JP2019011457A - Polycarbodiimide composition, production method for polycarbodiimide composition, aqueous dispersion composition, solution composition, resin composition, and cured resin object - Google Patents

Abstract

To provide a production method for obtaining a polycarbodiimide composition with excellent thermal stability; a polycarbodiimide composition; an aqueous dispersion composition and a solution composition containing a polycarbodiimide composition; a resin composition containing a polycarbodiimide composition; and a cured resin object that is obtained by curing the resin composition.SOLUTION: The present invention relates to a production method for a polycarbodiimide composition, containing the steps of causing a urethane reaction to occur between a polyisocyanate having a primary isocyanate group with an alcohol which contains an alcohol having an oxyethylene group and having a molecular weight of 200 or higher; and heating a resultant product in the presence of a carbodiimide catalyst for a carbodiimide reaction, to obtain a polycarbodiimide composition. In the method, the alcohol contains water, the water content being 1.0 mol or less relative to 100 mol of polyisocyanate.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polycarbodiimide composition, a polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition, and a cured resin product.

  Conventionally, in the fields of paints, adhesives, coating agents, and the like, resin compositions containing a main agent and a curing agent are known. For example, carbodiimide-based curing agents are known as curing agents.

  More specifically, as the carbodiimide-based curing agent, for example, pentamethylene diisocyanate, polyethylene glycol monomethyl ether, and 1-methoxy-2-propanol are urethanated, and a carbodiimidization catalyst (3-methyl-1- A polycarbodiimide composition obtained by adding (phenyl-2-phosphorin-1-oxide) to a carbodiimidization reaction has been proposed (see, for example, Patent Document 1 (Example 2)).

  And resin cured products, such as a coating film, can be obtained by drying and hardening the resin composition which consists of such a polycarbodiimide composition (curing agent) and a main ingredient.

International Publication WO2017 / 119443 Pamphlet

  However, the polycarbodiimide composition as described above, when the alcohol as the raw material contains an excessive amount of water, the thermal stability is not sufficient, the viscosity is increased by the heat during production, and the productivity (manufacturing workability, There is a problem of lowering the quality.

  The present invention relates to a method for producing a polycarbodiimide composition for obtaining a polycarbodiimide composition excellent in thermal stability and productivity, a polycarbodiimide composition, an aqueous dispersion composition containing a polycarbodiimide composition, a solution composition, and a polycarbodiimide A resin composition containing the composition, and further a cured resin obtained by curing the resin composition.

  The present invention [1] includes a urethanation step in which a polyisocyanate having a primary isocyanate group and an alcohol containing an oxyethylene group-containing alcohol having a molecular weight of 200 or more, and a reaction product in the urethanization step. A carbodiimidization step in which a product is heated in the presence of a carbodiimidization catalyst to obtain a polycarbodiimide composition, wherein the alcohols contain water, and the proportion of the water is the polyisocyanate 100. The manufacturing method of the polycarbodiimide composition which is 1.0 mol or less with respect to mol is included.

  In the present invention [2], the alcohol includes an EOPO combined alcohol having both an oxyethylene (EO) group and an oxypropylene (PO) group. In the EOPO combined alcohol, the oxyethylene group and the oxypropylene group The method for producing a polycarbodiimide composition according to the above [1], wherein the ratio of the oxyethylene group to the total mass is 20% by mass or more and 80% by mass or less.

  This invention [3] contains the manufacturing method of the polycarbodiimide composition as described in said [1] or [2] whose said polyisocyanate is aliphatic polyisocyanate.

  This invention [4] includes the manufacturing method of the polycarbodiimide composition as described in any one of said [1]-[3] whose said polyisocyanate is pentamethylene diisocyanate.

  The present invention [5] is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing an oxyethylene group-containing alcohol having a molecular weight of 200 or more, wherein the alcohol contains water, The polycarbodiimide composition whose ratio of water is 1.0 mol or less with respect to 100 mol of said polyisocyanates is included.

  The present invention [6] is an aqueous dispersion composition in which the polycarbodiimide composition according to the above [5] is an aqueous dispersion in which the solid concentration is 5% by mass or more and 90% by mass or less. Contains.

  This invention [7] contains the solution composition which is a solution by which the polycarbodiimide composition as described in said [5] was melt | dissolved in the organic solvent in the ratio of solid content concentration 5 mass% or more and 90 mass% or less. Yes.

  This invention [8] contains the resin composition containing the main ingredient which has a carboxyl group, and the hardening | curing agent containing the polycarbodiimide composition as described in said [5].

  This invention [9] contains the resin cured material which is a hardened | cured material of the resin composition as described in said [8].

  In the method for producing the polycarbodiimide composition of the present invention, the water content of the alcohol is determined in the reaction of the polyisocyanate having a primary isocyanate group and the alcohol containing an oxyethylene group-containing alcohol having a molecular weight of 200 or more. Since it is below fixed quantity, the polycarbodiimide composition excellent in thermal stability and productivity can be obtained.

  Therefore, the polycarbodiimide composition of the present invention, the aqueous dispersion composition and solution composition containing the polycarbodiimide composition, and the resin composition containing the polycarbodiimide composition are excellent in thermal stability and productivity.

  Moreover, since the cured resin of the present invention is a cured product of the above resin composition, it is excellent in productivity.

  In the method for producing a polycarbodiimide composition of the present invention, first, a polyisocyanate having a primary isocyanate group and an alcohol are subjected to a urethanization reaction, and then the resulting reaction product is subjected to a carbodiimidization reaction. Thereby, a polycarbodiimide composition is obtained as a reaction product of polyisocyanate having a primary isocyanate group and alcohols.

  More specifically, in this method, first, a polyisocyanate having a primary isocyanate group (hereinafter sometimes simply referred to as polyisocyanate) and an alcohol are subjected to a urethanization reaction (urethanization step).

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

  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.))

  Examples of polyisocyanates having primary isocyanate groups 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, oct 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).

  Examples of the araliphatic polyisocyanate having a primary isocyanate group include araliphatic diisocyanates such as 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI).

  These 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.

  From the viewpoint of availability, 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).

