JP7017460B2 - Method for producing polycarbodiimide composition, polycarbodiimide composition, aqueous dispersion composition, solution composition, resin composition and cured resin - Google Patents

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, and as a curing agent, for example, a carbodiimide-based curing agent is known.

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

Then, by drying and curing the resin composition composed of such a polycarbodiimide composition (curing agent) and the main agent, a cured resin product such as a coating film can be obtained.

International release WO2017 / 119443 pamphlet

However, the polycarbodiimide composition as described above does not have sufficient thermal stability when the alcohol as a raw material contains an excessive amount of water, and becomes highly viscous due to the heat during production, resulting in productivity (manufacturing workability, There is a problem of degrading quality etc.).

INDUSTRIAL APPLICABILITY The present invention relates to a method for producing a polycarbodiimide composition for obtaining a polycarbodiimide composition having excellent thermal stability and productivity, a polycarbodiimide composition, an aqueous dispersion composition and a solution composition containing the polycarbodiimide composition, and a polycarbodiimide. It is a resin composition containing the composition, and further, a cured resin product obtained by curing the resin composition.

The present invention [1] comprises a urethanization step in which a polyisocyanate having a primary isocyanate group and alcohols containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group are subjected to a urethanization reaction, and a reaction generation in the urethanization step. It comprises a carbodiimidization step of heating an object in the presence of a carbodiimidization catalyst and causing a carbodiimidization reaction to obtain a carbodiimide composition, wherein the alcohols contain water and the proportion of the water is the polyisocyanate 100. It comprises a method for producing a polycarbodiimide composition which is 1.0 mol or less per mol.

In the present invention [2], the alcohols include an EOPO co-alcohol having both an oxyethylene (EO) group and an oxypropylene (PO) group, and the EOPO co-alcohol contains an oxyethylene group and an 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.

The present invention [3] includes the method for producing a polycarbodiimide composition according to the above [1] or [2], wherein the polyisocyanate is an aliphatic polyisocyanate.

The present invention [4] includes the method for producing a polycarbodiimide composition according to any one of the above [1] to [3], wherein the polyisocyanate is pentamethylene diisocyanate.

The present invention [5] is a reaction product of a polyisocyanate having a primary isocyanate group and alcohols containing an oxyethylene group and containing an alcohol having a molecular weight of 200 or more, wherein the alcohols contain water and are described above. It contains a polycarbodiimide composition in which the ratio of water is 1.0 mol or less with respect to 100 mol of the polyisocyanate.

The present invention [6] is an aqueous dispersion in which the polycarbodiimide composition according to the above [5] is dispersed in water at a solid content concentration of 5% by mass or more and 90% by mass or less. Includes.

The present invention [7] includes a solution composition in which the polycarbodiimide composition according to the above [5] is dissolved in an organic solvent at a solid content concentration of 5% by mass or more and 90% by mass or less. There is.

The present invention [8] includes a resin composition containing a main agent having a carboxyl group and a curing agent containing the polycarbodiimide composition according to the above [5].

The present invention [9] contains a cured resin product, which is a cured product of the resin composition according to the above [8].

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

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

Further, since the cured resin product 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 alcohols are subjected to a urethanization reaction, and then the obtained reaction product is subjected to a carbodiimideization reaction. As a result, a polycarbodiimide composition is obtained as a reaction product between the polyisocyanate having a primary isocyanate group and alcohols.

More specifically, in this method, first, a polyisocyanate having a primary isocyanate group (hereinafter, may be simply referred to as polyisocyanate) and alcohols are subjected to a urethanization reaction (urethaneization 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. To.

The polyisocyanate having a primary isocyanate group may 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) in which one hydrogen atom (H) is bonded to the carbon atom (C) to which the isocyanate group (-NCO) is bonded. Indicates a group.))).

Further, 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. _R1 and _R2 are defined as homologous or heterologous substituents))).

Examples of the polyisocyanate having a primary isocyanate group include an aliphatic polyisocyanate having a primary isocyanate group, an alicyclic polyisocyanate having a primary isocyanate group, and an aromatic aliphatic polyisocyanate having a primary isocyanate group. Will be.

The aliphatic polyisocyanate having a primary isocyanate group is a chain (linear or branched chain: acyclic) aliphatic polyisocyanate having a primary isocyanate group, and is, for example, ethylene diisocyanate, trimethylene diisocyanate, and the like. 1,2-propylene diisocyanate, butyrene diisocyanate (tetramethylene diisocyanate, 1,2-butyrene diisocyanate, 2,3-butyrene diisocyanate, 1,3-butyrene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6 -Hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, heptamethylene diisocyanate, octamethylene diisocyanate, dodecamethylene diisocyanate, etc. The aliphatic diisocyanate of the above can be mentioned.

Examples of the alicyclic polyisocyanate having a primary isocyanate group include 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate; IPDI), 1,3- or 1,4-bis (isocyanate). Examples thereof include natomethyl) cyclohexane or a mixture thereof (hydrogenated XDI), an alicyclic diisocyanate such as norbornan diisocyanate (NBDI), and the like.

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

These polyisocyanates having a primary isocyanate group can be used alone or in combination of two or more.

Examples of the polyisocyanate having a primary isocyanate group include an aliphatic polyisocyanate having a primary isocyanate group and an alicyclic polyisocyanate having a primary isocyanate group from the viewpoint of light resistance, handleability and water dispersibility. Therefore, from the viewpoint of chemical resistance, an aliphatic polyisocyanate having a primary isocyanate group is more preferable.

As the aliphatic polyisocyanate having a primary isocyanate group, 1,5-pentamethylene diisocyanate (PDI) and 1,6-hexamethylene diisocyanate (HDI) are preferable, and more preferable, from the viewpoint of availability. , 1,5-Pentamethylene diisocyanate (PDI).

