WO2019004290A1

WO2019004290A1 - Polycarbodiimide composition, production method for polycarbodiimide composition, aqueous dispersion composition, solution composition, resin composition, and cured resin object

Info

Publication number: WO2019004290A1
Application number: PCT/JP2018/024395
Authority: WO
Inventors: 達也山下; 俊彦中川; 森田　広一; 山崎　聡
Original assignee: 三井化学株式会社
Priority date: 2017-06-30
Filing date: 2018-06-27
Publication date: 2019-01-03
Also published as: JP2019011457A; JP7017460B2; JP6868692B2; JPWO2019004290A1

Abstract

A polycarbodiimide composition comprising a product of the reaction of a polyisocyanate having a primary isocyanate group with one or more alcohols which comprise an alcohol having an oxyethylene group and having a molecular weight of 200 or higher, the polycarbodiimide composition having a carbodiimide equivalent (g/mol) of 350-450.

Description

Polycarbodiimide composition, method for producing polycarbodiimide composition, water dispersion composition, solution composition, resin composition and resin cured product

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

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, 1008 g of hexamethylene diisocyanate (HDI) and 800 g of polyethylene glycol monomethyl ether having an average molecular weight of 400 are reacted (reaction equivalent ratio (NCO / OH) = 6), Furthermore, a polycarbodiimide compound obtained by adding 13.5 g of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) and further causing a reaction is proposed (for example, Patent Document 1) (See Synthesis Example 83).

Then, a resin composition such as a coating film can be obtained by drying and curing a resin composition comprising such a polycarbodiimide compound (curing agent) and a main agent.

Japanese Patent Application Laid-Open No. 10-316930

However, the polycarbodiimide compound obtained by reacting at the above reaction equivalent ratio has a carbodiimide equivalent exceeding 450, which is measured according to the examples described later. Such polycarbodiimide compounds have the disadvantage that the chemical resistance of the resulting cured resin (coating or the like) is not sufficient.

In addition, excellent storage stability is required of the polycarbodiimide compound.

The present invention relates to a polycarbodiimide composition capable of obtaining a cured resin having excellent storage stability and chemical resistance, a method for producing the polycarbodiimide composition, and an aqueous dispersion containing the polycarbodiimide composition. A composition, a solution composition, a resin composition containing a polycarbodiimide composition, and a resin cured product obtained by curing the resin composition.

The present invention [1] is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group, having a carbodiimide equivalent (g / mol) of 350 It contains the polycarbodiimide composition which is 450 or less.

In the present invention [2], the alcohol comprises an EOPO co-alcohol having both an oxyethylene (EO) group and an oxypropylene (PO) group, and in the EOPO co-alcohol, the ethylene is an oxyethylene group and an oxypropylene group The polycarbodiimide composition as described in said [1] whose ratio of the oxyethylene group with respect to gross mass is 20 mass% or more and 80 mass% or less is included.

The present invention [3] comprises the polycarbodiimide composition according to the above [1] or [2], wherein the alcohol does not contain an alcohol having a molecular weight of less than 200.

The present invention [4] comprises the polycarbodiimide composition according to any one of the above [1] to [3], wherein the polyisocyanate is an aliphatic polyisocyanate.

The invention [5] contains the polycarbodiimide composition according to any one of the above [1] to [4], wherein the polyisocyanate is pentamethylene diisocyanate.

The present invention [6] comprises a urethanation step of causing a urethanization reaction of a polyisocyanate having a primary isocyanate group and an alcohol containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group, and a reaction product in the urethanation step. The product is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidization reaction to obtain a polycarbodiimide composition, and a carbodiimide conversion step is performed to obtain a polycarbodiimide composition, and the carbodiimide equivalent (g / mol) of the polycarbodiimide composition is 350 or more and 450 or less And a method of making the polycarbodiimide composition.

The present invention [7] is an aqueous dispersion in which the polycarbodiimide composition according to any one of the above [1] to [5] is dispersed in water at a solid content concentration of 5% by mass to 90% by mass. It contains a water dispersion composition which is a liquid.

The present invention [8] is a solution in which the polycarbodiimide composition according to any one of the above [1] to [5] is dissolved in an organic solvent at a solid content concentration of 5% by mass to 90% by mass. And contains a solution composition.

The present invention [9] contains a resin composition containing a main agent having a carboxyl group and a curing agent containing the polycarbodiimide composition according to any one of the above [1] to [5]. .

The present invention [10] contains a resin cured product which is a cured product of the resin composition described in the above [9].

The polycarbodiimide composition of the present invention is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group, and having a carbodiimide equivalent (g / mol) Is the above-mentioned predetermined range.

Therefore, the polycarbodiimide composition of the present invention, the aqueous dispersion composition of the present invention containing the polycarbodiimide composition, the solution composition of the present invention, and the resin composition of the present invention containing the polycarbodiimide composition are storage stable. It is possible to obtain a resin cured product which is excellent in the properties and excellent in the chemical resistance.

Moreover, according to the method for producing a polycarbodiimide composition of the present invention, the polycarbodiimide composition of the present invention can be efficiently produced.

Moreover, the resin cured material of this invention is excellent in chemical resistance.

The polycarbodiimide composition of the present invention is a reaction product of a polyisocyanate having a primary isocyanate group (hereinafter sometimes referred to simply as polyisocyanate) and an alcohol.

The primary isocyanate group is defined as a monovalent functional group (-CH ₂ NCO) in which _two hydrogen atoms (H) are bonded to the carbon atom (C) to which the isocyanate group (-NCO) is bonded. Ru.

The polyisocyanate having a primary isocyanate group may have at least one primary isocyanate group, and may have, for example, a secondary isocyanate group, a tertiary isocyanate group, and the like.

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. Group is shown))).

In addition, the tertiary isocyanate group is a trivalent functional group in which a hydrogen atom (H) is not bonded to a carbon atom (C) to which an isocyanate group (-NCO) is bonded (-CR ₁ R _2- NCO ( R ₁ and R ₂ represent the same or different substituents.)).