  1,5-pentamethylene diisocyanate has fewer carbon atoms and a smaller molecular weight than 1,6-hexamethylene diisocyanate. Therefore, when producing a polycarbodiimide composition having the same molecular weight, when 1,5-pentamethylene diisocyanate is used, the carbodiimide group concentration in the polycarbodiimide composition is increased compared to when 1,6-hexamethylene diisocyanate is used. be able to. As a result, a cured resin (described later) excellent in various physical properties (water resistance, chemical resistance, etc.) can be obtained. In addition, 1,5-pentamethylene diisocyanate having an odd number of carbon atoms is less crystalline than an 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.

  Furthermore, when 1,5-pentamethylene diisocyanate is used, compared with the case where 1,6-hexamethylene diisocyanate is used, thermal decomposition of the uretonimine group described later tends to occur, and therefore, a polycarbodiimide composition can be obtained with high yield. it can. In addition, since it can be handled at a low temperature, the high molecular weight of uretonimine can be suppressed.

  Examples of alcohols include alcohols having a molecular weight of 200 or more and alcohols having a molecular weight of less than 200.

  In addition, when alcohol is a monomer, the molecular weight can be calculated from the molecular structure. Moreover, when alcohol is a polymer, the molecular weight is measured by a gel permeation chromatograph as a number average molecular weight (polystyrene conversion).

  And alcohol contains the alcohol of molecular weight 200 or more as an essential component.

  As the alcohol having a molecular weight of 200 or more, an alcohol having a molecular weight of 200 or more containing an oxyethylene group (hereinafter sometimes referred to as an oxyethylene-containing alcohol having a molecular weight of 200 or more), an alcohol having a molecular weight of 200 or more not containing an oxyethylene group ( Hereinafter, it may be referred to as an oxyethylene-free alcohol having a molecular weight of 200 or more).

  The alcohol having a molecular weight of 200 or more contains an oxyethylene-containing alcohol having a molecular weight of 200 or more as an essential component.

The oxyethylene group (—CH ₂ CH ₂ O—) is a group composed of two carbon atoms, four hydrogen atoms, and one oxygen atom.

That is, an oxyethylene group (—CH ₂ CH ₂ O—) is a group in which one or more hydrogen atoms are substituted with other atomic groups (for example, an oxypropylene group (—CH (CH ₃ ) CH ₂ O—)). Etc.).

In addition, 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—), It is also distinguished from a propyl ether group (such as CH ₃ —CH ₂ CH ₂ O—).

An alcohol having such an oxyethylene group (—CH ₂ CH ₂ O—) structure in the molecule is defined as an oxyethylene-containing alcohol.

The oxyethylene-containing alcohol having a molecular weight of 200 or more can contain an oxypropylene group (—CH (CH ₃ ) CH ₂ O—) in addition to the oxyethylene group, and is further classified according to the presence or absence of the oxypropylene group. Is done.

  Specifically, as an oxyethylene-containing alcohol having a molecular weight of 200 or more, an alcohol having a molecular weight of 200 or more that contains an oxyethylene (EO) group and does not contain an oxypropylene (PO) group (hereinafter referred to as an EO-containing PO non-polymer having a molecular weight of 200 or more). And an alcohol having a molecular weight of 200 or more having both an oxyethylene (EO) group and an oxypropylene (PO) group (hereinafter referred to as an EOPO-containing alcohol having a molecular weight of 200 or more).

  An EO-containing PO-free alcohol having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more, which contains one or more oxyethylene groups in one molecule, does not contain oxypropylene, and contains one or more hydroxyl groups. is there.

  Examples of such an EO-containing PO-free alcohol include an EO-containing PO-free polyol having a molecular weight of 200 or more and an EO-containing PO-free monool having a molecular weight of 200 or more.

  An EO-containing PO-free polyol having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more, which contains one or more oxyethylene groups in one molecule, does not contain oxypropylene, and contains two or more hydroxyl groups. is there.

  Examples of the EO-containing PO-free polyol having a molecular weight of 200 or more include polyoxyethylene polyol.

  Polyoxyethylene polyol can be obtained, for example, by addition reaction of ethylene oxide (and not addition reaction of 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 (preferably less than 400), 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-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and them A mixture of hydrogenated bisphenol A, 1,4-dihydroxy Dihydric alcohols such as 2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, such as glycerin, trimethylolpropane, triisopropanolamine A trihydric alcohol such as tetramethylolmethane (pentaerythritol), a dihydric alcohol such as diglycerin, a pentahydric alcohol such as xylitol, such as sorbitol, mannitol, allitol, iditol, dulcitol, altoitol, inositol, Examples include hexavalent alcohols such as dipentaerythritol, for example, 7-valent alcohols such as perseitol, and octavalent alcohols such as sucrose. These can be used alone or in combination of two or more.

  The low molecular weight polyol is preferably a dihydric alcohol.

  In addition, it does not restrict | limit especially as a method of carrying out addition reaction of ethylene oxide with these low molecular weight polyols, A well-known method is employable.

  In addition, 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). For example, when a dihydric alcohol is used as the initiator, Bifunctional polyoxyethylene glycol is obtained as the polyoxyethylene polyol.

  These EO-containing PO-free polyols can be used alone or in combination of two or more.

  As the EO-containing PO-free polyol, preferably, polyoxyethylene glycol is used.

  An EO-containing PO-free monool having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more, which contains one or more oxyethylene groups in one molecule, does not contain oxypropylene, and contains one hydroxyl group. .

  Examples of the EO-containing PO-free monool having a molecular weight of 200 or more include one-end-capped polyoxyethylene glycol.

  One-end-capped polyoxyethylene glycol is polyoxyethylene glycol monoalkyl ether in which one terminal hydroxyl group of polyoxyethylene glycol is substituted with an oxyalkylene group.

  One end-capped polyoxyethylene glycol is prepared by using, for example, a monohydric alcohol (such as a monoalkyl ether of dipropylene glycol) in which one terminal hydroxyl group of the dihydric alcohol is capped with an alkyl group as an initiator. Can be obtained by addition reaction (and propylene oxide is not addition reaction).

  In the polyoxyethylene glycol monoalkyl ether, 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. That is, examples of the alkyl group for sealing one end include a methyl group and an ethyl group. Specific examples of such polyoxyethylene glycol monoalkyl ether include polyoxyethylene glycol monomethyl ether and polyoxyethylene glycol monoethyl ether.

  These EO-containing PO-free monools can be used alone or in combination of two or more.

  As the EO-containing PO-free monool, polyoxyethylene glycol monoalkyl ether is preferable, and polyoxyethylene glycol monomethyl ether is more preferable.

