BR122022025792B1 - COMPOSITION OF ISOCYANATE, AND METHOD FOR PRODUCING AN ISOCYANATE POLYMER - Google Patents

Abstract

This isocyanate composition contains: an isocyanate compound that is at least functional; and, relating to the isocyanate compound, 1.0 ppm by mass to 1.0 x 104 ppm by mass of a compound that is other than isocyanate and that has at least one unsaturated bond that is not an unsaturated bond that constitutes an aromatic ring .

Description

Split from BR112019007400-7, filed on 10/13/2017. TECHNICAL FIELD

[001] The present invention relates to an isocyanate composition, and a method for producing an isocyanate polymer.

[002] The present invention claims priority based on Japanese Patent Application No. 2016-203092 and Japanese Patent Application No. 2016-203098 filed in Japan on October 14, 2016, the contents of which are incorporated herein by reference.

BASICS OF THE INVENTION

[003] A polyurethane with a urethane linkage is mainly prepared by the reaction of a difunctional or more functional isocyanate (or with more functional groups) and a bifunctional or more functional alcohol is a polymer excellent in tensile strength, abrasion resistance and toughness. to oil, and is used in a large number of materials, including soft foams, hard foams, elastomers, adhesive agents, coating materials and binders. Among these, a polyurethane obtained using an aliphatic or chain cyclic isocyanate as raw material is excellent in weather resistance and light fastness, and is used in areas where external appearance is important, such as coatings for kitchenware, materials automotive coating clears, coil coating materials and the like.

[004] Although diisocyanates, which are difunctional isocyanates, are often used as isocyanates, the dissociated ones are often polymerized by the reaction of the following formulas (a) to (c) to be used as isocyanate polymers in order to improve the properties physical properties of polyurethane and limit vapor pressure to ensure operator safety.

[005] In formulas (a) to (c), R represents a divalent organic group, and R' represents a trivalent organic group.

[006] An isocyanate polymer of the isocyanurate type is obtained in the reaction of formula (a), an isocyanate polymer of the biuret type is obtained in the reaction of formula (b), and a urethane isocyanate polymer is obtained in the reaction of formula (c).

[007] The biuret-type isocyanate polymer is described in Patent Documents 1 to 6. The isocyanurate-type isocyanate polymer is described in Patent Documents 7 to 10. The allophanate-type isocyanate polymer is described in the Patent Documents 11 and 12.

[008] On the other hand, there is an example of an isocyanate with a trifunctional or more functional isocyanate group (see, for example, Patent Document 13). The trifunctional or more functional isocyanate is advantageous in terms that the trifunctional or more functional isocyanate does not need polymerization of diisocyanates necessary to suppress the vapor pressure of the difunctional diisocyanate, because the vapor pressure of the trifunctional or more functional isocyanate is low. Furthermore, although a straight-chain polyurethane is obtained by reacting a difunctional diisocyanate with a diol, a polyurethane with a cross-linked structure is obtained by reacting a trifunctional or more functional isocyanate with a diol, and exhibits health-enhancing effects. physical properties or external appearance of a coating film when used as a coating material, for example.

[009] Thus, it is known that a trifunctional or more functional isocyanate is advantageous compared to a diisocyanate.

RELATED ART DOCUMENTS Patent documents

[0010] Patent Document 1: US Patent No. 3976622 Patent Document 2: US Patent No. 4176132 Patent Document 3: US Patent No. 4290969 Patent Document 4: US Patent No. 4837359 Patent Document 5: US Patent No. 4983762 Patent Document 6: US Patent No. 5641851 Patent Document 7: US Patent No. 4324879 Patent Document 8: US Patent No. 4412073 Patent Document 9: Publication of Application Unexamined Japanese Patent No Sho 57-47319 Patent Document 10: Publication of Unexamined Japanese Patent Application No Sho 63-57577 Patent Document 11: English Patent No. 994890 Patent Document 12: Publication of Unexamined Japanese Patent Application No Hei 7-304724 Patent Document 13: Publication of Unexamined Japanese Patent Application No Sho 56-61341

SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0011] However, a trifunctional or more functional isocyanate has a structure that causes cross-linking and, therefore, the viscosity of an isocyanate composition tends to increase or the isocyanate composition tends to generate gelatinous components when stored. There is a case where uneven coating occurs, the performance of the coating film is deteriorated, or the appearance/beauty is deteriorated by using an isocyanate with an increased viscosity or gelatinous components generated as the coating raw material. Furthermore, there is a case in which incorporation of a small amount of moisture into a difunctional diisocyanate forms a biuret bond shown in the right portion of formula (b) to generate a trifunctional isocyanate, and the resulting trifunctional isocyanate causes crosslinking to increase viscosity or generate gelatinous components in an isocyanate composition when stored in the same way as trifunctional or more functional isocyanate. Although a difunctional isocyanate exhibits less tendency than the trifunctional or more functional one, the difunctional isocyanate may cause uneven coating, deteriorate coating film performance or appearance when used as a coating raw material.

[0012] In view of the above-mentioned circumstances, the present invention aims to provide an isocyanate composition containing a difunctional diisocyanate and/or a trifunctional or more functional isocyanate, the isocyanate composition being excellent in storage stability. Furthermore, the present invention aims to provide a method for producing an isocyanate polymer by polymerizing the isocyanate composition.

MEANS TO SOLVE PROBLEMS

[0013] The present inventors have made intensive studies to solve the above problems, have found that an isocyanate composition containing specific components solves the above-mentioned problems, and the use of the isocyanate composition makes it possible to produce an isocyanate polymer in which the coloring is sufficiently deleted, and thus created the present invention.

[0014] The present invention covers the following aspects.

[0015] (1) An isocyanate composition containing: a trifunctional or more functional isocyanate compound; and a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being other than isocyanate, in an amount of 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound .

[0016] (2) The isocyanate composition according to (1), wherein the compound with at least one unsaturated bond is a compound with a UV absorption in a decamer area or higher isocyanates in a chromatography measurement spectrum gel permeation.

[0017] (3) The isocyanate composition according to (1), wherein the compound having at least one unsaturated bond is a compound of formula (1).

[0018] In the formula, R1 represents a C2-10 aliphatic group or a C6-10 aromatic group, which may have an isocyanate group, R2 represents a C2-10 aliphatic group or a C2-25 aromatic group, which does not have an isocyanate group. isocyanate, and a represents an integer of 1 or 2.

[0019] (4) The isocyanate composition according to (1), wherein the compound having at least one unsaturated bond is a compound having an isocyanurate group and/or biuret group.

[0020] (5) The isocyanate composition according to any one of (1) to (4), additionally containing, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 104 ppm by mass of at least one inert compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds, the inert compound not having neither an unsaturated bond between carbon atoms nor a double bond between a carbon atom and an oxygen atom, excluding unsaturated bonds constituting an aromatic ring; and/or 1.0 ppm by mass to 1.0x103 ppm by mass of a sulfuric acid and/or a sulfuric acid ester; and/or 1.0 ppm by mass to 1.0x103 ppm by mass of a phosphoric acid and/or a phosphoric acid ester.

[0021] (6) The isocyanate composition, according to any one of (1) to (5), additionally containing: 1.0 ppm by mass to 1.0 x 102 ppm by mass, based on the isocyanate compound , of a halogen atom that is not derived from a halogenated hydrocarbon compound.

[0022] (7) The isocyanate composition according to any one of (1) to (6), wherein the amount of the isocyanate compound is 97% by mass or more, based on the total isocyanate composition.

[0023] (8) An isocyanate composition containing: a trifunctional or more functional isocyanate compound; 1.0 ppm by mass to 1.0x103 ppm by mass, based on the isocyanate compound, a sulfuric acid and/or a sulfuric acid ester; and/or 1.0 ppm by mass to 1.0x103 ppm by mass, based on the isocyanate compound, a phosphoric acid and/or a phosphoric acid ester.

[0024] (9) An isocyanate composition containing: a difunctional or more functional isocyanate compound; 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of a compound having a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum ; and/or 1.0 ppm by mass to 1.0x104 ppm by mass, based on the isocyanate compound, of a compound having an isocyanurate group and/or biuret group.

[0025] (10) The isocyanate composition according to (9), containing, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 103 ppm by mass of a sulfuric acid and/or an ester of sulfuric acid, and/or, 1.0 ppm by mass to 1.0 x 103 ppm by mass of a phosphoric acid and/or a phosphoric acid ester.

[0026] (11) A method for producing an isocyanate polymer, containing the reaction of an isocyanate compound contained in the isocyanate composition of any one of (1) to (10) described above, wherein the isocyanate polymer contains: a unit of formula (A) or (B); and at least one unit selected from the group consisting of units of formulas (2), (3), (4), (5), (6), (7) and (8), and a nitrogen atom constituting the bonds of isocyanate polymer with one carbon atom.

[0027] In the formulas, each R3 independently represents a residual group obtained by removing two isocyanate groups from the isocyanate compound, and each R4 independently represents a monovalent organic group.