Examples of polyisocyanates having a primary isocyanate group include aliphatic polyisocyanates having a primary isocyanate group, alicyclic polyisocyanates having a primary isocyanate group, and aromatic aliphatic polyisocyanates having a primary isocyanate group. Be

The aliphatic polyisocyanate having a primary isocyanate group is a linear (linear or branched: acyclic) aliphatic polyisocyanate having a primary isocyanate group, and examples thereof include 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, Data diisocyanate, and aliphatic diisocyanates such as dodecamethylene diisocyanate.

As an alicyclic polyisocyanate having a primary isocyanate group, for example, 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), alicyclic diisocyanates such as norbornane diisocyanate (NBDI), and the like can be mentioned.

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.

As the polyisocyanate having a primary isocyanate group, from the viewpoint of light resistance, handling property and water dispersibility, preferably, aliphatic polyisocyanate having a primary isocyanate group, and alicyclic polyisocyanate having a primary isocyanate group are mentioned. And from the viewpoint of chemical resistance, more preferably, aliphatic polyisocyanates having a primary isocyanate group.

Preferred aliphatic polyisocyanates having a primary isocyanate group include 1,5-pentamethylene diisocyanate (PDI) and 1,6-hexamethylene diisocyanate (HDI) from the viewpoint of easy availability, and more preferably And 1,5-pentamethylene diisocyanate (PDI).

1,5-pentamethylene diisocyanate has a smaller number of carbons and a smaller molecular weight than 1,6-hexamethylene diisocyanate. Therefore, when producing polycarbodiimide compositions of the same molecular weight, using 1,5-pentamethylene diisocyanate increases the carbodiimide group concentration in the polycarbodiimide composition as compared to using 1,6-hexamethylene diisocyanate. be able to. As a result, a cured resin (described later) excellent in various physical properties (water resistance, chemical resistance, etc.) can be obtained. In addition, 1,5-pentamethylene diisocyanate, which has an odd number of carbons, has lower crystallinity due to the amorphous structure derived from the odd number of carbons compared to 1,6-hexamethylene diisocyanate, which has an even number of carbons, It is possible to improve the physical properties of the resin cured product (described later) obtained with excellent properties and dispersibility.

Furthermore, when 1,5-pentamethylene diisocyanate is used, thermal decomposition of the uretone imine group described later is more likely to occur than when 1,6-hexamethylene diisocyanate is used, and therefore, a polycarbodiimide composition can be obtained with a high yield. it can. Moreover, since it can handle also at low temperature, high molecular weight formation of uretone imine can be suppressed.

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 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).

The alcohol contains an alcohol having a molecular weight of 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 containing no 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 consisting of 2 carbon atoms, 4 hydrogen atoms and 1 oxygen atom.

That is, the oxyethylene group (—CH ₂ CH ₂ O—) is one in which one or more hydrogen atoms are substituted by another atomic group (eg, oxypropylene group (—CH (CH ₃ ) CH ₂ O—) Etc.) is distinguished.

In addition, an oxyethylene group (—CH ₂ CH ₂ O—) is one in which the terminal carbon atom is bonded to a hydrogen atom or a hydrocarbon group (eg, ethyl ether group (H—CH ₂ CH ₂ O—), It is also distinguished from propyl ether groups (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 molecular weight of 200 or more oxyethylene-containing alcohols, in addition to oxyethylene groups, may contain oxypropylene groups _{_{(-CH (CH 3) CH 2}} O-), the presence or absence of oxypropylene groups, further classification Be 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 containing an oxyethylene (EO) group and not containing an oxypropylene (PO) group (hereinafter referred to as EO-containing PO non-having a molecular weight of 200 or more) And alcohols having a molecular weight of 200 or more having both an oxyethylene (EO) group and an oxypropylene (PO) group (hereinafter referred to as EOPO co-alcohols 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, containing one or more oxyethylene groups in one molecule, containing no oxypropylene, and containing one or more hydroxyl groups. is there.

As such an EO-containing PO-free alcohol, 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 can be mentioned.

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, containing one or more oxyethylene groups in one molecule, containing no oxypropylene, and containing 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 and the like.

The polyoxyethylene polyol can be obtained, for example, by addition reaction of ethylene oxide (and no addition reaction of propylene oxide) using a low molecular weight polyol as an initiator.

The low molecular weight polyol is a compound having a molecular weight of 60 or more and less than 500 (preferably less than 400) having two or more hydroxyl groups, and, 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 Mixtures of hydrogenated bisphenol A, 1,4-dihydro Dihydric alcohols such as 2--2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, for example, glycerin, trimethylolpropane, triisopropanol Trihydric alcohols such as amines, eg tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentahydric alcohols such as xylitol, eg sorbitol, mannitol, allitol, iditol, dulsitol, altoritol, inositol And a hexahydric alcohol such as dipentaerythritol, for example, a hexahydric alcohol such as perseitol, such as an octahydric alcohol such as sucrose. These can be used alone or in combination of two or more.

Preferred low molecular weight polyols include dihydric alcohols.

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

Further, 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 using a dihydric alcohol as an initiator As polyoxyethylene polyol, bifunctional polyoxyethylene glycol is 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, containing no oxypropylene, and containing one hydroxyl group. .

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

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

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

In the polyoxyethylene glycol monoalkyl ether, the carbon number of the alkyl group is 1 or more, and for example, 20 or less, preferably 8 or less, more preferably 6 or less, more preferably 4 or less, 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, preferably, polyoxyethylene glycol monoalkyl ether is mentioned, and more preferably, polyoxyethylene glycol monomethyl ether is mentioned.

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 an EO-containing PO-free monool.

An EOPO co-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. .

As such an EOPO co-alcohol, an EOPO co-polyol having a molecular weight of 200 or more and an EOPO co-monool having a molecular weight of 200 or more can be mentioned.

An EOPO co-owned 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. .

As the EOPO co-owned polyol having a molecular weight of 200 or more, for example, polyoxyethylene-polyoxypropylene (random and / or block) copolymer and the like can be mentioned.

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

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

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.), for example, dihydric alcohol is used as the initiator In some cases, bifunctional polyoxyethylene-polyoxypropylene glycol is obtained as the polyoxyethylene-polyoxypropylene polyol.

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

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

The EOPO co-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.

As the EOPO co-monopoly monool having a molecular weight of 200 or more, for example, one end-capped polyoxyethylene-polyoxypropylene glycol etc. may be mentioned.