  These EO-containing PO-free alcohols can be used alone or in combination of two or more.

  As the EO-containing PO-free alcohol, preferably, an EO-containing PO-free monool is used.

  The EOPO co-alcohol having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more having one or more oxyethylene groups, one or more oxypropylene groups, and one or more hydroxyl groups in one molecule. .

  Examples of such EOPO combined alcohol include EOPO combined polyol having a molecular weight of 200 or more and EOPO combined monool having a molecular weight of 200 or more.

  The EOPO combined polyol having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more having one or more oxyethylene groups, one or more oxypropylene groups, and two or more hydroxyl groups in one molecule. .

  Examples of the EOPO combined polyol having a molecular weight of 200 or more include a polyoxyethylene-polyoxypropylene (random and / or block) copolymer.

  The polyoxyethylene-polyoxypropylene copolymer (hereinafter referred to as polyoxyethylene-polyoxypropylene polyol) is, for example, ethylene oxide using the above-described low molecular weight polyol (preferably dihydric alcohol) as an initiator. And propylene oxide can be obtained by addition reaction.

  In addition, it does not restrict | limit especially as a method of carrying out addition reaction of ethylene oxide and propylene oxide to a low molecular weight polyol, A well-known method is employable.

  Further, the number of functional groups (number of hydroxyl groups) of polyoxyethylene-polyoxypropylene polyol is the same as the number of functional groups (number of hydroxyl groups) of the initiator (low molecular weight polyol or the like). For example, a dihydric alcohol is used as the initiator. In this case, a bifunctional polyoxyethylene-polyoxypropylene glycol is obtained as the polyoxyethylene-polyoxypropylene polyol.

  The EOPO combined polyol can be used alone or in combination of two or more.

  As an EOPO combined polyol, Preferably, a polyoxyethylene-polyoxypropylene polyol is mentioned, More preferably, a polyoxyethylene-polyoxypropylene glycol is mentioned.

  The EOPO combined monool having a molecular weight of 200 or more is an organic compound having a molecular weight of 200 or more, which has one or more oxyethylene groups, one or more oxypropylene groups, and one hydroxyl group in one molecule.

  Examples of the EOPO combined monool having a molecular weight of 200 or more include one-end-capped polyoxyethylene-polyoxypropylene glycol.

  One end-capped polyoxyethylene-polyoxypropylene glycol is polyoxyethylene-polyoxypropylene glycol monoalkyl ether in which one terminal hydroxyl group of polyoxyethylene-polyoxypropylene glycol is substituted with an oxyalkylene group.

  One-end-capped polyoxyethylene-polyoxypropylene glycol is, for example, a monohydric alcohol (such as a monoalkyl ether of dipropylene glycol) in which one terminal hydroxyl group of the dihydric alcohol is sealed with an alkyl group. Can be obtained by addition reaction of ethylene oxide and propylene oxide.

  In the polyoxyethylene-polyoxypropylene glycol monoalkyl ether, 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, Particularly preferably, it is 2 or less. That is, the alkyl group for sealing one end preferably includes a methyl group and an ethyl group. Specific examples of such polyoxyethylene-polyoxypropylene glycol monoalkyl ether include polyoxyethylene-polyoxypropylene glycol monomethyl ether and polyoxyethylene-polyoxypropylene glycol monoethyl ether.

  These EOPO combined monools can be used alone or in combination of two or more.

  The EOPO combined monool is preferably polyoxyethylene-polyoxypropylene glycol monoalkyl ether, more preferably polyoxyethylene-polyoxypropylene glycol monomethyl ether.

  These EOPO combined alcohols can be used alone or in combination of two or more.

  As an EOPO combined alcohol, Preferably, an EOPO combined monool is mentioned.

  In the EOPO combined alcohol, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is, for example, 1% by mass or more, preferably from the viewpoint of improving thermal stability and storage stability. 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, for example, 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, Preferably, it is 70 mass% or less.

  In addition, the ratio of the oxyethylene group with respect to the total mass of an oxyethylene group and an oxypropylene group can be calculated from preparation.

  These oxyethylene-containing alcohols having a molecular weight of 200 or more can be used alone or in combination of two or more.

  From the viewpoint of improving thermal stability and storage stability, the oxyethylene-containing alcohol having a molecular weight of 200 or more is preferably an EOPO combined alcohol, more preferably an EOPO combined monool.

  In other words, the oxyethylene-containing alcohol having a molecular weight of 200 or more preferably contains EOPO combined alcohol (more preferably, EOPO combined monool) alone.

  When the oxyethylene-containing alcohol having a molecular weight of 200 or more has a repeating unit of an oxyethylene group, the number of repeating units is, for example, 2 or more, preferably 3 or more, more preferably 5 or more, still more preferably It is 10 or more, for example, 60 or less, preferably 50 or less.

  When the number of repeating units of the oxyethylene group is in the above range, 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 having a molecular weight of 200 or more is 200 or more, preferably 250 or more, more preferably 300 or more, still more preferably 400 or more, for example, 5000 or less, preferably Is 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less.

  When the molecular weight (number average molecular weight) of the oxyethylene-containing alcohol having a molecular weight of 200 or more is in the above range, the stability during synthesis and the water dispersibility of the polycarbodiimide composition can be improved.

  The alcohol having a molecular weight of 200 or more can contain, as an optional component, an oxyethylene-free alcohol having a molecular weight of 200 or more, in addition to the oxyethylene-containing alcohol having a molecular weight of 200 or more.

An alcohol having no oxyethylene group (—CH ₂ CH ₂ O—) in the molecule is defined as an oxyethylene-free alcohol.

  More specifically, as an oxyethylene-free alcohol having a molecular weight of 200 or more, for example, an oxyethylene group such as tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, etc. Monools having a molecular weight of 200 or more that do not contain, for example, polyols having a molecular weight of 200 or more that do not contain oxyethylene groups such as bisphenol A and hydrogenated bisphenol A.

  These oxyethylene-free alcohols having a molecular weight of 200 or more can be used alone or in combination of two or more.

  The molecular weight (number average molecular weight) of the oxyethylene-free alcohol having a molecular weight of 200 or more is 200 or more, preferably 250 or more, more preferably 300 or more, still more preferably 400 or more, for example, 5000 or less, preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less.

