-ペンタメチレンジイソシアネート(以後PDIと略する場合がある。)を得た。
・ポリカルボジイミド組成物の製造
撹拌器、温度計、還流管、および窒素導入管を備えた四つ口フラスコに、室温下で、製造例1で得られたペンタメチレンジイソシアネートを100.0質量部、ユニオックスM400(日本油脂社製 ポリエチレングリコールモノメチルエーテル 分子量400)を34.6質量部、イソブタノールを9.6質量部装入した。窒素を導入しながら、常圧下で80℃に加温し、6時間撹拌した(ウレタン化工程)。
ポリカルボジイミド組成物をフラスコに入れ、80℃に加温し、樹脂固形分が40%になるように蒸留水を徐々に加えた。5分間撹拌した後に、室温まで冷却した。これにより、ポリカルボジイミド組成物の水分散体を得た。また、25℃で2ヵ月間、窒素雰囲気下で保存したポリカルボジイミド組成物についても、同様に水分散体を調製した。
ポリカルボジイミド組成物をフラスコに入れ、80℃に加温し、樹脂固形分が40%になるように酢酸ブチルを徐々に加えた。5分間撹拌した後に、室温まで冷却した。これにより、ポリカルボジイミド組成物の溶液を得た。また、25℃で2ヵ月間、窒素雰囲気下で保存したポリカルボジイミド組成物についても、同様に水分散体を調製した。
得られたポリカルボジイミド組成物の水分散体を硬化剤とした。そして、硬化剤1.5質量部と、主剤としてのポリウレタンディスパージョン(固形分30質量%、カルボキシル基当量3100g/mol)98.5質量部とを混合し、樹脂組成物を調製した。
得られたポリカルボジイミド組成物の溶液を硬化剤とした。そして、硬化剤1.0質量部と、主剤としてのアクリル樹脂(固形分50質量%、固形分のカルボキシル基当量2004g/mol)39.2質量部と、溶剤としての酢酸ブチル59.8質量部とを混合し、樹脂組成物を調製した。
イソブタノールの代わりに2-ブタノールを9.6質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに2-メチル-1-ブタノールを11.4質量部、PMAを306.5質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに2,2-ジメチルー1-プロパノールを11.4質量部、PMAを306.5質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに3-メトキシ-1-ブタノールを13.5質量部、PMAを310.8質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに1-オクタノールを16.9質量部、PMAを317.8質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに2-エチル-1-ヘキサノールを16.9質量部、PMAを317.8質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに1-ドデカノールを24.2質量部、PMAを332.9質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに1-オクタデカノールを35.1質量部、PMAを355.5質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
ユニオックスM400を43.2質量部、イソブタノールを24.0質量部、PMAを350.6質量部装入し、カルボジイミド化工程の反応時間を6.5時間に変更した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
ユニオックスM400を23.1質量部、イソブタノールを6.4質量部、PMAを272.2質量部装入し、カルボジイミド化工程の反応時間を8時間に変更した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
ユニオックスM400を12.4質量部、イソブタノールを13.7質量部、PMAを265.2質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
ユニオックスM400を74.1質量部、イソブタノールを2.3質量部、PMAを369.5質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりにtert‐ブタノールを9.6質量部装入し、ウレタン化工程の反応時間を12時間に変更した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
撹拌器、温度計、還流管、および窒素導入管を備えた四つ口フラスコに、室温下で、1,3-キシリレンジイソシアネートを100.0質量部、ユニオックスM400を28.3質量部、イソブタノールを7.9質量部装入した。窒素を導入しながら、常圧下で80℃に加温し、2時間撹拌した(ウレタン化工程)。
撹拌器、温度計、還流管、および窒素導入管を備えた四つ口フラスコに、室温下で、1,3-ビス(イソシアナトメチル)シクロヘキサンを100.0質量部、ユニオックスM400を27.5質量部、イソブタノールを7.6質量部装入した。窒素を導入しながら、常圧下で80℃に加温し、7時間撹拌した(ウレタン化工程)。