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

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

In the polyoxyethylene-polyoxypropylene glycol monoalkyl ether, the number of carbon atoms of the alkyl group is 1 or more, and for example, 20 or less, preferably 8 or less, more preferably 6 or less, more preferably 4 or less, Particularly preferably, it is 2 or less.
That is, as an alkyl group for sealing one end, preferably, a methyl group and an ethyl group can be mentioned. Specific examples of such polyoxyethylene-polyoxypropylene glycol monoalkyl ether include polyoxyethylene-polyoxypropylene glycol monomethyl ether and polyoxyethylene-polyoxypropylene glycol monoethyl ether.

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

As the EOPO co-owned monool, preferably, polyoxyethylene-polyoxypropylene glycol monoalkyl ether is mentioned, and more preferably, polyoxyethylene-polyoxypropylene glycol monomethyl ether is mentioned.

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

As the EOPO co-alcohol, preferably, EOPO co-monool is mentioned.

In addition, in the EOPO co-alcohol, the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group is, for example, 1 mass% or more, preferably 10 mass, from the viewpoint of the balance of water dispersibility and water resistance. % 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, more preferably , 70 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 charge.

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, from the viewpoint of the balance between water dispersibility and water resistance, an EOPO co-alcohol is preferably mentioned, and more preferably an EOPO co-monool.

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

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

If the number of repeating units of the oxyethylene group is in the above-mentioned range, it is possible to improve the stability at the time of synthesis and the water dispersibility of the polycarbodiimide composition.

In addition, 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, still more preferably 1000 or less.

If 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, stability during synthesis and improvement of the water dispersibility of the polycarbodiimide composition can be achieved.

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 oxyethylene-containing alcohol having a molecular weight of 200 or more.

An alcohol not having an oxyethylene group (—CH ₂ CH ₂ O—) in the molecule is defined as an oxyethylene-free alcohol.

More specifically, as the oxyethylene-free alcohol having a molecular weight of 200 or more, for example, oxyethylene groups such as tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol etc. Monools having a molecular weight of 200 or more not contained, such as polyols having a molecular weight of 200 or more not containing an oxyethylene group such as bisphenol A, hydrogenated bisphenol A, etc. may be mentioned.

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, 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 as long as the excellent effects of the present invention are not inhibited.

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, from the viewpoint of water dispersibility.

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

The alcohol having a molecular weight of less than 200 includes an alcohol having an oxyethylene group and having a molecular weight of less than 200 (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 and having no oxyethylene group Hereinafter, it may be referred to as an oxyethylene-free alcohol having a molecular weight of less than 200.

Examples of oxyethylene-containing alcohols 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 having a molecular weight of less than 200, 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 And monools having a molecular weight of less than 200 containing an oxyethylene group such as (also known as carbitol) (CH ₃ O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -OH).

The oxyethylene-containing alcohol 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 having no oxyethylene group, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, etc. , Polyols with a molecular weight of less than 200 containing no oxyethylene group such as 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, etc. It can be mentioned.

The 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 the 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 as long as the excellent effects of the present invention are not impaired.

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

Although the content rate of the oxyethylene group in the alcohol is not particularly limited, it is adjusted so that the content rate of the oxyethylene group in the obtained polycarbodiimide composition falls within a predetermined range.

Specifically, the content ratio of the oxyethylene group of 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 Preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.

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

The content rate of the oxyethylene group can be calculated from the preparation amount.

And a polycarbodiimide composition can be obtained by making said polyisocyanate and said alcohol react on predetermined conditions, and also making it carry out carbodiimide-ization reaction.

In the following, the method for producing the polycarbodiimide composition is described in detail.

In this method, first, the above polyisocyanate and the above alcohol are subjected to a urethane reaction (urethane step).

In the urethanization step, the reaction ratio of polyisocyanate and alcohol is the carbodiimide equivalent (g / mol) of the polycarbodiimide composition as an equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the alcohol. It is set according to the type (molecular weight etc.) of polyisocyanate and alcohol so as to be in the range described later.

More specifically, although depending on the type of polyisocyanate and alcohol, the reaction ratio of polyisocyanate and alcohol is calculated as the equivalent ratio of isocyanate group of polyisocyanate to hydroxyl group of alcohol (NCO / OH), For example, it is more than 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, preferably, the reaction is carried out at a ratio at which the isocyanate group is in excess with respect to the hydroxyl group.

If the reaction ratio of polyisocyanate and alcohol is within the above range, a resin cured product (described later) excellent in chemical resistance can be obtained.

In addition, in this reaction, for example, known urethanization catalysts such as amines and organic metal compounds may be added, if necessary.

As amines, for example, tertiary amines such as triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, N-methylmorpholine, for example, quaternary ammonium salts such as tetraethylhydroxyammonium, for example, imidazole, And imidazoles such as 2-ethyl-4-methylimidazole.

Examples of the organic metal compounds include tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dimercaptide, dibutyltin maleate, dibutyltin dilaurate (dilaurate Organotin compounds such as dibutyltin (IV), dibutyltin dineodecanoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride and the like, for example, organic lead compounds such as lead octanoate and lead naphthenate, for example, Organic nickel compounds such as nickel naphthenate, eg, organic cobalt compounds such as cobalt naphthenate, eg, organic copper compounds such as copper octenate, eg, organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, etc. It is below.

Furthermore, as the urethanization catalyst, for example, potassium salts such as potassium carbonate, potassium acetate, potassium octylate and the like can be mentioned.

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

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

In addition, the reaction conditions in the urethanization step are the type of polyisocyanate and alcohol, the above equivalent ratio (NCO / OH), etc., so that the carbodiimide equivalent (g / mol) of the polycarbodiimide composition becomes a range described later. It is set according to

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, the temperature is 150 ° C. or less, preferably 120 ° C. or less. 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, 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 liquid containing the reaction product in the above-mentioned urethanization step is heated in the presence of a carbodiimidization catalyst to cause a carbodiimidization reaction (carbodiimidation step).

The carbodiimidization catalyst is not particularly limited, and examples thereof include trialkyl phosphate ester compounds, phospholene oxide compounds, phophorene sulfide compounds, phosphine oxide compounds, and phosphine compounds.