EFFECTS OF THE INVENTION

[0028] The present invention provides an isocyanate composition containing a difunctional diisocyanate and/or a trifunctional or more functional isocyanate, whose storage stability is improved. Furthermore, the present invention provides a method for producing a polyisocyanate composition by polymerizing the isocyanate composition.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Fig. 1 is a drawing showing a measurement spectrum of gel permeation chromatography obtained in Synthesis Example B3.

MODALITIES FOR CARRYING OUT THE INVENTION

[0030] Preferable embodiments of the present invention will be described below. The present invention is not limited to the following embodiments, and the present invention may be modified in various ways within the summary thereof.

[0031] The present invention provides in one embodiment an isocyanate composition containing: a difunctional or more functional isocyanate compound; and 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being other than the isocyanate, or 1 .0 ppm by mass to 1.0 x 103 ppm by mass, based on the isocyanate compound, a sulfuric acid and/or a sulfuric acid ester, and/or 1.0 ppm by mass at 1.0 x 103 ppm by mass, based on the isocyanate compound, a phosphoric acid and/or a phosphoric acid ester.

[0032] The isocyanate compound is preferably contained in an amount of 97% by mass or more, relative to the total mass of the isocyanate composition.

[0033] The isocyanate composition, according to the present embodiment, is excellent in storage stability, despite the presence of a difunctional or more functional isocyanate. In the present specification, the phrase “an isocyanate composition is excellent in storage stability” means that, even when the isocyanate composition is stored for a long period, the increase in viscosity, the generation of gelatinous components, or the increase in chromaticity are suppressed in the composition. The phrase “long-term storage” means that storage is carried out, for example, for 100 days or more, 200 days or more, 300 days or more, or 500 days or more.

[0034] Thus, the isocyanate composition, according to the present embodiment, is also referred to as “an isocyanate composition to be stored for a long period”. Alternatively, the compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, or sulfuric acid, sulfuric acid ester, phosphoric acid and/or phosphoric acid ester may also be referred to (s) as a quality improving agent, a stabilizer, a viscosity increase inhibitor, a gelatin component generation inhibitor or a chromaticity increase inhibitor, a difunctional diisocyanate and/or an isocyanate compound trifunctional or more functional.

[0035] Hereinafter, the compounds contained in the isocyanate composition, according to the present embodiment, will be explained.

<Difunctional or more functional isocyanate compound>

[0036] In the isocyanate composition according to the present embodiment, a compound of the following formula (10) is preferably used as a difunctional or more functional isocyanate compound.

[0037] In formula (10), c represents an integer of 2 or more, and R33 represents an organic group with a valence of c.

[0038] In formula (10), R33 preferably represents a C3-85 organic group, and more preferably a C3-30 organic group.

[0039] R33 represents an aliphatic group, an aromatic group or a group formed by the connection of an aliphatic group and an aromatic group. Specific examples of R33 include cyclic groups such as cyclic hydrocarbon groups (monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, cross-linked cyclic hydrocarbon groups, spiro hydrocarbon groups, ring structure hydrocarbon groups, cyclic hydrocarbon groups containing side chains), heterocyclic groups, heterocyclic spiro, and cyclic groups cross-linked with heteroatoms; acyclic hydrocarbon groups, groups in which one acyclic hydrocarbon group and at least one cyclic group are linked, and groups in which the above-mentioned groups are linked to specific non-metallic atoms (such as carbon, oxygen, nitrogen, sulfur or silicon) through covalent bonds.

[0040] The phrase “linked to specific non-metallic atoms through covalent bonds” means the state in which, for example, the above-mentioned group is linked to any of the groups of the following formulas (11) to (23) through a covalent bond.

[0041] In the isocyanate composition, according to the present embodiment, the isocyanate compound is preferably a compound of formula (10), wherein c represents an integer from 2 to 5, more preferably 2 or 3, and even more preferably 3, considering ease of preparation or handling. Among the bonds of formulas (11) to (23), an isocyanate compound having a bond of formula (11) to (16), (18), (20), or (23) is preferred, and an isocyanate compound having a bond of formula (12) or (18) is more preferable.

[0042] As a difunctional diisocyanate compound of formula (10) wherein c represents 2, it is preferably used, for example, a C4-30 aliphatic diisocyanate, a C8-30 alicyclic diisocyanate, or a di - C8-30 isocyanate containing an aromatic group.

[0043] Specific examples of C4-30 aliphatic diisocyanate include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,4-diisocyanate-2-methylbutane, diisocyanate of 1,6-hexamethylene, 1,6-diisocyanate-2,5-dimethylhexane, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, lysine diisocyanate methyl ester and lysine diisocyanate ethyl ester.

[0044] Specific examples of C8-30 alicyclic diisocyanate include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated diisocyanate tetramethylxylylene, norbornene diisocyanate.

[0045] Examples of the diisocyanate containing the aromatic group C8-30 include: 4,4'-diphenylmethane diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate and naphthalene diisocyanate.

[0046] In the case where the compound has structural isomers, the structural isomers are included in the above-mentioned examples.

[0047] Additionally, compounds formed by dimerization of two difunctional isocyanate molecules through a urea bond or a uretdione structure can be used as a difunctional isocyanate.

[0048] An isocyanate compound of formula (24) is preferably used as a trifunctional isocyanate.

[0049] In formula (24), a plurality of Y1 each independently represents a single bond, or a bivalent C120 hydrocarbon group which may contain an ester structure and/or an ether structure, and R24 represents a hydrogen atom or a monovalent C1-12 hydrocarbon group.

[0050] In formula (24), R24 preferably represents a C1-10 aliphatic group or a C6-10 aromatic group, and specific examples thereof include: aliphatic groups, such as a methyl group, an ethyl group, a propyl group , a butyl group, a pentyl group, a hexyl group and a decyl group; and aromatic groups such as a phenyl group, a methylphenyl group, an ethylphenyl group, a butylphenyl group, a dimethylphenyl group and a diethylphenyl group.

[0051] In formula (24), Y1 preferably represents a divalent C1-100 aliphatic group, a divalent C6-100 aromatic group, a divalent C2-100 group in which the aliphatic groups are linked through an ester structure, a divalent C2-100 group in which an aliphatic group is linked through an ether structure, a divalent C7-100 group in which an aliphatic group and an aromatic group are linked through an ester structure, a divalent C7-100 group in which an aliphatic group and an aromatic group are linked through an ether structure, a divalent C14-100 group in which the aromatic groups are linked through an ester structure, or a divalent C14-100 group in which the aromatic groups are linked through an ester structure ether.

[0052] Other specific examples of the isocyanate compound of formula (24) include: compounds in which Y1 in formula (24) represents a divalent C1-100 aliphatic group or a divalent C6-100 aromatic group, and compounds of the following formula (25 ), (26) or (27) and the compound of formula (25) or (27) is more preferable. Examples of the compounds in which Y1 in formula (24) is a divalent C1-100 aliphatic group or a divalent C6-100 aromatic group include 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-triisocyanato- hexane, 1,8-diisocyanate-4-(isocyanatomethyl)-2,4,7-trimethyloctane, 1,5-diisocyanate-3-(isocyanatomethyl)pentane, 1,6,11-triisocyanatondecane, 1,4 ,7-triisocyanate-heptane, 1,2,2-triisocyanate-butane, 1,2,6-tri-isocyanate-hexane, 1-isocyanate-2,2-bis(isocyanatomethyl)butane, 1,3,5 -triisocyanatocyclohexane, 1,7-diisocyanato-4-(3-isocyanatopropyl)heptane, 1,3-diisocyanate-2-(isocyanatomethyl)-2-methylpropane, 1,3,5-tri- isocyanatobenzene, 1,3,5-triisocyanate-2-methylbenzene, 1,3,5-tris(1-isocyanatopropane-2-yl)benzene, 1,3,5-tris(1-isocyanatopropane-2-yl) -2-methylbenzene, 1,3,5-tris(1-isocyanatomethyl)-2-methylbenzene and 2,2'-((2-isocyanato-1,3-phenylene)bis(methylene))bis(isocyanatobenzene).

[0053] In formula (25), d, g and i each independently represent an integer from 1 to 4, and, f, and h each independently represent an integer from 0 to 5, and j, k and l represent, each independently, 0 or 1.

[0054] Specific examples of the compound of formula (25) include: 1,2,3-propane triisocyanate, where j, kel represent 0, e and f represent 1 and h represents 0; tris(2-isocyanatoethyl)amine, where j, kel represent 0, e, f, and h represent 2; 1,6,11-triisocyanatondecane, where j, kel represent 0, e and f represent 5 and h represents 0; 1,3,6-hexamethylene triisocyanate, where j, kel represent 0, e represents 3, f represents 2 and h represents 0; 1,8-diisocyanate-4-(isocyanatomethyl)octane, wherein j, kel represent 0, e represents 4, f represents 1, and h represents 3; 2-isocyanatoethyl-2,5-diisocyanatopentanoate, where e represents 3, f and h represents 0, j and l represents 0, and k represents 1; 2-isocyanatoethyl-2,6-diisocyanatohexanoate, where e represents 4, f and h represents 0, g represents 2, j and l represents 0, and k represents 1; bis(2-isocyanatoethyl)-2-isocyanatobutanedioate, where deg represents 2, e represents 1, f and h represents 0, j and k represents 1, el represents 0; bis(2-isocyanatoethyl)-2-isocyanatopentanedioate, where deg represents 2, e represents 2, f and h represents 0, j and k represents 1, el represents 0; and tris(2-isocyanatoethyl)hexane-1,3,6-tricarboxylate, where d, g and i represent 2, j, kel represent 1, e represents 3, f represents 2, and h represents 0.