撹拌器、温度計、還流管、および窒素導入管を備えた四つ口フラスコに、室温下で、イソホロンジイソシアネートを100.0質量部、ユニオックスM400を33.0質量部、イソブタノールを8.1質量部装入した。窒素を導入しながら、常圧下で80℃に加温し、7時間撹拌した(ウレタン化工程)。
ペンタメチレンジイソシアネートの代わりにヘキサメチレンジイソシアネートを100質量部、ユニオックスM400を31.7質量部、イソブタノールを8.8質量部、PMAを295.1質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりにメタノールを4.2質量部、PMAを291.5質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに1-ブタノールを9.6質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに1-メトキシ-2-プロパノールを11.7質量部、PMAを307.1質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりにシクロヘキサノールを13.0質量部、PMAを309.8質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりにベンジルアルコールを14.0質量部、PMAを311.9質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得た。
イソブタノールの代わりに4-メトキシフェノールを16.1質量部、PMAを316.2質量部装入した以外は実施例1と同じ方法でポリカルボジイミド組成物を得たが、PMAを減圧下で留去している時に、徐々に増粘していき、固化してしまったため(固化物はゴム状であった)、ポリカルボジイミドの水分散体および溶液を得ることはできなかった。
特開平10-316930公報の合成例83に記載されている方法を参考にポリカルボジイミド組成物を合成した。
<安定性試験>
・40℃における安定性試験
得られたポリカルボジイミド組成物1.0質量部を10mLのスクリュー瓶に入れて、窒素ブローをした後に、スクリューキャップで蓋をし、40℃にて保管し、流動性が消失するまで(瓶を逆さまにして、ポリカルボジイミドが流れなくなるまで)を観測した。また、調製したポリカルボジイミド組成物の溶液についても同様に試験した。
4 流動性が消失するまでに1ヵ月以上要した。
3 流動性が消失するまで2週間以上1ヵ月未満であった。
2 流動性が消失するまで1週間以上2週間未満であった。
1 流動性が消失するまで1週間未満であった。
<評価>
・塗膜の評価
250ミルのドクターブレードを用いて、樹脂組成物を標準試験板(JIS-G-3303 SPTE)に塗布した後、80℃で10分間および30分間乾燥させ、さらに室温で1時間乾燥させ、樹脂硬化物からなる塗膜を得た。得られた塗膜を下記の方法で評価した。
塗膜(80℃10分間)の外観を目視で評価した。評価の基準を下記する。
良好 クリアで平滑な塗膜が確認された。
不良 ブツが確認された。
塗膜(80℃10分間)上に、蒸留水をスポットして、23℃24時間後の塗膜外観の変化を目視で確認した。評価の基準を下記する。
良好 変化が確認されなかった。
不良 白化が確認された。
上塗膜(80℃10分間および30分間)に、水系の樹脂組成物の場合には、メチルエチルケトン、溶剤系の樹脂組成物の場合には50%エタノール水溶液を浸透させたガーゼを、50gの荷重で押し当てながら擦り、塗膜が割れるまでの回数を測定した。評価の基準を下記する。
4 300回以上で塗膜が割れた
3 250回以上300回未満で塗膜が割れた。
2 100回以上250回未満で塗膜が割れた。
1 100回未満で塗膜が割れた。
Claims (13)
- 1級イソシアネート基を有するポリイソシアネートと、アルコール類との反応生成物であり、
前記アルコール類が、
オキシエチレン基を含有する少なくとも1種のオキシエチレン含有アルコールと、
オキシエチレン基を含有しない少なくとも1種のオキシエチレン不含アルコールと
を含み、
少なくとも1種の前記オキシエチレン不含アルコールの溶解度パラメータが、11.20(cal/cm3)1/2以下である
ことを特徴とする、ポリカルボジイミド組成物。 - オキシエチレン基の含有割合が、前記ポリカルボジイミド組成物に対して、10質量%以上35質量%以下である
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 溶解度パラメータが11.20(cal/cm3)1/2以下である前記オキシエチレン不含アルコールが、
第1級アルコールおよび/または第2級アルコールである
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 溶解度パラメータが11.20(cal/cm3)1/2以下である前記オキシエチレン不含アルコールが、
炭素原子を4個以上12個以下含む1価のアルコールである