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

Examples of phosphorene oxide compounds 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 -phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and their double bond isomers And compounds of the like.

Examples of phosphalene sulfide compounds include C4-18 phosphorene sulfide compounds such as 1-phenyl-2-phospholene-1-sulfide and the like.

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

Examples of the phosphine compounds include phosphine compounds having 3 to 30 carbon atoms such as bis (oxadiphenylphosphino) ethane.

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

Preferred examples of the carbodiimidization catalyst include phospholene oxide compounds, more preferably 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene- 1-oxide is mentioned.

By using the above-mentioned carbodiimidization catalyst, the activity of carbodiimidization can be improved to lower the reaction temperature, and side reactions such as ureton imination can be suppressed to obtain a polycarbodiimide composition with high yield. In addition, the content of the carbodiimide group can be improved.

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

The compounding 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 process), for example 20 parts by mass or less, preferably 10 parts by mass or less.

In addition, the reaction conditions in the carbodiimide forming step are set such that the content ratio of the carbodiimide group in the polycarbodiimide composition to be obtained is in the specific range described later. More specifically, from the viewpoint of promoting the carbodiimidization reaction and reducing uretone imine, the reaction temperature is, for example, 125 ° C. or higher, preferably under normal pressure and inert gas (such as nitrogen gas) atmosphere. The temperature is 130 ° C. or more, more preferably 135 ° C. or more, for example, 180 ° C. or less, preferably 170 ° C. or less, more preferably 160 ° C. or less. 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 decarboxylatively condensed via an isocyanate group to efficiently generate a carbodiimide group. .

More specifically, if the reaction temperature is at least the above lower limit, the carbodiimide reaction can be advanced while promoting the reaction of decomposing the produced uretonimine into a carbodiimide and an isocyanate group. If the temperature is less than the above lower limit, the thermal decomposition reaction becomes very difficult to occur, the content of uretonimine increases, and the content of carbodiimide group decreases. In addition, the molecular weight may increase due to the increase of uretone imine, and the reaction solution may solidify. On the other hand, if reaction temperature is below the said upper limit, a 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 carbodiimide group decreases, but also the reaction liquid tends to be solidified due to the increase in molecular weight.

In addition, in the carbodiimide forming step, the reaction liquid is preferably refluxed in the presence of an organic solvent from the viewpoint of smoothly performing a carbodiimide forming reaction and promoting decarboxylation condensation.
That is, a 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, for example, 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 Methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene Glycol ether esters such as recalled monomethyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxy propionate, eg 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, for example, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide Halogenated aliphatic hydrocarbons such as methylene iodide and dichloroethane, eg, N-methylpyrrolidone, dimethylformamide, , 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 the organic solvent, preferably, an organic solvent in which the temperature at reflux is in the range of the above-mentioned reaction temperature is mentioned.

Specific examples of such organic solvents include xylene, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate and the like.

Although the compounding ratio of the organic solvent is not particularly limited, it 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). And 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, it is possible to smoothly carry out a carbodiimidization reaction while promoting the decomposition reaction of uretonimine, and to release carbon dioxide gas generated along with the carbodiimidization of an isocyanate group. As a result, the carbodiimidization can be promoted.

And, by such a method, a polycarbodiimide composition containing a urethane group and a carbodiimide group and optionally containing a uretonimine group is obtained.

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

Then, when the reaction product (urethane modified product of polyisocyanate) obtained in the urethanization step is heated in the carbodiimide formation step, a carbodiimide group derived from an isocyanate group at the molecular end is generated, and in some cases, A part of the formed carbodiimide group reacts with the isocyanate group at the molecular terminal to form a uretonimine group. The uretone imine group is thermally decomposed by continuing heating in the carbodiimide formation step, the carbodiimide group and the isocyanate group at the molecular end are regenerated, and further, the 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 and carbodiimide groups (and optionally also uretonimine groups).

As a result, a polycarbodiimide composition is obtained which contains urethane and carbodiimide groups and optionally also uretonimine groups.

In addition, in this method, the polycarbodiimide composition obtained in the above-described carbodiimide forming step can be further reacted with an alcohol, as necessary. In the following, the urethanization process before the carbodiimidization process may be referred to as a first urethanization process, and the urethanation process after the carbodiimidization process may be referred to as a second urethanation process.

Specifically, when the polycarbodiimide composition obtained in the carbodiimidization step further has an isocyanate group at the molecular end, the isocyanate of the molecular end is obtained by reacting the polycarbodiimide composition with an alcohol. The groups can be urethaneized.

In the second urethanation step, the alcohol includes, for example, an oxyethylene-containing alcohol having a molecular weight of 200 or more.

The blend ratio of the alcohol in the second urethanization step is adjusted so that the carbodiimide equivalent (g / mol) of the polycarbodiimide composition is in the range described later. For example, the mixing ratio of the alcohol in the second urethanization step is the total of the alcohol used in the first urethanization step and the alcohol used in the second urethanization step is used in the first urethanization step The ratio is adjusted to be a predetermined ratio with respect to the polyisocyanate.

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

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

Moreover, as reaction conditions in a 2nd urethanation process, under normal pressure and inert gas (for example, nitrogen gas) atmosphere, it is preferable that reaction temperature is the same range as the reaction temperature of the said carbodiimide formation process. 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.

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

As a result, a polycarbodiimide composition having no isocyanate group at the molecular end or having a reduced isocyanate group at the molecular end is 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, and the workability decreases, or the water dispersion composition The dispersibility in the material may decrease. Therefore, preferably, only the first urethanization step and the carbodiimidization step are performed without performing the second urethanization step.

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

In addition, if necessary, for example, unreacted polyisocyanate, unreacted alcohol, low molecular weight compound (by-product), organic solvent, carbodiimidization catalyst, urethanization catalyst, etc. are distilled from the polycarbodiimide composition. It can also be removed by known methods such as extraction, filtration and the like.

The polycarbodiimide composition may further contain, if necessary, known additives, for example, storage stabilizers (o-toluenesulfonamide, p-toluenesulfonamide, etc.), plasticizers, antiblocking agents, heat stability, etc. An agent, a light stabilizer, an antioxidant, a mold 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. In addition, the addition ratio in particular of an additive is not restrict | limited, According to the objective and a use, it sets suitably.