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 concentration of carbodiimide groups in the polycarbodiimide composition is higher when 1,5-pentamethylene diisocyanate is used than when 1,6-hexamethylene diisocyanate is used. be able to. As a result, a cured resin product (described later) having excellent various physical properties (water resistance, chemical resistance, etc.) can be obtained. In addition, 1,5-pentamethylene diisocyanate having an odd number of carbon atoms has lower crystallinity due to the amorphous structure derived from the odd number of carbon atoms than 1,6-hexamethylene diisocyanate having an even number of carbon atoms, so that handling is possible. It has excellent properties and dispersibility, and can improve the physical properties of the obtained cured resin product (described later).

Further, when 1,5-pentamethylene diisocyanate is used, thermal decomposition of the uretonimine group described later is more likely to occur than in the case of using 1,6-hexamethylene diisocyanate, and therefore, a polycarbodiimide composition can be obtained in good yield. can. Moreover, since it can be handled even at a low temperature, it is possible to suppress the increase in the molecular weight of uretonimine.

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

When the alcohol is a monomer, its molecular weight can be calculated from the molecular structure. When the alcohol is a polymer, its molecular weight is measured by a gel permeation chromatograph as a number average molecular weight (in terms of polystyrene).

Alcohols contain alcohol having a molecular weight of 200 or more as an essential component.

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

An 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.

An oxyethylene group (-CH ₂ CH ₂ O-) is a group consisting of two carbon atoms, four hydrogen atoms and one oxygen atom.

That is, the oxyethylene group (-CH ₂ CH ₂ O-) is one 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.) and are distinguished.

Further, the oxyethylene group (-CH ₂ CH ₂ O-) has a carbon atom at the terminal 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 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.

Further, the oxyethylene-containing alcohol having a molecular weight of 200 or more can contain an oxypropylene group (-CH (CH ₃ ) CH _2O- ) in addition to the oxyethylene group, and is further classified according to the presence or absence of the oxypropylene group. Will be done.

Specifically, as the oxyethylene-containing alcohol having a molecular weight of 200 or more, an alcohol having a molecular weight of 200 or more containing an oxyethylene (EO) group and not containing an oxypropylene (PO) group (hereinafter, EO-containing PO non-alcohol having a molecular weight of 200 or more). (Referred to as alcohol-containing) and alcohol having a molecular weight of 200 or more having both an oxyethylene (EO) group and an oxypropylene (PO) group (hereinafter referred to as EOPO coexisting alcohol having a molecular weight of 200 or more) can be mentioned.

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. be.

Examples of such EO-containing PO-free alcohols include EO-containing PO-free polyols having a molecular weight of 200 or more and EO-containing PO-free monools 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. be.

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

The polyoxyethylene polyol can be obtained, for example, by subjecting ethylene oxide to an addition reaction (and not propylene oxide to an addition reaction) 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 having a molecular weight of 60 or more and less than 500 (preferably less than 400), and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, or 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, alcoholic (C7-20) diols, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and them. Divalents such as hydride, bisphenol A hydride, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, etc. Alcohols such as trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentahydric alcohols such as xylitol, eg sorbitol, Hexic alcohols such as mannitol, aritol, iditol, darsitol, altritor, inositol and dipentaerythritol, for example, heptavalent alcohols such as persetol, for example, octahydric alcohols such as sucrose and the like can be mentioned. These can be used alone or in combination of two or more.

Preferred low molecular weight polyols include dihydric alcohols.

The method for adding ethylene oxide to these low molecular weight polyols is not particularly limited, and a known method can be adopted.

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 (low molecular weight polyol, etc.). For example, when a dihydric alcohol is used as the initiator, the polyoxyethylene polyol is used. As the polyoxyethylene polyol, bifunctional polyoxyethylene glycol can be obtained.

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

Preferred examples of the EO-containing PO-free polyol include polyoxyethylene glycol.

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, containing one or more oxyethylene groups in one molecule, not containing oxypropylene, and containing one hydroxyl group. ..

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

The one-ended sealed polyoxyethylene glycol is a polyoxyethylene glycol monoalkyl ether in which one terminal hydroxyl group of the polyoxyethylene glycol is substituted with an oxyalkylene group.

One-ended sealed polyoxyethylene glycol is an ethylene oxide using, for example, a monohydric alcohol (such as monoalkyl ether of dipropylene glycol) in which one terminal hydroxyl group of the above-mentioned dihydric alcohol is sealed with an alkyl group as an initiator. Can be obtained by subjecting it to an addition reaction (and not subjecting it to an addition reaction with propylene oxide).

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. It is 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.

Examples of the EO-containing PO-free monool include polyoxyethylene glycol monoalkyl ether, and more preferably polyoxyethylene glycol monomethyl ether.

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

The EO-containing PO-free alcohol preferably includes EO-containing PO-free monool.

The EOPO coexisting alcohol 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 or more hydroxyl groups in one molecule. ..

Examples of such EOPO coexisting alcohols include EOPO coexisting polyols having a molecular weight of 200 or more and EOPO coexisting monools having a molecular weight of 200 or more.

An EOPO coexisting polyol 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 two or more hydroxyl groups in one molecule. ..

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

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

The method for adding ethylene oxide and propylene oxide to the low molecular weight polyol is not particularly limited, and a known method can be adopted.

Further, the number of functional groups (number of hydroxyl groups) of the polyoxyethylene-polyoxypropylene polyol is the same as the number of functional groups (number of hydroxyl groups) of the initiator (low molecular weight polyol, etc.), and for example, a dihydric alcohol is used as the initiator. In some cases, bifunctional polyoxyethylene-polyoxypropylene glycol can be obtained as the polyoxyethylene-polyoxypropylene polyol.