  In the alcohol having a molecular weight of 200 or more, the content ratio of the oxyethylene-free alcohol is not particularly limited, and is appropriately set within a range not inhibiting the excellent effect of the present invention.

  From the viewpoint of water dispersibility, the alcohol having a molecular weight of 200 or more preferably does not contain an oxyethylene-free alcohol having a molecular weight of 200 or more, but contains an oxyethylene-containing alcohol having a molecular weight of 200 or more alone.

  In addition to the alcohol having a molecular weight of 200 or more, the alcohol can contain an alcohol having a molecular weight of less than 200 as an optional component.

  As the alcohol having a molecular weight of less than 200, an alcohol having an oxyethylene group and having a molecular weight of less than 200 (hereinafter sometimes referred to as an oxyethylene-containing alcohol having a molecular weight of less than 200), an alcohol having a molecular weight of less than 200 and not containing an oxyethylene group ( Hereinafter, it may be referred to as an oxyethylene-free alcohol having a molecular weight of less than 200).

Examples of the oxyethylene-containing alcohol having a molecular weight of less than 200 include oxyethylene groups such as ethylene glycol (HO—CH ₂ CH ₂ —OH) and diethylene glycol (HO—CH ₂ CH ₂ —O—CH ₂ CH ₂ —OH). Polyol having a molecular weight of less than 200, for example, 2-methoxyethanol (CH ₃ O—CH ₂ CH ₂ —OH), 2-ethoxyethanol (CH ₃ CH ₂ O—CH ₂ CH ₂ —OH), diethylene glycol monoethyl ether (also known as _carbitol), such as _{(CH 3 O-CH 2 CH} 2 -O-CH 2 CH 2 -OH) monool having a molecular weight of less than 200 containing an oxyethylene group, and the like.

  Oxyethylene-containing alcohols having a molecular weight of less than 200 can be used alone or in combination of two or more.

  Examples of the oxyethylene-free alcohol having a molecular weight of less than 200 include monools having a molecular weight of less than 200, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, and t-butanol, which do not contain an oxyethylene group. 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol and other polyols having a molecular weight of less than 200 such as Can be mentioned.

  Oxyethylene-free alcohols having a molecular weight of less than 200 can be used alone or in combination of two or more.

  These alcohols having a molecular weight of less than 200 can be used alone or in combination of two or more.

  The molecular weight (number average molecular weight) of an alcohol having a molecular weight of less than 200 is less than 200, preferably 150 or less, more preferably 100 or less, for example, 30 or more, preferably 40 or more.

  In the alcohols, the content ratio of the alcohol having a molecular weight of less than 200 is not particularly limited, and is appropriately set within a range not impairing the excellent effects of the present invention.

  From the viewpoint of the balance between water dispersibility and water resistance, the alcohol preferably contains an alcohol having a molecular weight of 200 or more alone without containing an alcohol having a molecular weight of less than 200, more preferably an oxy having a molecular weight of 200 or more. Contains ethylene-containing alcohol alone.

  Although the content rate of the oxyethylene group in alcohol is not specifically limited, It adjusts so that the content rate of the oxyethylene group of the polycarbodiimide composition obtained may become a predetermined range.

  Specifically, the content ratio of the oxyethylene group in the polycarbodiimide composition is, for example, 3% 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.

  If the content ratio of the oxyethylene group is in the above range, 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.

  In addition, the content rate of an oxyethylene group is computable from the preparation amount.

  On the other hand, such alcohols may contain water.

  For example, in commercially available alcohols and alcohols obtained by conventional methods, the water content usually exceeds 5000 ppm with respect to the total amount of alcohols and water. Moreover, the ratio (after-mentioned) of the water with respect to 100 mol of polyisocyanates usually exceeds 1.0 mol.

  However, when the alcohol contains water in the above proportion, the resulting polycarbodiimide composition is not sufficiently heat-stable, and increases in viscosity due to heat during production, resulting in productivity (manufacturing workability, quality). Etc.).

  Therefore, in this method, preferably, before the urethanization step, the alcohols are dehydrated and the ratio of water in the alcohols is adjusted to a predetermined range (dehydration step).

  Although it does not restrict | limit especially as a dehydration process, For example, a heat processing, a pressure reduction process, a filtration process, a centrifugal dehydration process, a desiccant (dehydrating agent) process etc. are mentioned. These dehydration treatments can be used alone or in combination of two or more.

  The dehydration treatment is preferably heat treatment and reduced pressure treatment, more preferably combined use thereof (that is, heat reduced pressure treatment).

  On the other hand, in such a dehydration process, when water of alcohols is completely removed, it is necessary to heat and depressurize to a high level, and it is necessary to process for a long time. Inferior to sex.

  Therefore, in the dehydration step, at least part of the water remains in the alcohols without completely removing the water from the viewpoint of cost reduction and productivity. That is, the alcohol is an alcohol composition containing the above alcohol and water.

  From such a viewpoint, the temperature condition in the heat-reduced pressure treatment is, for example, 50 ° C. or more, preferably 100 ° C. or more, for example, 300 ° C. or less, preferably 200 ° C. or less.

  The pressure condition is, for example, 0.01 kPa or more, preferably 0.1 kPa or more, more preferably 1 kPa or more, for example, 10 kPa or less, preferably 5 kPa or less, more preferably 3 kPa or less, even more preferably. Is 2 kPa or less.

  The treatment time is, for example, 0.5 hours or more, preferably 1 hour or more, more preferably 3 hours or more, for example, 20 hours or less, preferably 10 hours or less, more preferably 5 hours. It is as follows.

  Thereby, alcohol with reduced water content is obtained.

  The water content is, for example, 10 ppm or more, preferably 100 ppm or more, more preferably 200 ppm or more, for example, 5000 ppm or less, preferably 3000 ppm or less, more preferably, relative to the total amount of alcohol and water. , 1000 ppm or less.

  The water content can be measured by the Karl Fischer method in accordance with examples described later.

  The water content is adjusted so that the molar ratio of the polyisocyanate to the water in the alcohol is within a predetermined range during the urethanization reaction between the polyisocyanate and the alcohol.

  Specifically, the ratio of water is, for example, 0.01 mol or more, preferably 0.05 mol or more, and 1.0 mol or less, preferably 0.9 mol, relative to 100 mol of polyisocyanate. It is as follows.