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 350 or more, preferably 360 or more, more preferably 370 or more, still more preferably 380 or more, particularly preferably 390 or more. Or less, preferably 440 or less, more preferably 430 or less, still more preferably 420 or less, particularly preferably 410 or less.

In addition, carbodiimide equivalent (g / mol) is measured based on the Example mentioned later.

In addition, the content ratio of the oxyethylene group of the polycarbodiimide composition thus obtained is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, as described above. For example, it is 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less.

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

And, in such a polycarbodiimide composition, it is a reaction product of a polyisocyanate having a primary isocyanate group and an alcohol containing an oxyethylene-containing alcohol having a molecular weight of 200 or more, and the carbodiimide equivalent (g / mol) is , The above-mentioned predetermined range.

Therefore, such a polycarbodiimide composition is excellent in storage stability, and further, a resin cured product (described later) excellent in chemical resistance can be obtained.

Further, in the above polycarbodiimide composition, if the proportion of the oxyethylene group in the oxyethylene-containing alcohol having a molecular weight of 200 or more is adjusted, the water dispersibility and the water resistance can be compatible, and the water is favorably dispersed. It is possible to improve the water resistance of the obtained resin cured product (described later).

Therefore, by using the polycarbodiimide composition before storage, a resin cured product (described later) having excellent chemical resistance (further, water resistance) can be obtained. Moreover, the fall of the handling property in the case of storing the polycarbodiimide composition can be suppressed. Furthermore, also when the polycarbodiimide composition after storage is used, a resin cured product (described later) excellent in water resistance and chemical resistance can be obtained.

Moreover, according to the manufacturing method of said polycarbodiimide composition, a polycarbodiimide composition can be manufactured efficiently.

And a polycarbodiimide composition is excellent in storage stability, Furthermore, since it can obtain the resin cured material which is excellent in chemical resistance, it is used suitably as a hardening | curing agent in a resin composition.

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, a water dispersion (hereinafter referred to as a water dispersion composition) in which the polycarbodiimide composition is dispersed in water, and a polycarbodiimide composition. The substance is prepared as a solution (hereinafter referred to as a solution composition) or the like dissolved in an organic solvent.

The water dispersion composition contains a polycarbodiimide composition and water.

It does not restrict | limit especially as a method to disperse | distribute a polycarbodiimide composition to water, The method of adding water to a polycarbodiimide composition and stirring it, the method of adding a polycarbodiimide composition to water, stirring etc. are mentioned. . 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, the solid concentration) of the polycarbodiimide composition (resin component) in the water dispersion composition is, for example, 5% by mass or more, preferably It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

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

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

As an organic solvent, the above-mentioned organic solvent is mentioned, Preferably, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene, xylene are mentioned.

The method for dissolving the polycarbodiimide composition in an organic solvent is not particularly limited, and a method of adding the organic solvent to the polycarbodiimide composition and stirring, a method of adding the polycarbodiimide composition to the organic solvent, 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 concentration) of the polycarbodiimide composition (resin component) in the solution composition is, for example, 5% by mass or more, preferably It is 10% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

When the curing agent is a solution composition, the compatibility with the oil-based resin (main agent) can be improved, and a cured product excellent in water resistance and chemical resistance can be obtained. Moreover, such a solution composition is excellent in storage stability.

Examples of the main agent having a carboxyl group include aqueous resins having a carboxyl group and oil-based resins 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 others, repeating unit has 4 or more carbon atoms And polyolefin resins. These aqueous 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 hydrophilic polyurethane resins having a carboxyl group and hydrophilic acrylic resins 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, a carboxyl group Hydrophobic polyurethane resin having a carboxyl group, hydrophobic acrylic resin having a carboxyl group, hydrophobic polyolefin having a carboxyl group (for example, polypropylene, polyethylene, polypropylene-polyethylene (random block) copolymer, and others, repeating unit having 4 carbon atoms The above-mentioned 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 preferably includes 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.

As the main agent and the curing agent, preferably, a combination in which the main agent is an aqueous resin and the curing agent is a water dispersion composition is mentioned. Moreover, Preferably, the main agent is oil resin and the combination whose hardening agent is a solution composition is also mentioned.

From the viewpoint of reducing the organic solvent and protecting the global environment, the resin composition preferably includes a combination of a water-based main agent and a water-dispersed 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 main agent and the curing agent may be separately prepared and may be a two-component type mixed at the time of use It may well be of a one-part type in which the main agent and the curing agent are pre-mixed.

As a resin composition, Preferably, the resin composition of 2 liquid type is mentioned.

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, and for example, 99.5 parts by mass or less, preferably 100 parts by mass with respect to the total 100 parts by mass of them. , 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.

The molar ratio of carbodiimide group in the curing agent to 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 below.

In addition, the main agent and the curing agent may be, for example, an epoxy resin, a catalyst, a coating improver, a leveling agent, an antifoamer, an antioxidant, an ultraviolet absorber, or the like, if necessary. And additives such as stabilizers, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, mildewproofing agents, and silane coupling agents. The blending amount of these additives is appropriately determined depending on the purpose and application.

Also, 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, It can also be used in combination with a melamine resin or the like.

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

And in such a resin composition, since the above-mentioned polycarbodiimide composition is used as a hardening | curing agent, the resin cured material which is excellent in storage stability and excellent in water resistance and chemical resistance can be obtained.

The method for producing a cured resin is not particularly limited. For example, when the resin composition is a one-pack type, the resin composition is applied as it is to a substrate or an adherend. In the case of the two-component resin composition, the main agent and the curing agent are mixed, and the obtained mixture is applied to a substrate or an adherend. And a resin cured material is obtained by heat-hardening a resin composition.

In the above resin composition, the curing temperature is relatively low, specifically, for example, 100 ° C. or less, preferably 80 ° C. or less. Also, for example, the temperature is 20 ° C. or more, preferably 30 ° C. or more.

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

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

In such a case, the drying temperature may be room temperature, for example, 10 ° C. or more, preferably 15 ° C. or more, for example, 40 ° C. or less, preferably 30 ° C. or less.

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.