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

As the EOPO coexisting polyol, preferably, polyoxyethylene-polyoxypropylene polyol is mentioned, and more preferably, polyoxyethylene-polyoxypropylene glycol is mentioned.

The EOPO coexisting 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 coexisting monool having a molecular weight of 200 or more include one-ended sealed polyoxyethylene-polyoxypropylene glycol.

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

The single-ended sealed polyoxyethylene-polyoxypropylene glycol is, for example, a monohydric alcohol in which one terminal hydroxyl group of the above-mentioned dihydric alcohol is sealed with an alkyl group (such as monoalkyl ether of dipropylene glycol) as an initiator. It can be obtained by subjecting ethylene oxide and propylene oxide to an addition reaction.

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 is preferably a methyl group or 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 co-existing monools can be used alone or in combination of two or more.

As the EOPO coexisting monool, preferably, polyoxyethylene-polyoxypropylene glycol monoalkyl ether can be mentioned, and more preferably, polyoxyethylene-polyoxypropylene glycol monomethyl ether can be mentioned.

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

As the EOPO co-alcohol, preferably, EOPO co-existing monool can be mentioned.

Further, in the EOPO coexisting 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 1% by mass or more, from the viewpoint of improving thermal stability and storage stability. 10% by mass or more, more preferably 20% by mass or more, still more 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, further. It is preferably 70% by mass or less.

The ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group can be calculated from the charging.

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

As the oxyethylene-containing alcohol having a molecular weight of 200 or more, EOPO coexisting alcohol is preferable, and EOPO coexisting monool is more preferable, from the viewpoint of improving thermal stability and storage stability.

In other words, the oxyethylene-containing alcohol having a molecular weight of 200 or more preferably contains EOPO-containing alcohol (more preferably, EOPO-containing 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 thereof 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 within 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 5000 or less. Is 3000 or less, more preferably 2000 or less, 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 at the time of synthesis and the water dispersibility of the polycarbodiimide composition can be improved.

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

As the oxyethylene-free alcohol having a molecular weight of 200 or more, more specifically, for example, oxyethylene groups such as tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, and eikosanol can be used. Examples thereof include monools having a molecular weight of 200 or more that are not contained, for example, polyols having a molecular weight of 200 or more that do not contain an oxyethylene group 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 5000 or less. It is 3000 or less, more preferably 2000 or less, and even 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 as long as it does not impair 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.

Further, the alcohols may contain alcohol having a molecular weight of less than 200 as an optional component in addition to the alcohol having a molecular weight of 200 or more as described above.

Examples of the alcohol having a molecular weight of less than 200 include an alcohol having a molecular weight of less than 200 containing an oxyethylene group (hereinafter, may be referred to as an oxyethylene-containing alcohol having a molecular weight of less than 200) and an alcohol having a molecular weight of less than 200 containing no oxyethylene group (hereinafter, may be referred to as an oxyethylene-containing alcohol having a molecular weight of less than 200). 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). Polyols containing less than 200 molecular weights, such as 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. Examples thereof include monools having an oxyethylene group and having a molecular weight of less than 200, such as (also known as carbitol) (CH ₃ O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -OH).

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 and containing no oxyethylene group such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, s-butanol, and t-butanol. , 1,4-Butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol and other oxyethylene group-free polyols with a molecular weight of less than 200 Can be mentioned.

Oxyethylene-free alcohol 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, and for example, 30 or more, preferably 40 or more.

In alcohols, the content ratio of alcohol having a molecular weight of less than 200 is not particularly limited and is appropriately set as long as it does not impair the excellent effect of the present invention.

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

The content ratio of the oxyethylene group in the alcohols is not particularly limited, but is adjusted so that the content ratio of the oxyethylene group in the obtained polycarbodiimide composition is within a predetermined range.

Specifically, the content 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, and for example, 50% by mass or less. It is preferably 40% by mass or less, more preferably 35% by mass or less.

When the content ratio of the oxyethylene group is within the above range, the solubility and water dispersibility of the polycarbodiimide composition in a solvent can be improved, and a cured resin product (described later) having excellent water resistance can be obtained. be able to.

The content ratio of the oxyethylene group can be calculated from the charged amount.

On the other hand, such alcohols may contain water.

For example, in commercially available alcohols and alcohols obtained by a conventional method, the content of water usually exceeds 5000 ppm with respect to the total amount of alcohols and water. Further, the ratio of water to 100 mol of polyisocyanate (described later) usually exceeds 1.0 mol.

However, when the alcohols contain water in the above ratio, the thermal stability of the obtained polycarbodiimide composition is not sufficient, and the viscosity increases due to the heat during production, resulting in productivity (manufacturing workability, quality). Etc.) There is a problem of lowering.

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

The dehydration treatment is not particularly limited, and examples thereof include heat treatment, decompression treatment, filtration treatment, centrifugal dehydration treatment, and desiccant (dehydration agent) treatment. These dehydration treatments can be used alone or in combination of two or more.

The dehydration treatment preferably includes heat treatment and decompression treatment, and more preferably a combination thereof (that is, heat and decompression treatment).

On the other hand, in such a dehydration treatment, when the water of alcohols is completely removed, it is necessary to heat and reduce the pressure to a high level, and it is necessary to treat for a long time, which causes high cost and produces. Inferior in sex.

Therefore, in the dehydration step, from the viewpoint of cost reduction and productivity, at least a part of water is left in alcohols without completely removing water. That is, the alcohols are alcohol compositions containing the above alcohol and water.