[0055] In formula (26), X' represents a C1-4 hydrocarbon group, m, n and q each represent an integer of 1 or more, the sum of m, n and q is 3 to 99, and p represents an integer from 0 to 3.

[0056] A compound of the following formula (27) is preferably used, and a compound of the following formula (27-1) is more preferably used, as an isocyanate compound of the isocyanate composition according to the present embodiment.

[0057] In formulas (27) and (27-1), may have an ester structure and/or an ether structure or a single bond.

[0058] In formulas (27) and (27-1), X2 to C6-20 divalent, a C2-20 divalent group in which aliphatic groups are linked through an ester structure, a C2-20 divalent group in which aliphatic groups are linked through an ether structure, a C7-20 divalent group in which an aliphatic group and an aromatic group are linked through an ester structure, a divalent C7-20 group in which an aliphatic group and an aromatic group are linked through an ether structure, a divalent C14-20 group in which the groups aromatic groups are linked through an ester structure, or a divalent C14-20 group in which the aromatic groups are linked through an ether structure, and more preferably represents a single bond, a divalent C1-20 aliphatic group, or a C6 aromatic group -20 divalent. Among these, X2 to X4 preferably represent a hydrogen atom or a C1-6 alkyl group and Y4 to Y6 preferably represent a single bond or a C1-6 alkylene group.

[0059] Furthermore, a compound in which three molecules of the difunctional isocyanate are trimerized through an isocyanurate ring structure or a biuret bond can be used as a trifunctional isocyanate.

[0060] Specific examples of the compound of formula (27) include 1,3,5-triisocyanatobenzene, 1,3,5-triisocyanate-2-methylbenzene, 1,3,5-tris(1-isocyanatopropan-2 -yl)benzene, 1,3,5-tris(1-isocyanatopropane-2-yl)-2-methylbenzene, 1,3,5-tris(1-isocyanatomethyl)-2-methylbenzene and 2,2'-(( 2- isocyanate-1,3-phenylene)bis(methylene))bis(isocyanatobenzene).

<Compound having an unsaturated bond>

[0061] In addition to the difunctional or more functional isocyanate compound, the isocyanate composition, according to the present embodiment, contains a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being different from the isocyanate compound .

[0062] The compound having an unsaturated bond (hereinafter may be referred to as an “unsaturated bond compound”), according to the present embodiment, has at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring. The unsaturated bond is preferably an unsaturated bond between carbon atoms, an unsaturated bond between a carbon atom and a nitrogen atom, or an unsaturated bond between a carbon atom and an oxygen atom. From the point of view of the stability of the compound, the unsaturated bond is preferably a double bond and more preferably a double bond between carbon atoms (C=C) or a double bond between a carbon atom and an oxygen atom (C=O ). Furthermore, the carbon atoms that make up the compound preferentially bond to at least three atoms, respectively.

[0063] Although there is a general case in which a double bond between carbon atoms is a double bond between carbon atoms that constitutes an aromatic ring, the unsaturated bond contained in the unsaturated bond compound in the isocyanate composition, according to The present embodiment does not contain a double bond between carbon atoms constituting an aromatic ring.

[0064] Examples of the unsaturated bond compound include: compounds of the following formula (28); carbonic acid derivatives (such as N-unsubstituted carbamic acid ester, carbonate ester and N-substituted carbamic ester), compounds that have a UV absorption in an area of higher decamers or isocyanates in a chromatography measurement spectrum gel permeation, compounds having an isocyanurate group and/or a biuret group, and compounds of the following formula (1). Among these, the unsaturated binding compound is preferably a compound with a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum, or a compound of the following formula (1).

[0065] In formula (1), R1 represents a C2-10 aliphatic group or a C6-10 aromatic group, which may contain an isocyanate group, R2 represents a C2-10 aliphatic group or a C6-25 aromatic group, which does not contains an isocyanate group, and a represents an integer of 1 or 2.

[0066] In formula (28), R5, R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom or an organic group C1-10, R5 to R8 do not simultaneously represent hydrogen atoms, r represents 1 when R5 represents a hydrogen atom or a halogen atom, and r represents an integer from 1 to 3 when R5 represents an organic group C1-10.

<Compound with a UV absorption in an area of higher decamers or isocyanates in a gel permeation chromatography measurement spectrum>

[0067] A compound having a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography (GPC) measurement spectrum is preferably a compound having a nylon 1 body structure of the following formula (37) as its main skeleton.

[0068] In the formula, R29 represents a residual group obtained by removing an isocyanate group from the difunctional or more functional isocyanate compound, and w represents an integer of 1 or more. Its terminal groups are not described.

[0069] The isocyanate that constitutes the compound having a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography (GPC) measurement spectrum may be the same or different from an isocyanate that constitutes the composition of isocyanate according to the present embodiment and may be selected from the isocyanate compounds mentioned in the description in relation to the <difunctional or more functional isocyanate compound>.

[0070] The compound is defined by measuring GPC. Specifically, the compound exhibits a UV absorption peak at the wavelength of 254 nm in the area of decamer or higher isocyanates when GPC is performed using tetrahydrofuran as a developing solvent and polystyrene as a molecular weight analytical standard substance. .

[0071] The concentration of the compound with a UV absorption in an area of higher decamers or isocyanates in a gel permeation chromatography (GPC) measurement spectrum can be determined using a GPC equipped with a UV detector and a differential refractometer ( the UV detector and differential refractometer can be connected in parallel or in series) by performing the (B)/(A) calculation where (A) represents the peak area corresponding to difunctional or more functional isocyanate compounds in the index of differential refraction, and (B) represents the peak area corresponding to a compound with UV absorption (at a wavelength of 254 nm) in the area of the decamer or higher isocyanates.

<Compound having an isocyanurate group and/or biuret group>

[0072] A compound having an isocyanurate group and/or a biuret group is a compound having a group of the following formula (6') or formula (7').

[0073] In the formulas, R29 represents a residual group obtained by removing an isocyanate group from a difunctional or more functional isocyanate compound.

[0074] An isocyanate constituting a compound having an isocyanurate group and/or a biuret group may be of the same type of an isocyanate as that of an isocyanate compound constituting the isocyanate composition according to the present embodiment or a different type of an isocyanate , and may be selected from isocyanate compounds mentioned in the description in relation to the <difunctional or more functional isocyanate compound>. The amount of the compound having an isocyanurate group and/or a biuret group in the isocyanate composition may be an addition amount of the compound having an isocyanurate group and/or a biuret group or an amount determined by GPC carried out using tetrahydrofuran as a solvent. of revelation. In the method for determining the amount by GPC, the amount can be specifically determined by GPC equipped with a differential refractometer by performing a (B)/(A) calculation where (A) represents the peak area corresponding to a compound of isocyanate in the differential refractive index and (B) represents the peak area corresponding to a compound that has an isocyanurate group and/or a biuret group.<Compound of formula (1)>

[0075] In the formula, R1 represents a C2-10 aliphatic group or a C6-10 aromatic group, which may have an isocyanate group, R2 represents a C2-10 aliphatic group or a C6-25 aromatic group, which does not contain an isocyanate group. isocyanate, and a represents an integer of 1 or 2.

[0076] In formula (1), R1 represents a C2-10 aliphatic group or a C6-10 aromatic group, examples of the aliphatic group include: residual groups obtained by removing the number a of hydrogen atoms from compounds such as methane, ethane, propane butane, heptane, hexane, octane, nonane or decane, examples of the aromatic group include residual groups obtained by removing the number a of hydrogen atoms from compounds such as benzene, methylbenzene, ethylbenzene, butylbenzene, octylbenzene, nonylbenzene, diphenyl, terphenyl , phenylpropylbenzene, di(phenylpropyl)benzene or diphenyl ether. Among these, R1 is preferably a residual group obtained by removing number a of hydrogen atoms from a C2-10 alkane or benzene.

[0077] In formula (1), R2 represents a C2-15 aliphatic group or a C6-25 aromatic group, which does not contain an isocyanate group, and preferably represents a C5-15 alkyl group.

[0078] Specific examples of the compound of formula (3) include ethyl acetate, butyl acetate, hexyl acetate, methyl propionate, ethyl butyrate, butyl butyrate, ethyl valerate, butyl valerate, ethyl hexanoate, octanoate ethyl, butyl caprate, phenyl acetate, benzyl acetate, methyl benzoate, ethyl benzoate, phenyl benzoate, benzyl benzoate, diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, di-2-ethyl phthalate -hexyl, di-isodecyl adipate and tri-isodecyl trimellitate.

[0079] In formula (1), R1 may contain an isocyanate group, and specifically, the compound of formula (1) may be a compound of the following formula (38) or (39).