And since the obtained resin cured product is a cured product of the resin composition which is excellent in storage stability, it is excellent in productivity, and is excellent in water resistance and chemical resistance.

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

Therefore, the resin composition and the resin cured product are coating materials, adhesive materials (adhesives), adhesive materials (adhesives), inks, sealants, molding materials, foams and optical materials, polyesters, polylactic acid, polyamides, 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 car exteriors, paints for car interiors, paints for electric and electronic materials, paints for optical materials (such as lenses), paints for building materials, glass coat paints, woodworking Paints, film coating paints, ink paints, paints for artificial and synthetic leather (coating agent), paints for cans (coating agent), paper coat paints, thermal paper coat paints and the like.

Examples of the paint for plastics include paints for molded articles in which plastic materials (for example, various polymer materials such as polyolefins, ABS, polycarbonates, polyamides, polyesters and composites thereof) are specifically used. Paint for housings (mobile phones, smartphones, PCs, tablets etc.), paints for automobile parts (car interior materials, headlamps etc.), paints for household appliances, paints for robot materials, paints for furniture, stationery Paints, paints for flexible materials such as rubbers, elastomers and gels, paints for eyewear materials (lenses, etc.), paints for optical lenses of electronic devices (surface coating agents), etc. may be mentioned.

In addition, as the paint for automobile exterior, for example, paint for new car (middle coat, base, top etc), paint for car repair (middle coat, base, top etc) paint, paint for exterior parts (aluminum wheel, bumper etc) Etc.

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

As a water-based resin which has a carboxyl group, Preferably, the hydrophilic acrylic resin which has a carboxyl group, the hydrophilic polyurethane resin which has a carboxyl group, the hydrophilic polyester resin which has a carboxyl group are mentioned, More preferably, the hydrophilic which has a carboxyl group Acrylic resin and a hydrophilic polyester 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.

When the above-mentioned resin composition is used as a paint for automobile exterior, 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 The content is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less.

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

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

Moreover, as the film coating paint, for example, a paint for optical members (optical films, optical sheets, etc.), a coating material for optics, a paint for fibers, a paint for electronic and electric materials, a paint for food packages, a paint for medical films, Paints for cosmetic packages, paints for decorative films, paints for release films, and the like.

As the adhesive, for example, adhesive for packaging material, adhesive for electric device, adhesive for liquid crystal display (LCD), adhesive for organic EL display, adhesive for organic EL illumination, display device (electronic paper or plasma display Etc.), adhesives for LEDs, adhesives for interior and exterior for automobiles, adhesives for home appliances, adhesives for building materials, adhesives for solar cell back sheets, adhesives for various batteries (such as lithium ion batteries), etc. Can be mentioned.

Moreover, as said ink coating material, the vehicle of various ink (The plate ink, the screen ink, the flexographic ink, the gravure ink, the jet ink, the printing ink, etc.) is mentioned.

The application of the polycarbodiimide composition is not limited to the above, and for example, polyester, polyamide resin or polylactic acid as solid, or hydrolysis resistant agent such as polyester polyol as liquid, acid modification, for example, Polyolefin-based emulsions in which acid-modified polyolefins are dispersed in water, or composites with acrylic acid-modified polyolefins, curing agents in combination with acrylic emulsions containing acid sites, convergence materials for various fibers such as carbon fibers and glass fibers, CFRP, etc. It can be suitably used as a reinforcing agent for fiber reinforced plastics such as FRP, a sizing agent, a curing agent, and the like.

Next, the present invention will be described based on production examples, examples and comparative examples, but the present invention is not limited by the following examples. In addition, "part" and "%" are mass references | standards unless there is particular mention. In addition, specific numerical values such as mixing ratios (content ratios), physical property values, parameters, etc. used in the following description are the mixing ratios corresponding to those described in the above-mentioned “embodiments for carrying out the invention” Substitutes the upper limit (numerical value defined as "below", "less than") or lower limit (numerical value defined as "above", "excess"), etc. of the corresponding description such as content ratio), physical property value, and parameters be able to.

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

Carbodiimide Equivalent (g / mol) of Polycarbodiimide Composition>
The carbodiimide equivalent of the polycarbodiimide composition was calculated from the charged amount and the measurement result of ¹³ C-NMR.

That is, ¹³ C-NMR was measured under the following apparatus and conditions, and the content ratio of the uretonimine group to 1 mol in total of the carbodiimide group, uretonimine group, allophanate group and urethane group was calculated by the following formula. As a standard of chemical shift ppm, tetramethylsilane (0 ppm) in a CDCL3 solvent was used.
Device; ECA-500 (manufactured by Nippon Denshi)
Conditions: Measurement frequency: 125 MHz, solvent: CDCL3, solute concentration: 50% by mass
Measurement temperature: room temperature, scan number 8500 times repetition time: 3.0 seconds, pulse width: 30 ° (3.70 μs)
Assigned peak of carbon for carbodiimide group (N = C = N group in carbodiimide group): 139 ppm
Assigned peak of carbon of uretone imine group (C = O group in uretone imine group, C = N group): 159 ppm, 145 ppm
Assigned peak of carbon for allophanate group (C = O group in allophanate group): 154 ppm
Peak assigned to carbon of urethane group (C = O group in urethane group)
: 156 ppm
(Carbodiimide equivalent weight) = {(weight of charged solid content) − (molar ratio of generated carbon dioxide to urethane group) × (total alcohol charged mole number) × 44.01}} / {(molar ratio of carbodiimide group to urethane group) ) × (total alcohol added mole number)
The molar ratio of carbon dioxide generated to the urethane group and the molar ratio of carbodiimide group to the urethane group are calculated as follows.

(Mole ratio of generated carbon dioxide to urethane group) = {(integral value of carbodiimide group) + (integral value of uretonimine group)} / {(integral value of urethane group) + (integral value of allophanate group)}
(Molar ratio of carbodiimide group to urethane group) = (integral value of carbodiimide group) / {(integral value of urethane group) + (integral value of allophanate group)}
Production Example 1 (Production of Pentamethylene Diisocyanate)
By the same operation as Example 1 in the specification of International Publication Pamphlet WO 2012/121291, 99.9% by mass of 1,5-pentamethylene diisocyanate (hereinafter sometimes abbreviated as PDI) was obtained.