  If the ratio of the water with respect to polyisocyanate is below the said upper limit, the thermal stability of a polycarbodiimide composition can be improved and the increase in viscosity of the polycarbodiimide composition at the time of manufacture can be suppressed.

  Further, the ratio of water is more preferably 0.10 mol or more, further preferably 0.12 mol or more with respect to 100 mol of the polyisocyanate, from the viewpoint of suppressing the viscosity increase rate of the polycarbodiimide composition. Moreover, More preferably, it is 0.40 mol or less, More preferably, it is 0.30 mol or less.

  In addition, from the viewpoint of reducing the viscosity of the polycarbodiimide composition, the proportion of water is preferably more than 0.40 mol, more preferably 0.50 mol or more, relative to 100 mol of polyisocyanate, Moreover, More preferably, it is 0.80 mol or less, More preferably, it is 0.60 mol or less.

  The ratio of water to polyisocyanate can be calculated from the amount charged.

  In this method, the alcohols dehydrated in the dehydration step and the polyisocyanate described above are urethanated (urethanization step).

  In the urethanization step, the reaction ratio between the polyisocyanate and the alcohol is set so that the molar ratio between the polyisocyanate and the water in the alcohol falls within the above range.

  More specifically, although depending on the types of polyisocyanate and alcohols, the reaction ratio between the polyisocyanate and the alcohol is the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the alcohol (NCO / OH). For example, it exceeds 2, preferably 3 or more, more preferably 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.

  When the reaction ratio between the polyisocyanate and the alcohol is within the above range, a polycarbodiimide composition having excellent thermal stability can be obtained.

  Moreover, in this reaction, you may add well-known urethanation catalysts, such as amines and an organometallic compound, as needed.

  Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, such as imidazole, Examples thereof include imidazoles such as 2-ethyl-4-methylimidazole.

  Examples of the organic metal compound 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, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate, etc. It is.

  Furthermore, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

  These urethanization catalysts can be used alone or in combination of two or more.

  In addition, the compounding ratio of a urethanization catalyst is not restrict | limited in particular, According to the objective and a use, it sets suitably.

  The reaction conditions in the urethanization step are set according to the types of polyisocyanate and alcohol, the equivalent ratio (NCO / OH), and the like.

  More specifically, the reaction conditions in the urethanization step are, for example, a reaction temperature of, for example, 30 ° C. or more, preferably 60 ° C. or more under normal pressure and an inert gas (eg, nitrogen gas) atmosphere. For example, it is 150 degrees C or less, Preferably, it is 120 degrees C or less. 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.

  Thereby, the urethane modified body (alcohol modified body) of polyisocyanate can be obtained. In addition, the urethane modified body (alcohol modified body) of polyisocyanate has an isocyanate group at the molecular terminal.

  Next, in this method, 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).

  Although it does not restrict | limit especially as a carbodiimidization catalyst, For example, a trialkyl phosphate ester type compound, a phospholene oxide type compound, a phospholene sulfide type compound, a phosphine oxide type compound, a phosphine type compound etc. are mentioned.

  Examples of the trialkyl phosphate ester include trialkyl phosphate ester compounds having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate, and trioctyl phosphate.

  Examples of the phospholene-based compound include 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholene-1-oxide (EMPO), 1 -Butyl-3-methyl-2-phospholene-1-oxide, 1-benzyl-3-methyl-2-phospholene-1-oxide, 1,3-dimethyl-2-phospholene-1-oxide, 1-phenyl-2 -Phosphorene oxide having 4 to 18 carbon atoms such as phosphorene-1-oxide, 1-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and their double bond isomers System compounds and the like.

  Examples of the phospholene sulfide-based compound include phospholene sulfide-based compounds having 4 to 18 carbon atoms such as 1-phenyl-2-phospholene-1-sulfide.

  Examples of the phosphine oxide compounds include phosphine oxide compounds having 3 to 21 carbon atoms such as triphenylphosphine oxide and tolylphosphine oxide.

  Examples of the phosphine compound 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.

  The carbodiimidization catalyst is preferably a phospholene oxide compound, more preferably 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene- 1-oxide is mentioned.

  By using the above carbodiimidization catalyst, 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. In addition, the content of the carbodiimide group can be improved.

  As the carbodiimidization catalyst, 3-methyl-1-phenyl-2-phospholene-1-oxide is particularly preferable from the viewpoint of obtaining a cured resin (described 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.

  Moreover, 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. More specifically, from the viewpoint of proceeding the carbodiimidization reaction and reducing uretonimine, 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, 180 degreeC or less, Preferably, it is 170 degreeC or less, More preferably, it is 160 degreeC or less. 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.

  By reacting under such conditions, the 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. .

  More specifically, when the reaction temperature is equal to or higher than the above lower limit, the carbodiimidization reaction can proceed while promoting the reaction in which the generated uretonimine is decomposed into carbodiimide and an isocyanate group. When 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. Moreover, the molecular weight increases due to the increase in uretonimine, and the reaction solution may solidify. On the other hand, if the reaction temperature is not more than the above upper limit, the polymerization loss can be reduced. When the upper limit temperature is exceeded, polymerization reactions other than carbodiimidization and uretonimination are promoted, and not only the content of the carbodiimide group is lowered, but the reaction liquid is easily solidified due to an increase in molecular weight.

  Further, in the carbodiimidization step, the reaction solution is preferably refluxed in the presence of an organic solvent from the viewpoint of causing a carbodiimidization reaction smoothly and promoting decarboxylation condensation. That is, a carbodiimidization reaction is performed under reflux.

  Examples of the organic solvent 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. Aliphatic hydrocarbons such as n-hexane, n-heptane and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, 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 group Glycol ether esters such as coal monomethyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol Ethers such as dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol diethyl ether 1,2-diethoxyethane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide , Halogenated aliphatic hydrocarbons such as methylene iodide and dichloroethane, such as N-methylpyrrolidone, dimethylformamide, N N'- dimethylacetamide, dimethyl sulfoxide, such as a polar aprotic such as hexamethylphosphoric phosphonyl amides. These organic solvents can be used alone or in combination of two or more.

  As an organic solvent, Preferably, the organic solvent whose temperature at the recirculation | reflux is in the range of the reaction temperature mentioned above is mentioned.

  Specific examples of such an organic solvent 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.

  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.