[0080] In the formulas, R2 represents a group defined in formula (1), R30 represents a hydrogen atom, an aliphatic group C1-8, or an aromatic group C6-8, which may additionally contain an isocyanate group, and R31 represents a hydrogen atom, a C1-7 aliphatic group, or a C6-7 aromatic group, which may additionally contain an isocyanate group.

[0081] In the case where the compound of formula (1) has the same structure as the isocyanate compound in the composition according to the present embodiment, the compound is defined as the isocyanate compound.

[0082] Specific examples thereof include compounds of the following formulas.

[0083] In the case where the compound of formula (1) has the same structure as the isocyanate compound in the composition according to the present embodiment, the compound is defined as an isocyanate compound.<Compound of formula (28)>

[0084] In formula (28), R5, R6, R7 and R8 each independently represent a hydrogen atom, a halogen atom, or an organic group C1-10, R5 to R8 do not simultaneously represent hydrogen atoms, r represents 1 when R5 represents a hydrogen atom or a halogen atom, and r represents an integer from 1 to 3 when R5 represents an organic group C1-10.

[0085] In the compounds of formula (28), R5 preferably represents a hydrogen atom or an organic group C1-10. When R5 represents an organic group, R5 preferably represents a C1-10 aliphatic group or a C6-10 aromatic group.

[0086] Examples of R5 include: groups obtained by removing the number r of hydrogen atoms from alkanes, such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane or structural isomers thereof; groups obtained by removing the number r of hydrogen atoms from cycloalkanes, such as cyclopentane, cyclohexane, cyclopentane and cyclooctane; groups obtained by removing the number r of hydrogen atoms from cycloalkanes substituted by chain alkyl groups, such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, propylcyclohexane, butylcyclohexane, pentylcyclohexane, hexylcyclohexane, dimethylcyclohexane, diethylcyclohexane, dibutylcyclohexane and structural isomers thereof; groups obtained by removing the number r of hydrogen atoms from aromatic compounds such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, hexylbenzene, octylbenzene, naphthalene, dimethylbenzene, diethylbenzene, dipropylbenzene, dibutylbenzene, dihexylbenzene, dioctylbenzene, methylnaphthalene, ethylnaphthalene, butylnaphthalene and structural isomers. Among these, R5 preferably represents a group obtained by removing the number r of hydrogen atoms from a C1-10 alkane or a benzene.

[0087] R6 to R8 represent, preferably, hydrogen atoms or organic groups C1-10.

[0088] When R6 to R8 represent organic groups, R6 to R8 preferably represent C1-10 aliphatic groups or C6-10 aromatic groups. Examples of R6 to R8 include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and structural isomers thereof; chain alkyloxy groups, such as a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group and structural isomers of the same; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclo group -hexyl, a butylcyclohexyl group, a pentylcyclohexyl group, hexylcyclohexyl group, a dimethylcyclohexyl group, a diethylcyclohexyl group, a dibutylcyclohexyl group and structural isomers thereof; groups consisting of chain alkyl groups and cycloalkyl groups; groups formed by removing a hydrogen atom from aromatic compounds such as benzene, toluene, ethylbenzene, propylbenzene, butylbenzene, hexylbenzene, octylbenzene, naphthalene, dimethylbenzene, diethylbenzene, dipropylbenzene, dibutylbenzene, dihexylbenzene, dioctylbenzene, methylnaphthalene, ethylnaphthalene, butylnaphthalene and structural isomers of the same. Among these, it is preferred that R6 to R8 represents C1-10 alkyl groups.

[0089] Specific examples of the compound of formula (28) include: propene, butene, pentene, 2-methylbutene, 2,4,4-trimethylpentene, hexene, octene, nonene, decene, hexadecene, octadecene, butadiene, pentadiene, hexadiene, chloroethylene, chloropropene, chlorobutene, chloropentene, chlorohexene, chloroctene, chlorononene, chlorodecene, chlorohexadecene, chlorooctadecene, chlorobutadiene, chloropentadiene, chlorohexadiene, dichloroethylene, dichloropropene, dichlorobutene, dichloropenentene, dichlorohexene, dichloro- octene, dichlorononene, dichlorodecene, dichlorohexadecene, dichlorooctadecene, dichlorobutadiene, dichloropentadiene, dichlorohexadiene, bromoethylene, bromopropene, bromobutene, bromopentene, bromohexene, bromooctene, bromononene, bromodecene, bromohexadecene, bromooctadecene, bromobutadiene, bromopentadiene, bromohexadiene, dibromoethylene, dibromopropene, dibromobutene, dibromopentene, dibromohexene, dibromooctene, dibromononene, dibromodecene, dibromohexadecene, dibromooctadecene, dibromobutadiene, dibromopentadiene, dibromohexadiene, fluoroethylene, fluoropropene, fluorobutene, fluoropenten o, fluoroohexene, fluoroooctene, fluorononene, fluorodecene, fluorohexadecene, fluorooctadecene, fluorobutadiene, fluoropentadiene, fluorohexadiene, difluoroethylene, difluoropropene, difluorobutene, difluoropentene, difluorohexene, difluorooctene, difluorononene,difluorodecene, difluorohexadecene, difluorooctadecene, difluorobutadiene, difluoropentadiene, difluorohexadiene, styrene, propenylbenzene, isopropenylbenzene (also referred to as “α-methylstyrene”), allylbenzene, phenylbutadiene, divinylbenzene, stilbene, vinylanisole, propenylanisole, allylanisole, isoanethol, elemycin, asarone, chlorostyrene, chloropropenylbenzene, chloroisopropenylbenzene, chloroallylbenzene, chlorophenylbutadiene, chlorodivinylbenzene, chlorine stilbene, chlorovinylanisole, chloropropenylanisole, chloroallylanisole, chloroisoanethol, chlorolemycin, chlorasarone, bromostyrene, bromopropenylbenzene, bromoisopropenylbenzene, bromoallylbenzene, bromophenylbutadiene, bromodivinylbenzene, bromostilbene, bromovinylanisole, bromopropenylanisole, bromoallylanisole, bromoisoanethol, bromoelemycin, bromoas arone, fluorostyrene, fluoropropenylbenzene, fluoroisopropenylbenzene, fluoroallylbenzene, fluorophenylbutadiene fluorodivinylbenzene, fluorostilbene , fluorovinylanisole, fluoropropenylanisole, fluoroallylanisole, fluoroisoanethol, fluoroelemycin, fluoroasarone, dichlorostyrene, dichloropropenylbenzene, dichloroisopropenylbenzene, dichloroallylbenzene, dichlorophenylbutadiene, dichlorodivinylbenzene, dichlorostilbene, dichlorovinylanisole, dichloropropenylanisole, dichloroallylanisol , dichloroisoanethol, dichloroelemycin, dichloroasarone, dibromostyrene, dibromopropenylbenzene, dibromoisopropenylbenzene, dibromoallylbenzene, dibromophenylbutadiene, dibromodivinylbenzene , dibromostilbene, dibromovinylanisole, dibromopropenylanisole, dibromoallylanisole, dibromoisoanethol, dibromoelemycin, dibromoasarone, difluorostyrene, difluoropropenylbenzene, difluoroisopropenylbenzene, difluoroalkylbenzene, difluorophenylbutadiene, difluorodivinylbenzene, difluorostilbene, difluorovinylanisole, difluoropropenylanisole , difluoroallylanisole, difluoroisoanethol, difluoroelemicin, difluoroasarone, and structural isomers thereof.

<Carbonic acid derivative>

[0090] A carbonic acid derivative used in the isocyanate composition according to the present embodiment is represented by the following formula (29).

[0091] In formula (29), Z1 and Z2 each independently represent a residual group obtained by removing a hydrogen atom from a hydroxy compound or an amino group that can be replaced by an organic group.

[0092] Examples of the compound of formula (29) include urea compounds, N-unsubstituted carbamic acid esters, carbonate esters and N-substituted carbamic acid esters.

<<Urea compounds>>

[0093] The urea compound is a compound having at least one urea bond in a molecule thereof. The urea compound used in the isocyanate composition according to the present embodiment is preferably a compound with a urea bond, and is represented by the following formula (30).

[0094] In formula (30), R9, R10, R11 and R12 each independently represent a C1-20 aliphatic group, a C7-20 aliphatic group substituted by an aromatic compound, a C6-20 aromatic group or an atom of hydrogen, the sum of the number of carbons that constitute R9 and R11 is an integer from 0 to 20, and the sum of the number of carbons that constitute R10 and R12 is an integer from 0 to 20.

[0095] Specific examples of R9, R10, R11 and R12 in formula (30) include: a hydrogen atom; chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group , a dodecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group and a nonadecyl group; C6-20 aromatic groups, such as a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl, a biphenyl group, a dimethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a dipentylphenyl group, a dihexylphenyl group, a diheptylphenyl group, a terphenyl group, a trimethylphenyl group, a triethylphenyl group, a tripropylphenyl group, and a tributylphenyl group; and C7-20 aralkyl groups such as a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group and a phenylnonyl group.