Production Example 2A (Production of Polyoxyethylene-Polyoxypropylene Monomethyl Ether)
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) using dipropylene glycol monomethyl ether as an initiator and potassium hydroxide (hereinafter, KOH) as a catalyst These alkylene oxides (ethylene oxide and propylene oxide) were subjected to random addition polymerization up to a hydroxyl value (hereinafter, OHV) of 102 mg KOH / g so as to obtain a ratio of 50:50, to prepare a crude polyol.

Then, ion-exchanged water and 1.05 equivalents of phosphoric acid (in the form of a 75.2% by weight aqueous solution) with respect to KOH are added to the crude polyol heated to 80 ° C. under a nitrogen atmosphere, and the temperature is 80 ° C. The reaction was neutralized for 2 hours.

Then, while the temperature was raised, dehydration under reduced pressure was started, and at a pressure of 40 kPa, the adsorbent was added. Finally, heating and pressure reduction were performed for 3 hours under conditions of 105 ° C. and 1.33 kPa or less.

Thereafter, filtration was performed to obtain polyoxyethylene-polyoxypropylene monomethyl ether.

The ratio of oxyethylene groups (hereinafter referred to as EO ratio) to the total of oxyethylene groups and oxypropylene groups of polyoxyethylene-polyoxypropylene monomethyl ether 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)
A 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 ratio of oxyethylene groups (hereinafter referred to as EO ratio) to the total of oxyethylene groups and oxypropylene groups 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)
A 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 ratio of oxyethylene groups (hereinafter referred to as EO ratio) to the total of oxyethylene groups and oxypropylene groups of the 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)
A 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 ratio of oxyethylene groups (hereinafter referred to as EO ratio) to the total of oxyethylene groups and oxypropylene groups 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)
A 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 ratio of oxyethylene groups (hereinafter referred to as EO ratio) to the total of oxyethylene groups and oxypropylene groups 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
Preparation of Polycarbodiimide Composition 100.0 parts by mass of pentamethylene diisocyanate obtained in Preparation Example 1 at room temperature in a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introducing tube. 71.35 parts by mass of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 6 hours (urethane formation step).

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) are charged, and the mixture is refluxed (150 The reaction was terminated by stirring for 8 hours at ° C. (carbodiimidization step).

After completion of the reaction, the reaction solution was cooled to 80 ° C., and PMA was distilled off under reduced pressure to obtain a polycarbodiimide composition. As a result of measuring the obtained polycarbodiimide composition by ¹³ C-NMR, the carbodiimide equivalent was 400 g / mol.

Moreover, as a result of taking out a part of obtained polycarbodiimide composition and measuring E-type viscosity in 5 degreeC and 25 degreeC, they were 5950 mPa * s and 1100 mPa * s, respectively. Furthermore, after a part of the obtained polycarbodiimide composition was stored at 25 ° C. for 2 months under a nitrogen atmosphere, it was 1800 mPa · s as a result of measuring an E-type viscosity at 25 ° C.

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 cooled to room temperature. An aqueous dispersion of the polycarbodiimide composition was thus obtained. In addition, aqueous dispersions of the polycarbodiimide composition were similarly prepared for polycarbodiimide compositions stored for two months at 25 ° C. and one month at 40 ° C. under a nitrogen atmosphere.

Preparation of Solution (Solution Composition) of 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 was 40%. After stirring for 5 minutes, it cooled to room temperature. This gave a solution of the polycarbodiimide composition. Further, a solution of the carbodiimide composition was similarly prepared for each of the polycarbodiimide compositions stored at 25 ° C. for 2 months and at 40 ° C. for 6 weeks under a nitrogen atmosphere.

Preparation of aqueous resin composition An aqueous dispersion of the obtained polycarbodiimide composition was used as a curing agent. Then, 1.5 parts by mass of a 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 main component were mixed to prepare a resin composition. .

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

Example 2
Instead of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A, the polyoxyethylene-polyoxyx obtained in Production Example 2B obtained in Production Example 2B A polycarbodiimide composition was obtained in the same manner as in Example 1 except that propylene monomethyl ether (EO ratio: 30% by mass, molecular weight: 550) was used.

Moreover, the carbodiimide equivalent and the viscosity were measured similarly to Example 1 with respect to the obtained polycarbodiimide composition. The results are shown in Tables 1 and 2.

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

Example 3
Instead of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A, the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 70) obtained in Production Example 2C A polycarbodiimide composition was obtained in the same manner as in Example 1 except that mass% and molecular weight 550) were used.

Example 4
Instead of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A, the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 90) obtained in Production Example 2E A polycarbodiimide composition was obtained in the same manner as in Example 1 except that mass% and molecular weight 550) were used.

Moreover, the carbodiimide equivalent and the viscosity were measured similarly to Example 1 with respect to the obtained polycarbodiimide composition. The polycarbodiimide composition was a waxy solid at 5 ° C. The results are shown in Tables 1 and 2.

Example 5
In place of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A, Uniox M 550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, molecular weight 550) was used. A polycarbodiimide composition was obtained in the same manner as in Example 1 except that it was used.

Example 6
In place of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A, Uniox M 400 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, molecular weight 400) was used. The polycarbodiimide composition was obtained by the same method as Example 1 except having used 51.89 mass parts, and having changed the compounding quantity of PMA into 327.0 mass parts.

Example 7
100.0 parts by mass of hexamethylene diisocyanate is used instead of pentamethylene diisocyanate, and the blending amount of polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A A polycarbodiimide composition was obtained in the same manner as in Example 1 except that the amount was 51.89 parts by mass and the amount of PMA was changed to 327.0 parts by mass.
Moreover, the carbodiimide equivalent and the viscosity were measured similarly to Example 1 with respect to the obtained polycarbodiimide composition. The results are shown in Tables 1 and 2.

Example 8
Instead of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A, the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 10) obtained in Production Example 2D A polycarbodiimide composition was obtained in the same manner as in Example 1 except that mass% and molecular weight 550) were used.

Moreover, the carbodiimide equivalent and the viscosity were measured similarly to Example 1 with respect to the obtained polycarbodiimide composition. The results are shown in Table 3.

Also, in the same manner as in Example 1, a solution of the polycarbodiimide composition was prepared, and a resin composition was prepared.