From such a viewpoint, the temperature condition in the heating and reducing pressure treatment is, for example, 50 ° C. or higher, preferably 100 ° C. or higher, and for example, 300 ° C. or lower, preferably 200 ° C. or lower.

The pressure conditions are, for example, 0.01 kPa or more, preferably 0.1 kPa or more, more preferably 1 kPa or more, and for example, 10 kPa or less, preferably 5 kPa or less, more preferably 3 kPa or less, still more preferable. 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, and for example, 20 hours or less, preferably 10 hours or less, more preferably 5 hours. It is as follows.

As a result, alcohols having a reduced water content can be obtained.

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

The water content can be measured by the Karl Fischer method according to the examples described later.

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

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, with respect to 100 mol of polyisocyanate. It is as follows.

When the ratio of water to the polyisocyanate is not more than the above upper limit, the thermal stability of the polycarbodiimide composition can be improved, and the increase in viscosity of the polycarbodiimide composition at the time of production can be suppressed.

The ratio of water is more preferably 0.10 mol or more, still more preferably 0.12 mol or more, relative to 100 mol of polyisocyanate, from the viewpoint of suppressing the rate of increase in viscosity of the polycarbodiimide composition. Further, it is more preferably 0.40 mol or less, still more preferably 0.30 mol or less.

Further, the ratio of water is preferably more than 0.40 mol, more preferably 0.50 mol or more, with respect to 100 mol of polyisocyanate, from the viewpoint of reducing the viscosity of the polycarbodiimide composition. Further, it is more preferably 0.80 mol or less, still more preferably 0.60 mol or less.

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

Then, in this method, the alcohols dehydrated in the above-mentioned dehydration step and the above-mentioned polyisocyanate are subjected to a urethanization reaction (urethaneization step).

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

More specifically, although it depends on the type of polyisocyanate and alcohols, the reaction ratio between polyisocyanate and alcohols is defined as the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the alcohols. For example, it exceeds 2, preferably 3 or more, more preferably 4 or more, and for example, 16 or less, preferably 14 or less, and more preferably 10 or less. That is, in the urethanization step, the reaction is preferably carried out at a ratio in which the isocyanate group is excessive with respect to the hydroxyl group.

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

Further, in this reaction, a known urethanization catalyst such as an amine or an organometallic compound may be added, if necessary.

Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether and N-methylmorpholine, and quaternary ammonium salts such as tetraethylhydroxylammonium, for example, 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 laurylate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, and dibutyltin dilaurate (dilauric acid). Organic tin compounds such as dibutyl tin (IV)), dibutyl tin dineodecanoate, dioctyl tin dimercaptide, dioctyl tin dilaurylate, dibutyl tin dichloride, eg organic lead compounds such as lead octanoate, lead naphthenate, eg. Examples thereof include organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compounds such as copper octate, and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate.

Further, 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.

The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.

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

More specifically, the reaction conditions in the urethanization step are, for example, under normal pressure and an atmosphere of an inert gas (for example, nitrogen gas), the reaction temperature is, for example, 30 ° C. or higher, preferably 60 ° C. or higher. For example, the temperature is 150 ° C. or lower, preferably 120 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.

Thereby, a urethane modified product (alcohol modified product) of polyisocyanate can be obtained. The urethane modified product (alcohol modified product) of polyisocyanate has an isocyanate group at the molecular terminal.

Then, in this method, the reaction solution containing the reaction product in the above-mentioned 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 trialkylphosphate ester compounds, phosphorene oxide compounds, phosphorene sulfide compounds, phosphine oxide compounds, and phosphine oxide compounds.

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

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

Examples of the phosphoren sulfide compound include a phosphoren sulfide compound having 4 to 18 carbon atoms such as 1-phenyl-2-phosphorene-1-sulfide.

Examples of the phosphine oxide-based compound include phosphine oxide-based compounds having 3 to 21 carbon atoms such as triphenylphosphine oxide and tritrylphosphine oxide.

Examples of the phosphine-based compound include phosphine-based 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 preferably includes a phospholen oxide-based compound, more preferably 3-methyl-1-phenyl-2-phosphorene-1-oxide, 1-ethyl-3-methyl-2-phosphorene-. 1-Oxide is mentioned.

By using the above-mentioned carbodiimide catalyst, the activity of carbodiimideization can be improved and the reaction temperature can be lowered, and side reactions such as uretonimization can be suppressed to obtain a polycarbodiimide composition in good yield. In addition, the content of the carbodiimide group can be improved.

As the carbodiimidization catalyst, 3-methyl-1-phenyl-2-phosphorene-1-oxide is particularly preferable from the viewpoint of obtaining a cured resin product (described later) having excellent water resistance.

The blending ratio of the carbodiimidization catalyst is, for example, 0.01 part by mass or more, preferably 0.05 part by mass or more, for example, 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.

Further, the reaction conditions in the carbodiimideization step are set so that the content ratio of the carbodiimide group in the obtained polycarbodiimide composition is within a specific range described later. More specifically, from the viewpoint of advancing the carbodiimidization reaction and reducing uretonimine, the reaction temperature is, for example, 125 ° C. or higher, preferably 125 ° C. or higher, under normal pressure and an atmosphere of an inert gas (nitrogen gas, etc.). It is 130 ° C. or higher, more preferably 135 ° C. or higher, and for example, 180 ° C. or lower, preferably 170 ° C. or lower, more preferably 160 ° C. or lower. The reaction time is, for example, 1 hour or more, preferably 3 hours or more, and for example, 50 hours or less, preferably 40 hours or less.

By reacting under such conditions, the reaction product (urethane modified product of polyisocyanate) obtained in the urethanization step can be decarboxylated and condensed via the isocyanate group to efficiently generate a carbodiimide group. ..