[0096] Examples of the urea compound of formula (30) include urea, methylurea, ethylurea, propylurea, butylurea, pentylurea, hexylurea, heptylurea, octylurea, nonylurea, decylurea, undecylurea, dodecylurea, tridecylurea, tetradecylurea, pentadecylurea, hexadecylurea, heptadecylurea , octadecylurea, nonadecylurea, phenylurea, N-(methylphenyl)urea, N-(ethylphenyl)urea, N-(propylphenyl)urea, N-(butylphenyl)urea, N-(pentylphenyl)urea, N-(hexylphenyl)urea, N- (heptylphenyl)urea, N-(octylphenyl)urea, N-(nonylphenyl)urea, N-(decylphenyl)urea, N-biphenylurea, N-(dimethylphenyl)urea, N-(diethylphenyl)urea, N-(dipropylphenyl)urea , N-(dibutylphenyl)urea, N-(dipentylphenyl)urea, N-(dihexylphenyl)urea, N-(diheptylphenyl)urea, N-terphenylurea, N-(trimethylphenyl)urea, N-(triethylphenyl)urea , N-(tripropylphenyl)urea, N-(tributylphenyl)urea, N-(phenylmethyl)urea, N-(phenylethyl)urea, N-(phenylpropyl)urea, N-(phenylbutyl)urea, N-(phenylpentyl)urea, N-(phenylhexyl)urea, N-(phenylheptyl)urea, N-(phenyloctyl)urea, N-(phenylnonyl)urea, dimethylurea, diethylurea, dipropylurea, dibutylurea, dipentylurea, dihexylurea, diheptylurea, dioctylurea, dinonylurea, didecylurea, diundecylurea, didodecylurea, ditridecylurea, ditetradecylurea, dipentadecylurea, dihexadecylurea, diheptadecylurea, dioctadecylurea, dinonadecyl, diphenylurea, di(methylphenyl)urea, di(ethylphenyl)urea, di(propylphenyl)urea, di( butylphenyl)urea, di(pentylphenyl)urea, di(hexylphenyl)urea, di(heptylphenyl)urea, di(octylphenyl)urea, di(nonylphenyl)urea, di(decylphenyl)urea, di(biphenyl)urea, di(dimethylphenyl) urea, di(diethylphenyl)urea, di(dipropylphenyl)urea, di(dibutylphenyl)urea, di(dipentylphenyl)urea, di(dihexylphenyl)urea, di(diheptylphenyl)urea, di(terphenyl)urea, di( trimethylphenyl)urea, di(triethylphenyl)urea, di(tripropylphenyl)urea, di(tributylphenyl)urea, di(phenylmethyl)urea, di(phenylethyl)urea, di(phenylpropyl)urea, di(phenylbutyl)urea, di(phenylpentyl) urea, di(phenylhexyl)urea, di(phenylheptyl)urea, di(phenyloctyl)urea, and di(phenylnonyl)urea.

[0097] Among these, R9, R10, R11 and R12 in formula (30) preferably represent hydrogen atoms.

<<N-unsubstituted carbamic acid ester>>

[0098] A compound of the following formula (31) is preferably used as an N-unsubstituted carbamic acid ester.

[0099] In formula (31), R13 represents a C1-20 aliphatic group, a C7-20 aliphatic group substituted by an aromatic group, or a C6-20 aromatic group.

[00100] Examples of the aliphatic group of R13 in formula (31) include groups that are free of active hydrogen and are constituted by chain hydrocarbon groups, cyclic hydrocarbon groups, or both chain hydrocarbon groups and cyclic hydrocarbon groups.

[00101] The aliphatic group of R13 may contain atoms other than carbon and hydrogen, and the atoms are preferably specific non-metallic atoms (such as oxygen, nitrogen, sulfur, silicon or halogen atoms).

[00102] The aliphatic group of R13 is preferably an aliphatic group containing an oxygen atom such as an atom other than carbon and hydrogen or an aliphatic group free of any atoms other than carbon and hydrogen.

[00103] Examples of the aliphatic group substituted by an aromatic group of R13 include groups in which the C1-14 chain or branched chain alkyl groups are replaced by C6-19 aromatic groups.

[00104] The aliphatic group substituted by an aromatic group may contain atoms other than carbon and hydrogen.

[00105] The branched-chain or branched-chain alkyl group is an active hydrogen-free group and may contain an atom other than carbon and hydrogen, and the atom is preferably a specific non-metallic atom (an atom of oxygen, nitrogen, sulfur, silicon or halogen).

[00106] Examples of the aromatic group include free active hydrogen groups, and preferable examples of these include monocyclic aromatic groups, condensed polycyclic aromatic groups, cross-linked cyclic aromatic groups, ring structure aromatic groups and heterocyclic aromatic groups. The aromatic group may contain an atom other than carbon and hydrogen, and the atom other than hydrogen is preferably a specific non-metallic atom (an atom of oxygen, nitrogen, sulfur, silicon or halogen). The aromatic group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted anthryl group. The aliphatic group and the aromatic group are preferably groups containing an oxygen atom as an atom other than carbon and oxygen, or hydrocarbon groups free of any atoms other than carbon and hydrogen.

[00107] Examples of the substituent group include a hydrogen atom, aliphatic groups (such as chain hydrocarbon groups, cyclic hydrocarbon groups, and groups consisting of chain hydrocarbon groups and cyclic hydrocarbon groups), and groups consisting of aliphatic groups and aromatic groups .

[00108] Specific examples of R13 include: C1-50 chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group , a nonyl group, a decyl group, an undecyl group, a dodecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group; aromatic groups C6-50, such as a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl, a biphenyl group, a dimethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a dipentylphenyl group, a dihexylphenyl group, a diheptylphenyl group, a terphenyl group, a trimethylphenyl group, a triethylphenyl group, a tripropylphenyl group, and a tributylphenyl group; and C7-50 aralkyl groups such as a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group and a phenylnonyl group.

[00109] Specific examples of the N-unsubstituted carbamic acid ester of formula (31) include a methylcarbamate, ethylcarbamate, propylcarbamate, butylcarbamate, pentylcarbamate, hexylcarbamate, heptylcarbamate, octylcarbamate, nonylcarbamate, decylcarbamate, undecylcarbamate, dodecylcarbamate, tridecylcarbamate, tetradecylcarbamate, ( tripropylphenyl)carbamate, (tributylphenyl)carbamate, (phenylmethyl)carbamate, (phenylethyl)carbamate, (phenylpropyl)carbamate, (phenylbutyl)carbamate, (phenylpentyl)carbamate, (phenylhexyl)carbamate, (phenylheptyl)carbamate, (phenyloctyl )carbamate, (phenylnonyl)carbamate and structural isomers thereof.

<<Carbonate ester>>

[00110] In this specification, the term “carbonate ester” means a compound obtained by replacing one or two hydrogen atoms of carbonic acid (CO(OH)2) with an aliphatic group or an aromatic group.

[00111] In the isocyanate composition, according to the present embodiment, a compound of the following formula (32) is preferably used.

[00112] In formula (32), R14 and R15 each independently represent a C1-20 aliphatic group, a C7-20 aliphatic group substituted by an aromatic group, or a C6-20 aromatic group.

[00113] Examples of R14 and R15 include the same groups as those of R13 of formula (31). Among these, it is preferred that each of R14 and R15 independently represents a C1-6 alkyl group or a phenyl group.

[00114] Specific examples of the carbonate ester of formula (32) include dimethylcarbonate, diethylcarbonate, dipropylcarbonate, dibutylcarbonate, dipentylcarbonate, dihexylcarbonate, diheptylcarbonate, dioctylcarbonate, dinonylcarbonate, didecylcarbonate, diundecylcarbonate, didodecylcarbonate, ditridecylcarbonate, ditetradecylcarbonate, dipentadecylcarbonate, di -hexadecylcarbonate, diheptadecylcarbonate,dioctadecylcarbonate, dinonadecylcarbonate, diphenylcarbonate, di(methylphenyl)carbonate, di(ethylphenyl)carbonate, di(propylphenyl)carbonate, di(butylphenyl)carbonate, di(pentylphenyl)carbonate, di(hexylphenyl)carbonate, di (heptylphenyl)carbonate, di(octylphenyl)carbonate, di(nonylphenyl)carbonate, di(decylphenyl)carbonate, di(biphenyl)carbonate, di(dimethylphenyl)carbonate, di(diethylphenyl)carbonate, di(dipropylphenyl)carbonate, di(dibutylphenyl )carbonate, di(dipentylphenyl)carbonate, di(dihexylphenyl)carbonate, di(diheptylphenyl)carbonate, di(phenylphenyl)carbonate, di(trimethylphenyl)carbonate, di(triethylphenyl)carbonate, di(tripropylphenyl)carbonate, di (tributylphenyl)carbonate, di(phenylmethyl)carbonate, di(phenylethyl)carbonate, di(phenylpropyl)carbonate, di(phenylbutyl)carbonate, di(phenylpentyl)carbonate, di(phenylhexyl)carbonate, di(phenylheptyl)carbonate , di(phenyloctyl)carbonate, di(phenylnonyl)carbonate and structural isomers thereof. Among these, di(C1-6alkyl)carbonates, (C1-6alkylphenyl)carbonate and diphenylcarbonate are preferred.