In addition, the water dispersion of the polycarbodiimide composition was not prepared.

Comparative Example 1
In place of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A, Uniox M 550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, molecular weight 550) was used. The polycarbodiimide was used in the same manner as in Example 1 except that 118.9 parts by mass was used, the blending amount of PMA was changed to 469.5 parts by mass, and the reaction time of the carbodiimide forming step was further changed to 7 hours. The composition was obtained.

Comparative example 2
In place of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50% by mass, molecular weight 550) obtained in Production Example 2A, Uniox M 550 (manufactured by NOF Corporation, polyoxyethylene glycol monomethyl ether, molecular weight 550) was used. The polycarbodiimide was used in the same manner as in Example 1 except that 35.7 parts by mass was used, the blending amount of PMA was changed to 292.6 parts by mass, and the reaction time of the carbodiimidization step was further changed to 9 hours. The composition was obtained.

Comparative example 3
100.0 parts by mass of hexamethylene diisocyanate is used instead of pentamethylene diisocyanate, and instead of the polyoxyethylene-polyoxypropylene monomethyl ether (EO ratio 50 mass%, molecular weight 550) obtained in Production Example 2A 79.3 parts by mass of Ox M 400 (Nippon Yushi Co., Ltd., polyoxyethylene glycol monomethyl ether, molecular weight 400) is used, and the blending amount of PMA is changed to 385.2 parts by mass, and further, the reaction of the carbodiimidization step A polycarbodiimide composition was obtained in the same manner as in Example 1 except that the time was changed to 7 hours.

<Evaluation>
<Water dispersibility>
The polycarbodiimide composition immediately after synthesis was placed in a flask, distilled water was gradually added so that the resin solid content was 40% at 25 ° C., and stirring was performed to observe whether a uniform aqueous dispersion was obtained.

The criteria for evaluation are as follows.
A uniform aqueous dispersion was obtained in less than 4: 10 minutes.
3: 10 minutes or more and less than 1 hour to obtain a uniform water dispersion.
2: It took 1 hour or more to obtain a uniform aqueous dispersion.
1: A uniform aqueous dispersion was not obtained while the polycarbodiimide composition remained sedimented.

<Stability test>
Stability test at 40 ° C. 1.0 part by mass of the obtained polycarbodiimide composition is put in a 10 mL screw bottle, nitrogen-blown, and then capped with a screw cap and stored at 40 ° C., fluidity Was observed (by turning the bottle upside down, until the polycarbodiimide stopped flowing).

The criteria for evaluation are as follows.
4: It took more than six weeks for the liquidity to disappear.
3: 4 weeks or more and less than 6 weeks until the liquidity disappears.
2: 2 weeks or more and less than 4 weeks until the liquidity disappears.
1: Less than 2 weeks until the liquidity disappears.

<Evaluation of coating film>
The resin composition is applied to a standard test plate (JIS-G-3303 SPTE) using a 250 mil doctor blade, dried at 80 ° C. for 10 minutes and 30 minutes, and further dried at room temperature for 1 hour to cure the resin. The coating film which consists of things was obtained. The obtained coating film was evaluated by the following method.

<Water resistance>
Distilled water was spotted on the coating (80 ° C. for 10 minutes), and the change in the coating appearance after 24 hours at 23 ° C. was visually confirmed. The criteria for evaluation are as follows.
Good: No change was confirmed.
Poor: Whitening was confirmed.

<Solvent resistance (chemical resistance)>
The coating (80 ° C for 10 minutes and 30 minutes), in the case of water-based resin composition, methyl ethyl ketone, in the case of solvent-based resin composition, 50 g of gauze impregnated with 50% aqueous ethanol solution It rubs while pressing, and the number of times until the coating film breaks is measured. The criteria for evaluation are as follows.
The coating film was broken after 4: 300 times.
The coating film was broken in the range of 3: 250 to less than 300.
2: The coating film was broken in 100 or more and less than 250 times.
The coating was broken in less than 100 times.

Although the above invention is provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Variations of the invention that are apparent to those skilled in the art are within the scope of the following claims.

The polycarbodiimide composition of the present invention, a method for producing a polycarbodiimide composition, an aqueous dispersion composition, a solution composition, a resin composition and a cured resin product, a coating material, an adhesive material (adhesive), an adhesive material (adhesive material) And inks, sealants, molding materials, foams, optical materials, resin modifiers, print processing agents, fiber processing agents and the like.

Claims

Polyisocyanate having a primary isocyanate group,
A reaction product with an alcohol containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group,
Polycarbodiimide composition characterized in that carbodiimide equivalent (g / mol) is 350 or more and 450 or less.
The alcohol is
Including EOPO co-alcohols having both oxyethylene (EO) and oxypropylene (PO) groups,
The polycarbodiimide composition according to claim 1, wherein the ratio of the oxyethylene group to the total mass of the oxyethylene group and the oxypropylene group in the EOPO co-alcohol is 20 mass% or more and 80 mass% or less. object.
The alcohol is
The polycarbodiimide composition according to claim 1, characterized in that it contains no alcohol having a molecular weight of less than 200.
The polycarbodiimide composition according to claim 1, wherein the polyisocyanate is an aliphatic polyisocyanate.
The polycarbodiimide composition according to claim 1, wherein the polyisocyanate is pentamethylene diisocyanate.
A urethanization step of urethanizing a polyisocyanate having a primary isocyanate group and an alcohol containing an alcohol having a molecular weight of 200 or more containing an oxyethylene group;
The reaction product in the urethanization step is heated in the presence of a carbodiimidization catalyst to perform a carbodiimidization reaction to obtain a polycarbodiimide composition;
The method for producing a polycarbodiimide composition, wherein the carbodiimide equivalent (g / mol) of the polycarbodiimide composition is 350 or more and 450 or less.
The polycarbodiimide composition according to claim 1 is
An aqueous dispersion composition, which is an aqueous dispersion dispersed in water at a ratio of solid content concentration of 5% by mass to 90% by mass.
The polycarbodiimide composition according to claim 1 is
A solution composition characterized in that it 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 containing the polycarbodiimide composition according to claim 1.
A cured resin product, which is a cured product of the resin composition according to claim 9.