  By such a method, a polycarbodiimide composition containing a urethane group and a carbodiimide group and optionally containing a uretonimine group can be obtained.

  More specifically, first, in the urethanization step, a urethane group derived from an isocyanate group of polyisocyanate is generated.

  Next, when the 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. .

  In this way, the isocyanate groups of the polyisocyanate are converted into urethane groups and carbodiimide groups (and possibly uretonimine groups).

  As a result, a polycarbodiimide composition containing a urethane group and a carbodiimide group and optionally containing a uretonimine group is obtained.

  In this method, if necessary, the polycarbodiimide composition obtained in the carbodiimidization step can be further reacted with an alcohol. In the following, the urethanization step before the carbodiimidization step may be referred to as a first urethanization step, and the urethanization step after the carbodiimidization step may be referred to as a second urethanization step.

  Specifically, when 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.

  In the second urethanization step, examples of alcohols include oxyethylene-containing alcohols having a molecular weight of 200 or more.

  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.

  Specifically, the equivalent ratio of isocyanate groups of polyisocyanate (NCO / OH) to the total amount of hydroxyl groups of alcohols used in the first urethanization step and hydroxyl groups of alcohols used in the second urethanization step. ) 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.

  In this reaction, the above-mentioned urethanization catalyst may be added as necessary. In addition, the compounding ratio of a urethanization catalyst is not restrict | limited in particular, According to the objective and a use, it sets suitably.

  Moreover, as reaction conditions in the second urethanization step, the reaction temperature is preferably in the same range as the reaction temperature in the carbodiimidization step under normal pressure and an inert gas (eg, nitrogen gas) atmosphere. Moreover, 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.

  Thereby, the isocyanate group of the molecular terminal which a polycarbodiimide composition has, and the hydroxyl group which alcohol has has urethanation reaction.

  As a result, a polycarbodiimide composition having no isocyanate group at the molecular end or having a reduced number of isocyanate groups at the molecular end is obtained.

  In addition, 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.

  In addition, the manufacturing method of a polycarbodiimide composition is not limited above, For example, polyisocyanate, a carbodiimidization catalyst, and alcohol can be mix | blended collectively and it can also heat.

  In addition, if necessary, from the 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 include known additives such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), plasticizers, anti-blocking agents, 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.

  Moreover, the polycarbodiimide composition can be used alone or in combination of two or more.

  The carbodiimide equivalent (g / mol) of the polycarbodiimide composition thus obtained is, for example, 350 or more, preferably 360 or more, more preferably 370 or more, further preferably 380 or more, and particularly preferably 390. It is above, 450 or less, Preferably it is 440 or less, More preferably, it is 430 or less, More preferably, it is 420 or less, Especially preferably, it is 410 or less.

The carbodiimide equivalent (g / mol) is measured by a known method such as ¹³ C-NMR.

  Further, the content ratio of the oxyethylene group of the polycarbodiimide composition thus obtained is, for example, 3% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more. Yes, for example, 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.

  If the content ratio of the oxyethylene group in the polycarbodiimide composition is within the above range, both an aqueous dispersion composition (described later) and a solution composition can be obtained.

  And in the manufacturing method of said polycarbodiimide composition, in the reaction with polyisocyanate which has a primary isocyanate group, and alcohol containing oxyethylene group-containing alcohol with a molecular weight of 200 or more, the water content of alcohol is Since it is below a predetermined amount, a polycarbodiimide composition having excellent thermal stability and productivity can be obtained.

  Therefore, said polycarbodiimide composition is used suitably as a hardening | curing agent in the resin composition for obtaining resin cured | curing material.

  The resin composition contains a curing agent containing a polycarbodiimide composition and a main agent having a carboxyl group.

  The curing agent is not particularly limited as long as it contains 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. . Preferably, 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.

  If the curing agent is an aqueous dispersion composition, compatibility with the aqueous resin (main agent) can be improved, and a cured product having excellent water resistance and chemical resistance can be obtained. Moreover, since such an aqueous dispersion composition contains the said polycarbodiimide composition, it is excellent in thermal stability and productivity.

  The solution composition contains a polycarbodiimide composition and an organic solvent.

  Examples of the organic solvent include the organic solvents described above, 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. Preferably, 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.

  If the curing agent is a solution composition, compatibility with the oil-based resin (main agent) can be improved, and a cured product having excellent water resistance and chemical resistance can be obtained. Moreover, since such a solution composition contains the said polycarbodiimide composition, it is excellent in thermal stability and productivity.

  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.

  Examples of the water-based resin having a carboxyl group 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. Hydrophilic polyurethane resin, hydrophilic acrylic resin having a carboxyl group, hydrophilic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block) copolymer, etc.) and other repeating units having 4 or more carbon atoms Polyolefin) resin. These aqueous resins having a carboxyl group can be used alone or in combination of two or more.

  Preferred examples of the water-based resin having a carboxyl group include a hydrophilic polyurethane resin having a carboxyl group and a hydrophilic acrylic resin having a carboxyl group.

  Examples of the oil-based resin having a carboxyl group 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. Hydrophobic polyurethane resin having a hydrophobic group, hydrophobic acrylic resin having a carboxyl group, hydrophobic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block) copolymer, etc.), and other repeating units having 4 carbon atoms 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.

  The oil-based resin having a carboxyl group is preferably a hydrophobic polyurethane resin having a carboxyl group or a hydrophobic acrylic resin having a carboxyl group.

  These can be used alone or in combination of two or more.

  As 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. In addition, a combination in which the main agent is an oil-based resin and the curing agent is a solution composition is also preferable.

  From the viewpoint of reducing the organic solvent and protecting the global environment, the resin composition is preferably a combination of an aqueous main agent and an aqueous dispersion composition.

  Further, 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. Alternatively, it may be a one-component type in which a main agent and a curing agent are premixed.

  As the resin composition, a two-component type resin composition is preferably used.

  As for the content ratio of the main agent and the curing agent, the main 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 of the total amount thereof. 95.0 parts by mass or less. Moreover, a hardening | 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.

  In addition, 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.

  Further, as the main agent, the above-described aqueous resin having a carboxyl group, and / or the above-described oil-based resin having a carboxyl group, and other resins (for example, 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.

  Moreover, as a hardening | curing agent, an above-described polycarbodiimide composition and other hardening | curing agents (for example, polyisocyanate resin, an epoxy resin, etc.) can also be used together.