<<N-substituted carbamic acid ester>>

[00115] Examples of an N-substituted carbamic acid ester include compounds of formula (33). The N-substituted carbamic acid ester is also one of the most preferred aspects of the compound of formula (1).

[00116] In formula (33), R28 represents a residual group obtained by removing an isocyanate group from the isocyanate compound, R28 represents an organic group, s represents an integer from 1 to c, where c represents the number of isocyanate groups of the isocyanate compound and t represents an integer obtained by subtracting s from c. R28 preferably represents a residual group obtained by removing an isocyanate group from the isocyanate compound of formula (24), (25), (26), or (27).

[00117] As is evident from the description of formula (33), c depends on the number of isocyanate groups of the isocyanate compound that constitutes the isocyanate composition according to the present embodiment. When the isocyanate compound is a trifunctional isocyanate compound, c represents 3 and when the isocyanate compound is a pentafunctional isocyanate compound, c represents 5. When R28 is an isocyanate compound of formula (24), (25), ( 26) or (27), c represents 3. As is evident from the fact that the isocyanate compound is a difunctional or more functional isocyanate compound in the isocyanate composition according to the present embodiment, c represents an integer of 2 or more .

[00118] R27 is derived from a hydroxy compound, and may be a residual group obtained by removing a hydroxy group (-OH) constituting a hydroxy compound. Hereinafter, R27 is defined as a hydroxy compound in which a hydroxy group is added to R27 (R27OH) so as to explain R27 in a simple way.

[00119] The hydroxy compound (R27OH) can be an alcohol or an aromatic hydroxy compound. When the hydroxy compound (R27OH) is an alcohol, the hydroxy compound is a compound of formula (34).

[00120] In formula (34), R16 represents a group substituted with the number u of hydroxy groups, the group being constituted by a C1-20 aliphatic group or a C7-20 aliphatic group linked to an aromatic group, and u represents a number integer from 1 to 3. R16 is a free group of an active hydrogen different from hydroxy groups.

[00121] Examples of the aliphatic group as R16 in formula (34) include chain hydrocarbon groups, cyclic hydrocarbon groups and groups to which chain hydrocarbon groups and cyclic hydrocarbon groups are attached (such as cyclic hydrocarbon groups substituted by chain hydrocarbon groups , or chain hydrocarbon groups substituted by cyclic hydrocarbons).

[00122] The aliphatic group such as R16 may contain an atom other than carbon atoms and hydrogen atoms, and the atom is preferably a specific non-metallic atom (such as oxygen, nitrogen, sulfur, silicon or halogen atom). The aliphatic group such as R16 is preferably an aliphatic group containing an oxygen such as an atom other than carbon and hydrogen or a free aliphatic group of atoms other than carbon and hydrogen.

[00123] Examples of the aliphatic group linked to an aromatic group include: alkyl groups and cycloalkyl groups, which are linked to a C6-12 aromatic group. Examples of the aromatic group attached to the aliphatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, cross-linked cyclic aromatic groups, ring structure aromatic groups and heterocyclic aromatic groups. The aromatic group is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted anthryl group. The aromatic group may contain atoms other than carbon atoms and hydrogen atoms, and the atoms other than the hydrogen atom are preferably specific non-metallic atoms (such as oxygen, nitrogen, sulfur, silicon or halogen atoms).

[00124] Specific examples of R16 include: chain alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl, a decyl group, a dodecyl group, an octadecyl group, and structural isomers thereof; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a heptyl group, a cyclooctyl group, and structural isomers thereof; groups consisting of chain alkyl groups and cycloalkyl groups, such as a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, a butylcyclohexyl group, a pentylcyclohexyl group , a hexylcyclohexyl group, a dimethylcyclohexyl group, a diethylcyclohexyl group, a dibutylcyclohexyl group, and structural isomers thereof; and aralkyl groups such as a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, a phenylnonyl group, and the structural isomers of same. Among these, R16 is preferably a C1-10 alkyl group or a C3-10 cycloalkyl group.

[00125] In view of industrial use, when alcohol is used to produce the compound of formula (34), an alcohol having one or two alcoholic hydroxy groups (hydroxyl group directly added to a carbon atom constituting the hydroxy compound, the atom carbon not constituting an aromatic ring) is preferred because of low viscosity in general, and a monoalcohol with an alcoholic hydroxy group is more preferred.

[00126] Specific examples of alcohol include: unsubstituted alkyl alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, octadecyl alcohol and structural isomers thereof; unsubstituted cycloalkyl alcohols, such as cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, cyclooctyl alcohol and structural isomers thereof; alcohols consisting of chain alkyl groups and cycloalkyl alcohols, such as methylcyclopentyl alcohol, ethylcyclopentyl alcohol, methylcyclohexyl alcohol, ethylcyclohexyl alcohol, propylcyclohexyl alcohol, butylcyclohexyl alcohol, pentylcyclohexyl alcohol, hexylcyclohexyl alcohol, alcohol dimethylcyclohexyl, diethylcyclohexyl alcohol, dibutylcyclohexyl alcohol and structural isomers thereof; and alkyl alcohols substituted by aromatic groups, such as phenylmethyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, phenylbutyl alcohol, phenylpentyl alcohol, phenylhexyl alcohol, phenylheptyl alcohol, phenyloctyl alcohol, phenylnonyl alcohol and structural isomers thereof.

[00127] In the case where the hydroxy compound (R27OH) is an aromatic hydroxy compound, the monofunctional to trifunctional aromatic hydroxy compound (that is, the number of hydroxyl groups linked with an aromatic ring is an integer from 1 to 3) is preferable due to industrial availability and generally low viscosity. Examples of the aromatic hydroxy compound include compounds of the following formula (35).

[00128] In formula (35), ring A represents an aromatic hydrocarbon ring that can have a substituent group, ring A can be monocyclic or polycyclic, and v represents an integer from 1 to 3.

[00129] Among the aromatic hydroxy compounds of formula (35), monovalent aromatic hydroxy compounds where v is 1 are more preferable.

[00130] As the substituent group that ring A can have, halogen atoms, aliphatic groups and aromatic groups can be mentioned. Examples of the substituent group include cyclic hydrocarbon groups (monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups, cross-linked cyclic hydrocarbon groups, spiro hydrocarbon groups, ring structure hydrocarbon groups and side chain-containing cyclic hydrocarbon group), heterocyclic groups, heterocyclic spiro groups, and cyclic groups cross-linked with a heteroatom, acyclic hydrocarbon groups and groups formed by bonding to at least one acyclic hydrocarbon group and at least one cyclic group.

[00131] Among these substituent groups, the substituent groups preferably used according to the present embodiment due to the difficulty in the occurrence of secondary reactions are groups selected from the group consisting of acyclic hydrocarbon groups, cyclic hydrocarbon groups (monocyclic hydrocarbon groups, condensed polycyclic hydrocarbon groups , cross-linked cyclic hydrocarbon groups, spiro hydrocarbon groups, assembly structure hydrocarbon groups, and a side chain-containing cyclic hydrocarbon group) or groups linked to at least two groups selected from the above-mentioned group (mutually substituted groups).

[00132] The preferable substituent groups that replace ring A are groups selected from the group consisting of alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups and ether groups (alkyl ethers, aryl ethers or aralkyl ethers, substituted or unsubstituted); groups formed by linking at least two groups selected from the above-mentioned group with each other; groups formed by linking at least two groups selected from the above-mentioned group through a saturated hydrocarbon bond or an ether bond; or halogen atoms, provided that the sum of the number of carbon atoms constituting ring A and the number of carbon atoms constituting all substituent groups replacing ring A is an integer from 6 to 50.

[00133] Examples of ring A include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a naphthalene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a pentalene ring, an azulene ring, a hepthalene ring, an indacene ring, a biphenylene ring, an acenaphthylene ring, an aceryltrilene ring and an acephenantrilene ring. Ring A preferably includes at least one structure selected from a benzene ring and a naphthalene ring.

[00134] When the aromatic hydroxy compound is used to prepare the compound of formula (33), an aromatic hydroxy compound with a readily available benzene ring as a skeleton is preferable from the point of view of industrial use. Examples of the aromatic hydroxy compound include an aromatic hydroxy compound of the following formula (36).

[00135] In formula (36), R17, R18, R19, R20 and R21 each independently represent a group selected from the group consisting of a chain alkyl group, a cycloalkyl group, an aryl group, a chain alkyl linked to an aromatic group, and an ether group (substituted or unsubstituted alkyl ether, aryl ether or alkyl ether substituted by an aromatic group); a group formed by linking at least two groups selected from the above-mentioned group with each other; a group formed by linking at least two groups selected from the above-mentioned group through a saturated aliphatic bond or an ether bond; a halogen atom; or a hydrogen atom and the sum of the number of carbon atoms constituting R17 to R21 is an integer from 0 to 44.