More specifically, when the reaction temperature is at least the above lower limit, the carbodiimideization reaction can be allowed to proceed while promoting the reaction in which the produced uretonimine decomposes into carbodiimide and isocyanate groups. If the temperature is lower than the above lower limit, this pyrolysis reaction is very unlikely to occur, the content of uretonimine increases, and the content of carbodiimide groups decreases. In addition, the molecular weight may increase 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 above upper limit temperature is exceeded, polymerization reactions other than carbodiimidization and uretonimization are promoted, not only the content of carbodiimide groups decreases, but also the reaction solution tends to solidify due to the 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 facilitating the carbodiimidization reaction and promoting decarboxylation condensation. That is, the carbodiimidization reaction is carried out under reflux.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, nitriles such as acetonitrile, and alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate and amyl acetate, for example. , N-hexane, n-heptane, octane and other aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane and other alicyclic hydrocarbons, such as toluene, xylene, ethylbenzene and other aromatic hydrocarbons, 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 monomethyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl Glycol ether esters such as -3-ethoxypropionate, such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, ethylene glycol Ethers such as diethyl ether 1,2-diethoxyethane, for example, halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane, for example, N. -Polar aprotons such as methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide and the like can be mentioned. These organic solvents may be used alone or in combination of two or more.

The organic solvent is preferably an organic solvent in which the temperature at the time of reflux is within the above-mentioned reaction temperature range.

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, for example, with respect to 100 parts by mass of the 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 carbodiimidization reaction can be smoothly carried out while promoting the decomposition reaction of uretonimine, and the carbon dioxide gas generated by the carbodiimidization of the isocyanate group is desorbed. Therefore, it is possible to promote carbodiimidization.

Then, by such a method, a polycarbodiimide composition containing a urethane group and a carbodiimide group and, in some cases, a uretonimine group can be obtained.

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

Next, when the reaction product (urethane modified product of polyisocyanate) obtained in the urethanization step is heated in the carbodiimideization step, a carbodiimide group derived from the isocyanate group at the molecular terminal is generated, and in some cases, the carbodiimide group is generated. A part of the generated carbodiimide group reacts with the isocyanate group at the end of the molecule to generate a uretonimine group. The uretonimine group is thermally decomposed by continuing heating in the carbodiimideization step, the carbodiimide group and the isocyanate group at the molecular terminal are regenerated, and further, the carbodiimide group derived from the isocyanate group at the molecular end is generated. ..

In this way, the isocyanate group of the polyisocyanate is converted to a urethane group and a carbodiimide group (and optionally a uretonimine group).

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

Further, in this method, if necessary, the polycarbodiimide composition obtained in the above-mentioned carbodiimideization step can be further reacted with alcohols. 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 carbodiimideization step further has an isocyanate group at the molecular terminal, the polycarbodiimide composition is reacted with alcohols to cause isocyanate at the molecular end. The group can be urethaneized.

Examples of the alcohols in the second urethanization step include the above-mentioned oxyethylene-containing alcohol having a molecular weight of 200 or more.

As for the mixing ratio of alcohols in the second urethanization step, the total amount of the alcohols used in the first urethanization step and the alcohols used in the second urethanization step is the polyisocyanate used in the first urethanization step. It is adjusted so as to be a predetermined ratio with respect to.

Specifically, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the total amount of the hydroxyl groups of the alcohols used in the first urethanization step and the hydroxyl groups of the alcohols used in the second urethanization step. ) Is, for example, more than 2, preferably 3 or more, more preferably 4 or more, and for example, 16 or less, preferably 14 or less, more preferably 10 or less.

Further, in this reaction, the above-mentioned urethanization catalyst may be added, if necessary. The blending ratio of the urethanization catalyst is not particularly limited, and is appropriately set according to the purpose and application.

Further, as the reaction conditions in the second urethanization step, it is preferable that the reaction temperature is in the same range as the reaction temperature in the carbodiimided step under normal pressure and an atmosphere of an inert gas (for example, nitrogen gas). The reaction time is, for example, 15 minutes or more, preferably 30 minutes or more, and for example, 5 hours or less, preferably 1 hour or less.

As a result, the isocyanate group at the molecular terminal of the polycarbodiimide composition and the hydroxyl group of the alcohols undergo a urethanization reaction.

As a result, a polycarbodiimide composition having no isocyanate group at the molecular terminal or having a reduced isocyanate group at the molecular terminal can be obtained.

When the second urethanization step is carried out, the amount of by-products derived from alcohols increases, the molecular weight rapidly increases, the fluidity decreases, the workability decreases, and the aqueous dispersion composition. Dispersibility in objects may decrease. Therefore, preferably, only the first urethanization step and the carbodiimidization step are carried out without carrying out the second urethanization step.

The method for producing the polycarbodiimide composition is not limited to the above, and for example, polyisocyanate, a carbodiimideization catalyst, and alcohols can be collectively mixed and heated.

Further, if necessary, for example, unreacted polyisocyanate, unreacted alcohols, low molecular weight compounds (by-products), organic solvents, carbodiimide catalysts, urethanization catalysts and the like are distilled from the polycarbodiimide composition. It can also be removed by known methods such as extraction and filtration.

Further, if necessary, the polycarbodiimide composition may further include known additives such as storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), plasticizers, blocking inhibitors, and heat-resistant stables. Agents, light-resistant stabilizers, antioxidants, mold release agents, catalysts, pigments, dyes, lubricants, fillers, antioxidants and the like can be added at appropriate timings. The addition ratio of the additive is not particularly limited, and is appropriately set according to the purpose and application.

In addition, 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, still more preferably 380 or more, and particularly preferably 390. It is 450 or less, preferably 440 or less, more preferably 430 or less, still more preferably 420 or less, and particularly preferably 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, as described above. Yes, for example, 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less.