  And in such a resin composition, since the above-mentioned polycarbodiimide composition is used as a hardening | curing agent, it is excellent in thermal stability and productivity.

  The method for producing the cured resin product is not particularly limited. For example, when the resin composition is a one-component type, the resin composition is directly applied to an object to be coated or an adherend. Moreover, when the resin composition is a two-component type, the main agent and the curing agent are mixed, and the obtained mixture is applied to an object to be coated or an adherend. And a resin hardened material is obtained by carrying out heat hardening of a resin composition.

  In the above resin composition, the curing temperature is relatively low, and specifically, for example, 100 ° C. or lower, preferably 80 ° C. or lower. For example, it is 20 degreeC or more, Preferably, it is 30 degreeC or more.

  Further, 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.

  Further, if necessary, the heat-cured resin cured product can be further dried.

  In such a case, 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.

  Moreover, drying time is 1 minute or more, for example, Preferably, it is 5 minutes or more, for example, is 2 hours or less, Preferably, it is 1 hour or less.

  And since the obtained resin hardened | cured material is a hardened | cured material of the resin composition which is excellent in thermal stability and productivity, it is excellent in productivity.

  Moreover, when the polycarbodiimide composition is obtained using aliphatic polyisocyanate, the cured resin obtained using the polycarbodiimide composition is also excellent in light resistance (weather resistance).

  Therefore, 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.

  When used as a 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.

  Examples of the paint 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.

  In addition, 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.

  When using the above resin composition as a coating for automobile exteriors, as the main agent, the above-described aqueous resin having a carboxyl group and the above-described oil-based resin having a carboxyl group can be used. Preferably, an aqueous resin having a carboxyl group is used.

  Preferred examples of the water-based resin having a carboxyl group 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. Moreover, two or more types of aqueous resins having a carboxyl group as described above can be used in combination.

  Further, as the main agent, the above-described aqueous resin having a carboxyl group, and / or the above-described oil-based resin having a carboxyl group, and other resins (for example, 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.

  When the above resin composition is used as an automotive exterior paint, 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.

  Examples of the curing agent include the above-described polycarbodiimide compositions, and the polycarbodiimide composition and other curing agents (for example, polyisocyanate resins, epoxy resins, etc.) can be used in combination.

  Examples of the film coating paint 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.

  Examples of adhesives 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 ink paint include vehicles of various inks (plate ink, screen ink, flexo ink, gravure ink, jet ink, textile printing ink, etc.).

  In addition, the use of the polycarbodiimide composition is not limited to the above. For example, as a solid, polyester, polyamide-based resin, polylactic acid, or as a liquid, 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.

  Next, although this invention is demonstrated based on a manufacture example, an Example, and a comparative example, this invention is not limited by the following Example. “Part” and “%” are based on mass unless otherwise specified. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.

<Content (% by mass) of oxyethylene group in polycarbodiimide composition>
The content ratio of the oxyethylene group to the polycarbodiimide composition was calculated from the charged amount and the chemical structural formula.

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 WO 2012/121291.

Production Example 2A (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Mass of ethylene oxide and propylene oxide in polyol at a temperature of 110 ° C. and a maximum reaction pressure of 0.4 MPa gauge (G) using dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (hereinafter referred to as KOH) as a catalyst, respectively. These alkylene oxides (ethylene oxide and propylene oxide) were subjected to random addition polymerization to a hydroxyl value (hereinafter referred to as OHV) of 102 mgKOH / g so that the ratio was 50:50, thereby preparing a crude polyol.

  Next, to the crude polyol heated to 80 ° C. in a nitrogen atmosphere, 1.05 equivalents of phosphoric acid (in the form of a 75.2% by weight aqueous solution) with respect to KOH were added to the crude polyol, and 80 ° C. The mixture was neutralized for 2 hours.

  Subsequently, dehydration under reduced pressure was started while raising the temperature, and the adsorbent was added when the pressure was 40 kPa. Finally, it was heated and decompressed for 3 hours under conditions of 105 ° C. and 1.33 kPa or less.

  Then, polyoxyethylene-polyoxypropylene monomethyl ether was obtained by filtering.

  The ratio of oxyethylene groups to the total amount of oxyethylene groups and oxypropylene groups in polyoxyethylene-polyoxypropylene monomethyl ether (hereinafter referred to as EO ratio) was 50% by mass. Moreover, the number average molecular weight (polystyrene conversion) measured by the gel permeation chromatograph was 550.

Production Example 2B (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained in the same manner as in Production Example 2A, except that the mass ratio of ethylene oxide to propylene oxide was changed to 30:70 (EO: PO).

  The EO ratio of polyoxyethylene-polyoxypropylene monomethyl ether was 30% by mass. Moreover, the number average molecular weight (polystyrene conversion) measured by the gel permeation chromatograph was 550.

Production Example 2C (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained in the same manner as in Production Example 2A, except that the mass ratio of ethylene oxide to propylene oxide was changed to 70:30 (EO: PO).

  The EO ratio of polyoxyethylene-polyoxypropylene monomethyl ether was 70% by mass. Moreover, the number average molecular weight (polystyrene conversion) measured by the gel permeation chromatograph was 550.

Production Example 2D (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained in the same manner as in Production Example 2A, except that the mass ratio of ethylene oxide to propylene oxide was changed to 10:90 (EO: PO).

  The EO ratio of polyoxyethylene-polyoxypropylene monomethyl ether was 10% by mass. Moreover, the number average molecular weight (polystyrene conversion) measured by the gel permeation chromatograph was 550.

Production Example 2E (Production of polyoxyethylene-polyoxypropylene monomethyl ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained in the same manner as in Production Example 2A, except that the mass ratio of ethylene oxide to propylene oxide was changed to 90:10 (EO: PO).

  The EO ratio of polyoxyethylene-polyoxypropylene monomethyl ether was 90% by mass. Moreover, the number average molecular weight (polystyrene conversion) measured by the gel permeation chromatograph was 550.

Example 1
・ Production of polycarbodiimide composition <Dehydration process>
100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio: 50% by mass, molecular weight: 550) obtained in Production Example 2A as an alcohol was subjected to heat-reducing treatment under conditions of 150 ° C. and 1.3 kPa for 3 hours. . Thereby, the content of water in the alcohol was adjusted to 243 ppm.