[00136] In formula (36), the preferred R17 to R21 are groups independently selected from groups shown in the following (i) to (v): hydrogen atom; halogen atoms; C1-44 carbon functional groups in which a carbon atom in the α position binds to a group selected from the group consisting of C1-43 chain alkyl groups, C1-43 cycloalkyl groups, C1-43 alkoxy groups, alkyl ether groups of C2-43 polyoxyalkylene free of hydroxy groups at their terminal ends, C6-43 aryl groups, C7-43 alkyl groups linked to an aromatic group, C7-43 cycloalkyl groups linked to an aromatic group and a C7-43 alkyloxy groups linked to an aromatic group; C1-44 aromatic groups, bonded to at least one group selected from the group consisting of a hydrogen atom, C1-38 chain alkyl groups, C4-38 cycloalkyl groups, C1-38 alkoxy groups, C2 polyoxyalkylene alkyl ether groups -38 free from hydroxy groups at their terminals, C6-38 aromatic groups, C7-38 alkyl groups linked to an aromatic group, C7-38 cycloalkyl groups linked to an aromatic group, and C7-38 alkyloxy groups linked to an aromatic group ; C1-44 oxygen functional groups, an oxygen atom which is bonded to at least one group selected from the group consisting of C1-44 alkyl groups, C1-44 cycloalkyl groups, C1-44 alkoxy groups, C1-44 alkyl ether groups C2-44 polyoxyalkylene free of hydroxy groups at their terminal ends, C6-44 aromatic groups, C7-44 alkyl groups linked to an aromatic group, and C7-44 aralkyloxy groups.

[00137] Here, the term “aralkyloxy group” means a group in which an oxygen atom is linked to the aralkyl group defined above.

[00138] Specific examples of R17 to R21 include: chain alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group and structural isomers thereof; cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; groups consisting of chain alkyl groups and cycloalkyl groups, such as a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, a butylcyclohexyl group, a pentylcyclohexyl group, a hexylcyclohexyl group, a dimethylcyclohexyl group, a diethylcyclohexyl group, a dibutylcyclohexyl group and structural isomers thereof; chain alkyloxy groups, such as a methoxy group, an ethoxy group, a propoxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, a dodecyloxy group , an octadecyloxy group and structural isomers thereof; cycloalkyloxy groups, such as a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group; alkyloxy groups corresponding to groups consisting of chain alkyl groups and cycloalkyl groups, such as a methylcyclopentyloxy group, an ethylcyclopentyloxy group, a methylcyclohexyloxy group, an ethylcyclohexyloxy group, a propylcyclohexyloxy group, a butylcyclohexyloxy group, a pentylcyclohexyloxy group, a hexylcyclohexyloxy group, dimethylcyclohexyloxy group, a diethylcyclohexyloxy group, a dibutylcyclohexyloxy group and structural isomers thereof; aromatic groups, such as a phenyl group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, a biphenyl group, a dimethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a dipentylphenyl group, a dihexylphenyl group, a diheptylphenyl group, a terphenyl group, a trimethylphenyl group, a triethylphenyl group, a tripropylphenyl group , a tributylphenyl group and structural isomers thereof; groups consisting of aromatic groups and alkyl groups, such as a 1-methyl-1-phenylethyl group, and a 1-phenylethyl group; oxo-aromatic groups, such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a propylphenoxy group, a butylphenoxy group, a pentylphenoxy group, a hexylphenoxy group, a heptylphenoxy group, an octylphenoxy group, a nonylphenoxy group, a decylphenoxy group , a phenylphenoxyl group, a dimethylphenoxyl group, a diethylphenoxyl group, a dipropylphenoxyl group, a dibutylphenoxyl group, a dipentylphenoxyl group, a dihexylphenoxyl group, a diheptylphenoxyl group, a diphenylphenoxyl group, a trimethylphenoxyl group, a triethylphenoxyl group, tripropylphenoxyl group, a tributylphenoxyl group and structural isomers thereof; aralkyl groups, such as a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group and a phenylnonyl group; and aralkyloxy groups, such as a phenylmethoxy group, a phenylethoxy group, a phenylpropyloxy group, a phenylbutyloxy group, a phenylpentyloxy group, a phenylhexyloxy group, a phenylheptyloxy group, a phenyloctyloxy group, a phenylnonyloxy group and structural isomers thereof . Among these, it is preferred that R17 to R21 each independently represents a hydrogen atom, a C110 alkyl group, a phenoxy group or a C7-10 alkyl group.

[00139] The compound of formula (33) can be produced by reacting the difunctional or more functional isocyanate compound and the hydroxy compound, as described above. Various compounds are produced depending on the combination of s and t in formula (33), because the difunctional or more functional isocyanate compound is used. However, in the isocyanate composition according to the present embodiment, these compounds do not need to be distinguished to adjust the addition amount. For example, a trifunctional isocyanate is mixed with a hydroxyl compound in a stoichiometric ratio, relative to the trifunctional isocyanate, of 1 to 3, to produce a compound of formula (33), and the resulting compound can be used without carrying out purification for produce the isocyanate composition according to the present embodiment.

<Inert compound>

[00140] The isocyanate composition, according to the present embodiment, may additionally contain an inert compound, which is at least one compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds, the inert compound not having a double bond between carbon atoms or between a carbon atom and an oxygen atom excluding unsaturated bonds constituting an aromatic ring (hereinafter, may be referred to as an “inert compound”), in an amount of 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound. The inert compound does not react with the isocyanate compound during storage of the isocyanate composition or reaction to produce the polyurethane.

[00141] Inert compounds are classified into compounds A to G. Hydrocarbon compounds are classified into compound A and compound B, ether compounds and sulfide compounds are classified into compounds C to E, halogenated hydrocarbon compounds are classified into compound F, silicon-containing hydrocarbon compounds, silicon-containing ether compounds, and silicon-containing sulfide compounds are classified under compound G. Compounds A to G do not contain any unsaturated bonds other than an aromatic ring, and do not fall into the category of “compound with at least one unsaturated bond”.(Compound A)

[00142] Compound A is an aliphatic hydrocarbon compound with a straight chain, branched chain or cyclic structure. Compound A is preferably a C5-20 hydrocarbon compound. Specific examples of compound A include: pentane, hexane, heptane, octane, nonane, decane, dodecane, tetradecane, pentadecane, hexadecane, octadecane, nonadecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane , propylcyclohexane, butylcyclohexane, pentylcyclohexane, hexylcyclohexane, dimethylcyclohexane, diethylcyclohexane, dibutylcyclohexane and structural isomers thereof.(Compound B)

[00143] Compound B is an aromatic hydrocarbon compound that can be replaced by an aliphatic hydrocarbon group. Compound B is preferably a C5-20 hydrocarbon compound. Specific examples of compound B include: benzene, toluene, ethylbenzene, butylbenzene, pentylbenzene, hexylbenzene, octylbenzene, biphenyl, terphenyl, diphenylethane, (methylphenyl)phenylethane, dimethylbiphenyl, benzyltoluene, dibenzyltoluene, naphthalene, methylnaphthalene, ethylnaphthalene, butylnaphthalene and structural isomers thereof .(Compound C)

[00144] Compound C is a compound having an ether bond or a sulfide bond, and an aliphatic hydrocarbon group, the compound being formed by bonding the same type or different type of aliphatic hydrocarbon compounds through an ether bond or a sulfide bond. sulfide. Compound C is preferably a C2-20 compound. Specific examples of compound C include: ethers in which hydrocarbon compounds are linked through an ether linkage, such as ethyl ether, butyl ether, octyl ether, nonyl ether, decyl ether, methyl ethyl ether, methyl butyl ether, methyl ethyl ether, methyl nonyl ether , methyldecyl ether, ethylbutyl ether, ethyl ethyl ether, ethylnonyl ether, ethyldecyl ether, butyl ethyl ether, butylnonyl ether, butyldecyl ether, octylnonyl ether, octyldecyl ether, dicyclopentyl ether, dicyclohexyl ether, dicycloctyl ether, cyclohexylethyl ether, cycloether hexylbutyl, cyclohexyloctyl ether, cyclohexylnonyl ether, cyclohexyldecyl ether, tetraethylene glycol dimethyl ether and structural isomers thereof; and sulfides in which hydrocarbon compounds are linked through a sulfide bond, such as methyl sulfide, ethyl sulfide, butyl sulfide, octyl sulfide, nonyl sulfide, decyl sulfide, methylethyl sulfide, methylbutyl sulfide, methyloctyl sulfide, methylnonyl sulfide, methyldecyl sulfide, ethylbutyl sulfide, ethyloctyl sulfide, ethylnonyl sulfide, ethyldecyl sulfide, butyloctyl sulfide, butylnonyl sulfide, butyldecyl sulfide, octylnonyl sulfide, octyldecyl sulfide, dicyclopentyl, dicyclohexyl sulfide, dicycloctyl sulfide, cyclohexylethyl sulfide, cyclohexylbutyl sulfide, cyclohexyloctyl sulfide, cyclohexylnonyl sulfide and structural isomers thereof. Among these, a C2-20 alkyl ether or alkyl sulfide is preferred. (Compound D)