When 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.

In the above method for producing a polycarbodiimide composition, the water content of the alcohols is increased in the reaction between the polyisocyanate having a primary isocyanate group and the alcohols containing an oxyethylene group and containing an alcohol having a molecular weight of 200 or more. Since the amount is not more than a predetermined amount, a polycarbodiimide composition having excellent thermal stability and productivity can be obtained.

Therefore, the above-mentioned polycarbodiimide composition is suitably used as a curing agent in a resin composition for obtaining a cured resin product.

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, but 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. The substance is prepared as a solution (hereinafter referred to as a solution composition) in which the substance is dissolved in an organic solvent.

The aqueous 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 in which water is added to the polycarbodiimide composition and stirred, and a method in which the polycarbodiimide composition is added to water and stirred. .. Preferably, water is added to the polycarbodiimide composition.

The ratio of the polycarbodiimide composition to water is not particularly limited, but the concentration (that is, solid content concentration) of the polycarbodiimide composition (resin component) in the aqueous dispersion composition is, for example, 5% by mass or more, preferably 5% by mass or more. It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

If the curing agent is an aqueous dispersion composition, the compatibility with the aqueous resin (main agent) can be improved, and a cured product having excellent water resistance and chemical resistance can be obtained. Further, since such an aqueous dispersion composition contains the above-mentioned 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 above-mentioned organic solvents, and preferred examples thereof include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, and xylene.

The method for dissolving the polycarbodiimide composition in an organic solvent is not particularly limited, and is a method of adding an organic solvent to the polycarbodiimide composition and stirring, a method of adding the polycarbodiimide composition to the organic solvent and stirring, and the like. Can be mentioned. Preferably, an organic solvent is added to the polycarbodiimide composition.

The ratio of the polycarbodiimide composition to the organic solvent is not particularly limited, but the concentration (that is, the solid content concentration) of the polycarbodiimide composition (resin component) in the solution composition is, for example, 5% by mass or more, preferably 5% by mass or more. It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

If the curing agent is a solution composition, the 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 above-mentioned polycarbodiimide composition, it is excellent in thermal stability and productivity.

Examples of the main agent having a carboxyl group include an aqueous resin having a carboxyl group and an oil-based resin having a carboxyl group.

Examples of the aqueous 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, and other repeating units having 4 or more carbon atoms). Polyethylene) resin and the like. These water-based resins having a carboxyl group can be used alone or in combination of two or more.

Preferred examples of the aqueous 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. It has a hydrophobic polyurethane resin, a hydrophobic acrylic resin having a carboxyl group, a hydrophobic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, a polypropylene-polyethylene (random block) copolymer, and other repeating units having 4 carbon atoms. Examples thereof include the above-mentioned polyolefin) resin. These oil-based resins having a carboxyl group can be used alone or in combination of two or more.

Examples of the oil-based resin having a carboxyl group include a hydrophobic polyurethane resin having a carboxyl group and a hydrophobic acrylic resin having a carboxyl group.

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

The main agent and the curing agent are preferably a combination in which the main agent is an aqueous resin and the curing agent is an aqueous dispersion composition. Further, preferably, a combination in which the main agent is an oil-based resin and the curing agent is a solution composition can be mentioned.

The resin composition preferably includes a combination of an aqueous main agent and an aqueous dispersion composition from the viewpoint of reducing the amount of organic solvent and protecting the global environment.

Further, the resin composition is not particularly limited as long as it contains the above-mentioned main agent and the above-mentioned curing agent, and may be a 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 mixed in advance.

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

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, preferably 99.5 parts by mass or less, preferably 99.5 parts by mass or more, based on 100 parts by mass of the total amount of the main agent. , 95.0 parts by mass or less. The curing agent is, for example, 0.5 parts by mass or more, preferably 5 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less.

Further, 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, and for example, 2.0 or less, preferably 1.5. It is as follows.

In addition, as necessary, the main agent and the curing agent may be one or both of them, for example, an epoxy resin, a catalyst, a coating improver, a leveling agent, a defoaming agent, an antioxidant, an ultraviolet absorber, or the like. Additives such as stabilizers, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, antifungal agents, and silane coupling agents may be added. The blending amount of these additives is appropriately determined depending on the purpose and use thereof.

Further, as the main agent, the above-mentioned aqueous resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group and other resins (for example, hydroxyl group-containing polyurethane resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing polyester resin, etc. It can also be used in combination with (melamine resin, etc.).

Further, as the curing agent, the above-mentioned polycarbodiimide composition and other curing agents (for example, polyisocyanate resin, epoxy resin, etc.) can be used in combination.

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

The method for producing the cured resin is not particularly limited, but for example, when the resin composition is a one-component type, the resin composition is directly applied to the object to be coated or the adherend. 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. Then, by heat-curing the resin composition, a cured resin product can be obtained.

In the above resin composition, the curing temperature is relatively low, specifically, for example, 100 ° C. or lower, preferably 80 ° C. or lower. Further, for example, the temperature is 20 ° C. or higher, preferably 30 ° C. or higher.

Further, the curing time is relatively short, specifically, for example, 1 hour or less, preferably 30 minutes or less. Further, for example, it is 1 minute or more, preferably 5 minutes or more.

Further, if necessary, the cured resin product that has been heat-cured 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, and for example, 40 ° C. or lower, preferably 30 ° C. or lower.

The drying time is, for example, 1 minute or more, preferably 5 minutes or more, and for example, 2 hours or less, preferably 1 hour or less.

The obtained cured resin is a cured product of a resin composition having excellent thermal stability and productivity, and thus is excellent in productivity.