  The water content was measured by the Karl Fischer method according to JIS K 0068 (2001) (the same applies hereinafter).

<Urethaneization process>
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 the pentamethylene diisocyanate obtained in Production Example 1 at room temperature and the above polyoxyethylene-polyoxy 71.35 parts by mass of propylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 6 hours.

  At this time, the amount of water in the alcohol was 0.148 mol with respect to 100 mol of polyisocyanate.

<Carbodiimidization process>
Subsequently, 368.4 parts by mass of PMA (propylene glycol monomethyl ether acetate) and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) were charged under reflux (150 ) For 8 hours to complete the reaction (carbodiimidization step).

  After completion of the reaction, the reaction mixture was cooled to 80 ° C., and PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition.

It was 1700 mPa * s as a result of taking out a part of obtained polycarbodiimide composition and measuring the E-type viscosity in 25 degreeC.
-Preparation of aqueous dispersion of polycarbodiimide 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.

-Preparation of 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.

-Preparation of aqueous resin composition An aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. And 1.5 mass parts of hardening | curing agents and 98.5 mass parts of polyurethane dispersions (solid content 30 mass%, carboxyl group equivalent 3100 g / mol of solid content) as a main ingredient were mixed, and the resin composition was prepared. .

-Preparation of solvent-based resin composition A solution of the obtained polycarbodiimide composition was used as a curing agent. And 1.0 mass part of hardening | curing agents, 39.2 mass parts of acrylic resins (solid content 50 mass%, carboxyl group equivalent 2004g / mol of solid content) as a main ingredient, and 59.8 mass parts of butyl acetate as a solvent Were mixed to prepare a resin composition.

Example 2
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A as an alcohol is 105 ° C under 1.3 kPa for 1 hour, Heated under reduced pressure. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Example 3
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 30% by mass, molecular weight 550) obtained in Production Example 2B as alcohols was used at 105 ° C. and 1.3 kPa for 1 hour, Heated under reduced pressure. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 30 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Example 4
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 70% by mass, molecular weight 550) obtained in Production Example 2C as an alcohol was subjected to 105 ° C. and 1.3 kPa for 1 hour, Heated under reduced pressure. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 70 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Example 5
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio: 10% by mass, molecular weight: 550) obtained in Production Example 2D as an alcohol is 105 ° C under 1.3 kPa for 1 hour, Heated under reduced pressure. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 10 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Example 6
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 90% by mass, molecular weight 550) obtained in Production Example 2E as an alcohol was subjected to 105 ° C. and 1.3 kPa for 1 hour, Heated under reduced pressure. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 90 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Example 7
In the dehydration step, 100 parts by mass of UNIOX M550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, EO ratio 100% by mass, molecular weight 550) as an alcohol is heated for 1 hour at 105 ° C. and 1.3 kPa. A vacuum was applied. Thereby, content of the water in alcohol was adjusted to 1000 ppm.

  Thereafter, a polycarbodiimide composition was obtained in the same manner as in Example 1 except that UNIOX M550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, EO ratio 100% by mass, molecular weight 550) was used. Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Comparative Example 1
In the dehydration step, 100 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A as an alcohol was heated under reduced pressure at 105 ° C. and 20 kPa for 1 hour. Processed. Thereby, content of the water in alcohol was adjusted to 10000 ppm.

  Then, the polycarbodiimide composition was obtained by the same method as Example 1 except having used the said polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550). Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

Comparative Example 2
In the dehydration step, 100 parts by mass of UNIOX M550 as an alcohol (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, EO ratio 100% by mass, molecular weight 550) is heated under reduced pressure for 1 hour under conditions of 105 ° C. and 20 kPa. did. Thereby, content of the water in alcohol was adjusted to 10000 ppm.

  Thereafter, a polycarbodiimide composition was obtained in the same manner as in Example 1 except that UNIOX M550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, EO ratio 100% by mass, molecular weight 550) was used. Table 1 shows the ratio of water to 100 moles of polyisocyanate and the E-type viscosity at 25 ° C.

  Moreover, the aqueous dispersion and solution of the polycarbodiimide composition were prepared by the same method as Example 1, and the resin composition was prepared.

<Evaluation>
<Thermal stability>
10 g of the polycarbodiimide composition was put into a 50 mL flask, blown with nitrogen, sealed, and stored at 80 ° C. And the E-type viscosity in 25 degreeC after predetermined time (45 minutes) was measured. The lower the viscosity at this time, the better the thermal stability.

Claims (9)

A urethanization step of urethanizing a polyisocyanate having a primary isocyanate group and an alcohol containing an oxyethylene group-containing alcohol having a molecular weight of 200 or more;
The reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst to carry out a carbodiimidization reaction, and a carbodiimidization step to obtain a polycarbodiimide composition,
The alcohols include water;
The ratio of the said water is 1.0 mol or less with respect to 100 mol of said polyisocyanates, The manufacturing method of the polycarbodiimide composition characterized by the above-mentioned. The alcohols are
EOPO combined alcohol having both oxyethylene (EO) group and oxypropylene (PO) group,
2. The polycarbodiimide composition according to claim 1, wherein in the EOPO combined alcohol, a ratio of oxyethylene groups to a total mass of oxyethylene groups and oxypropylene groups is 20% by mass or more and 80% by mass or less. Manufacturing method. The method for producing a polycarbodiimide composition according to claim 1, wherein the polyisocyanate is an aliphatic polyisocyanate. The method for producing a polycarbodiimide composition according to any one of claims 1 to 3, wherein the polyisocyanate is pentamethylene diisocyanate. A polyisocyanate having primary isocyanate groups;
A reaction product with an alcohol containing an oxyethylene group-containing alcohol having a molecular weight of 200 or more,
The alcohols include water;
The polycarbodiimide composition, wherein a ratio of the water is 1.0 mol or less with respect to 100 mol of the polyisocyanate. The polycarbodiimide composition according to claim 5,
An aqueous dispersion composition, which is an aqueous dispersion dispersed in water at a solid content concentration of 5% by mass to 90% by mass. The polycarbodiimide composition according to claim 5,
A solution composition, which is a solution dissolved in an organic solvent at a solid content concentration of 5% by mass to 90% by mass. A main agent having a carboxyl group;
A resin composition comprising a curing agent comprising the polycarbodiimide composition according to claim 5.   A cured resin, which is a cured product of the resin composition according to claim 8.