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 溶解度パラメータが11.20(cal/cm3)1/2以下である前記オキシエチレン不含アルコールが、
イソブタノール、2-ブタノール、2-メチル-1-ブタノール、2,2-ジメチル-1-プロパノール、3-メトキシ-1-ブタノール、1-オクタノール、2-エチル-1-ヘキサノールおよび1-ドデカノールからなる群から選択される少なくとも1種である
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 前記ポリイソシアネートが、脂肪族ポリイソシアネートである
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 前記ポリイソシアネートがペンタメチレンジイソシアネートである
ことを特徴とする、請求項1に記載のポリカルボジイミド組成物。 - 1級イソシアネート基を有するポリイソシアネートと、アルコール類とをウレタン化反応させるウレタン化工程と、
前記ウレタン化工程における反応生成物を、カルボジイミド化触媒の存在下において加熱し、カルボジイミド化反応させるカルボジイミド化工程と
を備え、
前記アルコール類が、
オキシエチレン基を含有する少なくとも1種のオキシエチレン含有アルコールと、
オキシエチレン基を含有しない少なくとも1種のオキシエチレン不含アルコールと
を含み、
少なくとも1種の前記オキシエチレン不含アルコールの溶解度パラメータが、11.20(cal/cm3)1/2以下である
ことを特徴とする、ポリカルボジイミド組成物の製造方法。 - 前記アルコール類の水酸基に対する、前記ポリイソシアネートのイソシアネート基の当量比(NCO/OH)が、2を超過し10以下であることを特徴とする、
請求項8に記載のポリカルボジイミド組成物の製造方法。 - 請求項1に記載のポリカルボジイミド組成物が、
固形分濃度5質量%以上90質量%以下の割合で水に分散された水分散液である
ことを特徴とする、水分散組成物。 - 請求項1に記載のポリカルボジイミド組成物が、
固形分濃度5質量%以上90質量%以下の割合で有機溶媒に溶解された溶液である
ことを特徴とする、溶液組成物。 - カルボキシル基を有する主剤と、
請求項1に記載のポリカルボジイミド組成物を含む硬化剤と
を含有することを特徴とする、樹脂組成物。 - 請求項12に記載の樹脂組成物の硬化物であることを特徴とする、樹脂硬化物。
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CN201780085691.1A CN110300769B (zh) | 2017-02-16 | 2017-06-20 | 聚碳二亚胺组合物、聚碳二亚胺组合物的制造方法、水分散组合物、溶液组合物、树脂组合物及树脂固化物 |
US16/485,811 US11390751B2 (en) | 2017-02-16 | 2017-06-20 | Polycarbodiimide composition, method for producing a polycarbodiimide composition, water-dispersed composition, solution composition, resin composition, and cured resin |
KR1020197022521A KR102240994B1 (ko) | 2017-02-16 | 2017-06-20 | 폴리카보다이이미드 조성물, 폴리카보다이이미드 조성물의 제조 방법, 수분산 조성물, 용액 조성물, 수지 조성물 및 수지 경화물 |
EP17896928.3A EP3584266B1 (en) | 2017-02-16 | 2017-06-20 | Polycarbodiimide composition, method for producing polycarbodiimide composition, water-dispersed composition, solution composition, resin composition, and resin cured article |
ES17896928T ES2968446T3 (es) | 2017-02-16 | 2017-06-20 | Composición de policarbodiimida, método para producir una composición de policarbodiimida, composición dispersa en agua, composición en disolución, composición de resina y artículo curado de resina |
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US20200048467A1 (en) | 2020-02-13 |
KR20190097273A (ko) | 2019-08-20 |
CN110300769A (zh) | 2019-10-01 |
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