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

Therefore, the resin composition and the cured resin material include coating materials, adhesive materials (adhesives), adhesive materials (adhesive materials), inks, sealants, molding materials, foams and optical materials, as well as polyesters, polylactic acid, polyamides, etc. It is suitably used in various fields such as resin modifiers for modifying resins such as polyimide and polyvinyl alcohol, printing treatment agents, and fiber treatment agents.

When used as a coating material, for example, paints for plastics, paints for automobile exteriors, paints for automobile interiors, paints for electrical and electronic materials, paints for optical materials (lenses, etc.), paints for building materials, glass coat paints, woodwork Examples thereof include paints, film coating paints, ink paints, artificial and synthetic leather paints (coating agents), can paints (coating agents), paper coating paints, and heat-sensitive paper coating paints.

Examples of the paint for plastics include paints for molded products using plastic materials (for example, various polymer materials such as polyolefins, ABS, polycarbonates, polyamides, polyesters and composites thereof). Is a paint for housings (mobile phones, smartphones, personal computers, tablets, etc.), paints for automobile parts (automobile interior materials, headlamps, etc.), paints for household electrical appliances, paints for robot materials, paints for furniture, and stationery. Examples thereof include paints, paints for flexible materials such as rubber, elastomers and gels, paints for eyewear materials (lenses, etc.), paints for optical lenses of electronic devices (surface coating agents), and the like.

The above-mentioned paints for automobile exteriors include, for example, paints for new cars (intermediate coat, base, top, etc.), paints for automobile repair (intermediate coat, base, top, etc.), paints for exterior parts (aluminum wheels, bumpers, etc.). And so on.

When the above resin composition is used as an automobile exterior paint, the above-mentioned aqueous resin having a carboxyl group and the above-mentioned oil-based resin having a carboxyl group can be used as the main agent. Preferably, an aqueous resin having a carboxyl group is used.

Examples of the aqueous 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 hydrophilic having a carboxyl group. Examples thereof include a sex acrylic resin and a hydrophilic polyester resin having a carboxyl group. Further, two or more kinds of the above-mentioned aqueous resins having a carboxyl group can be used in combination.

Further, as the main agent, the above-mentioned aqueous resin having a carboxyl group and / or the above-mentioned oil-based resin having a carboxyl group and other resins (for example, hydroxyl group-containing polyurethane resin, hydroxyl group-containing acrylic resin, hydroxyl group-containing polyester resin, etc. It can also be used in combination with (melamine resin, etc.).

When the above resin composition is used as an automobile 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, for example. It is 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

The acid value of the main agent in terms of solid content is, for example, 5 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, 200 mgKOH / g or less, preferably 100 mgKOH / g or less.

Examples of the curing agent include the above-mentioned polycarbodiimide composition, and the polycarbodiimide composition can also be used in combination with other curing agents (for example, polyisocyanate resin, epoxy resin, etc.).

The film coating paints 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, and the like. Examples thereof include paints for cosmetic packages, paints for decorative films, and paints for release films.

Examples of the adhesive 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). Adhesives for), LED adhesives, automobile interior / exterior adhesives, home appliance adhesives, building material adhesives, solar cell backsheet adhesives, various battery (lithium ion battery, etc.) adhesives, etc. Can be mentioned.

Examples of the ink paint include vehicles of various inks (plate ink, screen ink, flexographic ink, gravure ink, jet ink, printing ink, etc.).

The use of the polycarbodiimide composition is not limited to the above, and for example, as a solid, a polyester, a polyamide resin or polylactic acid, or as a liquid, a hydrolysis resistant agent such as a polyester polyol, acid modification, for example, Composite with maleic acid-modified polyester, or a polyolefin-based emulsion in which acid-modified polyolefin is water-dispersed, composite with acrylic emulsion containing acid moiety and curing agent, converging material for various fibers such as carbon fiber and glass fiber, CFRP, etc. It can be suitably used as a reinforcing material for fiber-reinforced plastics such as FRP, a sizing agent, a curing agent, and the like.

Next, the present invention will be described with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description are the compounding ratios corresponding to them described in the above-mentioned "form for carrying out the invention" (forms for carrying out the invention). Substitute the upper limit value (value defined as "less than or equal to" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") such as content ratio), physical property value, parameter, etc. be able to.

<Ratio of oxyethylene groups in the polycarbodiimide composition (% by mass)>
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)
By the same operation as in Example 1 in the specification of International Publication Pamphlet WO2012 / 121291, 99.9% by mass of 1,5-pentamethylene diisocyanate (hereinafter, may be abbreviated as PDI) was obtained.

Production Example 2A (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
Using dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (hereinafter, KOH) as a catalyst, the mass of ethylene oxide and propylene oxide in the polyol at a temperature of 110 ° C. and a maximum reaction pressure of 0.4 MPa gauge (G). Crude polyols were prepared by random addition polymerization of these alkylene oxides (ethylene oxide and propylene oxide) up to a hydroxyl value (OHV) of 102 mgKOH / g so that the ratio was 50:50.

Next, ion-exchanged water and 1.05 equivalent of phosphoric acid (in the form of a 75.2 wt% aqueous solution) with respect to KOH were added to the crude polyol heated to 80 ° C. under a nitrogen atmosphere, and the temperature was 80 ° C. In, the neutralization reaction was carried out for 2 hours.

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

Then, it was filtered to obtain polyoxyethylene-polyoxypropylene monomethyl ether.

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

Production Example 2B (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained by the same method 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. The number average molecular weight (in terms of polystyrene) measured by the gel permeation chromatograph was 550.

Production Example 2C (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained by the same method 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. The number average molecular weight (in terms of polystyrene) measured by the gel permeation chromatograph was 550.

Production Example 2D (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained by the same method 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. The number average molecular weight (in terms of polystyrene) measured by the gel permeation chromatograph was 550.

Production Example 2E (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
Polyoxyethylene-polyoxypropylene monomethyl ether was obtained by the same method 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. The number average molecular weight (in terms of polystyrene) measured by the gel permeation chromatograph was 550.

Example 1
-Manufacturing of polycarbodiimide composition <dehydration process>
100 parts by mass of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A as alcohols was heat-reduced for 3 hours under the condition of 150 ° C. and 1.3 kPa. .. As a result, the content of water in the alcohols was adjusted to 243 ppm.

The water content was measured by the Karl Fischer method based on JIS K 0068 (2001) (the same shall apply hereinafter).

<Urethane conversion 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 was placed at room temperature in the above-mentioned 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 alcohols 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-phosphorene-1-oxide (MPPO) were charged, and the mixture was refluxed (150). The reaction was terminated by stirring at (° C.) for 8 hours (carbodiimidization step).

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

A part of the obtained polycarbodiimide composition was taken out and the E-type viscosity at 25 ° C. was measured and found to be 1700 mPa · s.
-Preparation of an aqueous dispersion (aqueous dispersion composition) of the polycarbodiimide 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 became 40%. .. After stirring for 5 minutes, the mixture was cooled to room temperature. As a result, an aqueous dispersion of the polycarbodiimide composition was obtained.

-Preparation of a solution (solution composition) of the polycarbodiimide 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 became 40%. After stirring for 5 minutes, the mixture was cooled to room temperature. This gave a solution of the polycarbodiimide composition.

-Preparation of water-based resin composition The aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Then, 1.5 parts by mass of the curing agent and 98.5 parts by mass of polyurethane dispersion (solid content 30% by mass, solid content carboxyl group equivalent 3100 g / mol) as the main agent were mixed to prepare a resin composition. ..

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

Example 2
In the dehydration step, 100 parts by mass of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A as alcohols was added under the condition of 105 ° C. and 1.3 kPa for 1 hour. Heat and reduced pressure treatment. As a result, the content of water in the alcohols was adjusted to 1000 ppm.

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

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

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

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

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

Example 4
In the dehydration step, 100 parts by mass of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 70% by mass, molecular weight 550) obtained in Production Example 2C as alcohols was added under the condition of 105 ° C. and 1.3 kPa for 1 hour. Heat and reduced pressure treatment. As a result, the content of water in the alcohols was adjusted to 1000 ppm.

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

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

Reference example 5
In the dehydration step, 100 parts by mass of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 10% by mass, molecular weight 550) obtained in Production Example 2D as alcohols was added under the condition of 105 ° C. and 1.3 kPa for 1 hour. Heat and reduced pressure treatment. As a result, the content of water in the alcohols was adjusted to 1000 ppm.

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

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

Reference example 6
In the dehydration step, 100 parts by mass of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 90% by mass, molecular weight 550) obtained in Production Example 2E as alcohols was added under the condition of 105 ° C. and 1.3 kPa for 1 hour. Heat and reduced pressure treatment. As a result, the content of water in the alcohols was adjusted to 1000 ppm.

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

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

Reference 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 alcohols is heated under the condition of 105 ° C. and 1.3 kPa for 1 hour. It was depressurized. As a result, the content of water in the alcohols was adjusted to 1000 ppm.

Then, a polycarbodiimide composition was obtained by the same method as in Example 1 except that the above-mentioned 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 mol of polyisocyanate and the E-type viscosity at 25 ° C.

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

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

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

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

Comparative Example 2
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 alcohols is heat-reduced for 1 hour under the condition of 105 ° C. and 20 kPa. did. As a result, the content of water in the alcohols was adjusted to 10000 ppm.

Then, a polycarbodiimide composition was obtained by the same method as in Example 1 except that the above-mentioned 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 mol of polyisocyanate and the E-type viscosity at 25 ° C.

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

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

Claims (8)

A urethanization step in which a polyisocyanate having a primary isocyanate group and alcohols containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group are subjected to a urethanization reaction.
The reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst and subjected to a carbodiimidization reaction to obtain a polycarbodiimide composition.
The alcohols contain water and
The ratio of the water is 1.0 mol or less with respect to 100 mol of the polyisocyanate .
The alcohols
Includes EOPO co-alcohol with oxyethylene (EO) and oxypropylene (PO) groups,
In the EOPO coexisting alcohol, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is 20% by mass or more and 80% by mass or less.
A method for producing a polycarbodiimide composition. 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 claim 1 or 2 , wherein the polyisocyanate is pentamethylene diisocyanate. Polyisocyanate having a primary isocyanate group and
It is a reaction product with alcohols containing alcohols having a molecular weight of 200 or more and containing an oxyethylene group.
The alcohols contain water and
The ratio of the water is 1.0 mol or less with respect to 100 mol of the polyisocyanate .
The alcohols
Includes EOPO co-alcohol with oxyethylene (EO) and oxypropylene (PO) groups,
In the EOPO coexisting alcohol, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is 20% by mass or more and 80% by mass or less.
A polycarbodiimide composition, characterized in that. The polycarbodiimide composition according to claim 4 is
An aqueous dispersion composition characterized by being an aqueous dispersion dispersed in water at a solid content concentration of 5% by mass or more and 90% by mass or less. The polycarbodiimide composition according to claim 4 is
A solution composition comprising a solution dissolved in an organic solvent at a solid content concentration of 5% by mass or more and 90% by mass or less. The main agent having a carboxyl group and
A resin composition comprising a curing agent containing the polycarbodiimide composition according to claim 4 . A cured resin composition, which is a cured product of the resin composition according to claim 7 .