[00145] Compound D is a compound that has an ether bond or a sulfide bond, and an aromatic hydrocarbon group, and is formed by bonding the same type or different type of aromatic hydrocarbon compounds through an ether bond or a sulfide bond. sulfide. Compound D is preferably a C2-20 compound. Specific examples of compound D include: aromatic ethers in which aromatic hydrocarbon compounds are linked through an ether linkage, such as diphenyl ether, (methylphenyl)phenyl ether, (ethylphenyl)-phenyl ether, (butylphenyl)-phenyl ether, (hexylphenyl)-phenyl ether, (methylphenyl)ether, (ethylphenyl)ether, (butylphenyl)ether, (hexylphenyl)ether, dibenzyl ether, di(methylbenzyl)ether, di(ethylbenzyl)ether, di(butylbenzyl)ether, di( pentylbenzyl)ether, di(hexylbenzyl)ether, di(octylbenzyl)ether and structural isomers thereof; and aromatic sulfides in which the aromatic hydrocarbon compound is linked through a sulfide bond, such as diphenyl sulfide, (methylphenyl)-phenyl sulfide, (ethylphenyl)-phenyl sulfide, (butylphenyl)-phenyl sulfide, (butylphenyl)-phenyl sulfide, ( hexylphenyl)- phenyl, (methylphenyl)sulfide, (ethylphenyl)sulfide, (butylphenyl)sulfide, (hexylphenyl)sulfide, di(methylbenzyl)sulfide, di(ethylbenzyl)sulfide,di(butylbenzyl)sulfide, di(pentylbenzyl)sulfide, di (hexylbenzyl) sulfide, di(octylbenzyl) sulfide, diphenyl sulfide, dibenzyl sulfide and structural isomers thereof. Among these, diphenyl ether is preferable.(Compound E)

[00146] Compound E is a compound having an ether bond or a sulfide bond, and both an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Compound E is preferably a C7-20 compound. Specific examples of compound E include: phenyl methyl ether, phenyl ethyl ether, phenyl butyl ether, phenyl octyl ether, phenyl nonyl ether, phenyl decyl ether, benzyl ethyl ether, benzyl -butyl ether, benzyl octyl ether, benzyl nonyl ether, benzyl decyl ether, (methylphenyl)ethyl ether, (methylphenyl)butyl ether, (methylphenyl)octyl ether, (methylphenyl)nonyl ether, (methylphenyl)ether )decyl, (ethylphenyl)ethyl ether, (ethylphenyl)butyl ether, (ethylphenyl)octyl ether, (ethylphenyl)nonyl ether, (ethylphenyl)decyl ether, (butylphenyl)ethyl ether, (butylphenyl)butyl, (butylphenyl)octyl ether, (butylphenyl)nonyl ether, (butylphenyl)decyl ether and their structural isomers. Among these, a C1-20-phenyl alkyl ether is preferable.(Compound F)

[00147] Compound F is a halide in which at least one hydrogen atom constituting an aliphatic hydrocarbon compound or at least one hydrogen atom constituting an aromatic hydrocarbon compound is replaced by a halogen atom. Compound F is preferably a C2-20 compound. Specific examples of compound F include chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chlorheptane, chloro-octane, chlorononane, chlorodecane, chlorododecane, chlorotetradecane, chloropentadecane, chlorohexadecane, chloro-octadecane, chlorononadecane, chlorocyclopentane, chlorocyclo- hexane, chlorocycloheptane, chlorocyclooctane, chloromethylcyclopentane, chloroethylcyclopentane, chloromethylcyclohexane, chloroethylcyclohexane, chloropropylcyclohexane, chlorobutylcyclohexane, chloropentylcyclohexane, chlorohexylcyclohexane, chlorodimethylcyclohexane, chlorodiethylcyclohexane, chlorodibutylcyclohexane hexane, chlorobenzene, chloromethylbenzene, chloroethylbenzene, chlorobutylbenzene, chloropentylbenzene, chlorohexylbenzene, chlorooctylbenzene, chlorobiphenyl, chloroterphenyl, chlorodiphenylethane, chloro(methylphenyl)phenylethane, chlorodimethylbiphenyl, chlorobenzyltoluene, chloronaphthalene, chloromethylnaphthalene, chloroethylnaphthalene, chlorobutylnaphthalene, dichloroethane, dichloropropane, dichlorobutane, dichloropentane, dichlorohexane, dichloroheptane, dichloroctane, dichlorononane, dichlorodecane, dichlorododecane, dichlorotetradecane, dichloropentadecane, dichlorohexadecane, dichlorooctadecane, dichlorononedecane, dichlorocyclopentane, dichlorocyclohexane, dichlorocycloheptane, dichlorocyclooctane, dichloromethyl cyclopentane, dichloroethylcyclopentane, dichloromethylcyclohexane, dichloroethylcyclohexane, dichloropropylcyclohexane, dichlorobutylcyclohexane, dichloropentylcyclohexane, dichlorohexylcyclohexane, dichlorodimethylcyclohexane, dichlorobutylcyclohexane, dichlorobenzene, dichloro(methylphenyl)phenylethane, dichlorodimethylbiphen yl, dichlorobenzyltoluene, dichloronaphthalene, dichloromethylnaphthalene, dichloroethylnaphthalene, dichlorobutylnaphthalene, dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane, dibromodecane, dibromododecane, dibromotetradecane, dibromopentadecane, dibromohexadecane, dibromo-oc tadecane, dibromononadecane, dibromocyclopentane, dibromocyclo- hexane, dibromocycloheptane, dibromocyclooctane, dibromomethylcyclopentane, dibromoethylcyclopentane, dibromomethylcyclohexane, dibromoethylcyclohexane, dibromopropylcyclohexane, dibromobutylcyclohexane, dibromopentylcyclohexane, dibromohexylcyclohexane, dibromodimethylcyclohexane, dibromodiethyl cyclo -hexane, dibromobutylcycle -hexane, dibromobenzene, dibromomethylbenzene, dibromoethylbenzene, dibromobutylbenzene, dibromopentylbenzene, dibromohexylbenzene, dibromooctylbenzene, dibromobiphenyl, dibromoterphenyl, dibromodiphenylethane, dibromo(methylphenyl)phenylethane, dibromodimethylbiphenyl, dibromobenzyltoluene, dibromonaphthalene, dibro momethylnaphthalene, dibromoethylnaphthalene, dibromobutylnaphthalene, difluoroethane, difluoropropane, difluorobutane , difluoropentane, difluorohexane, difluoroheptane, difluorooctane, difluorononane, difluorodecane, difluorododecane, difluorotetradecane, difluoropentadecane, difluorohexadecane, difluorooctadecane, difluorononadecane, difluorocyclopentane, difluorocyclohexane, difluorocycloheptane, difluorocyclooctane, difluoromethylcyclopentane , difluoroethylcyclopentane, difluoromethylcyclohexane, difluoroethylcyclohexane, difluoropropylcyclohexane, difluorobutylcyclohexane, difluoropentylcyclohexane, difluorohexylcyclohexane, difluorodimethylcyclohexane, difluorodiethylcyclohexane, difluorodibutylcyclohexane, difluorobenzene, difluoromethylbenzene, difluoroethylbenzene, difluoro butylbenzene, difluoropentylbenzene , difluorohexylbenzene, difluorooctylbenzene, difluorobiphenyl, difluoroterphenyl, difluorodiphenylethane, difluoro(methylphenyl)phenylethane, difluorodimethylbiphenyl, difluorobenzyltoluene, difluoronaphthalene, difluoromethylnaphthalene, difluoroethylnaphthalene, difluorobutylnaphthalene and structural isomers thereof. (Compound G)

[00148] Compound G is a compound in which part or all of the carbon atoms of compounds A to E are replaced by silicon atoms. Specific examples of compound G include tetraethylsilane, tetrabutylsilane, tetrahexylsilane, tetracyclohexylsilane, tetraphenylsilane, dimethyldibutylsilane, dimethyldicyclohexylsilane, dimethyldiphenylsilane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexacyclohexylcyclotrisiloxane, trimethyltricyclohexylcyclotrisiloxane, trimethyltrisiloxane, phenylcyclotrisiloxane, hexaphenylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octacyclo- hexylcyclotetrasiloxane, tetramethyltetracyclohexylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetramethyltetraphenyltrisiloxane, pentamethylpentaphenyltetrasiloxane and structural isomers thereof. Among these, decamethyltetrasiloxane is preferably used.

[00149] Among these, there is a case in which compounds having an ether bond or a sulfide bond, such as compound C, compound D, or compound E, generate oxides or peroxides depending on the conditions. From the point of view of thermal stability, compounds A, B, C, D, E and G are preferred, and compounds A, B and G are more preferred.

[00150] The presence of the inert compound makes it possible to further improve the storage stability of the isocyanate composition. That is, the inert compound may be referred to as a quality enhancing agent, a stabilizer, a viscosity increase inhibitor, a gelatin component generation inhibitor, or a chromaticity increase inhibitor, of the difunctional diisocyanate compound. and/or trifunctional or more functional.

<Halogen atom that is not derived from halogenated hydrocarbons>

[00151] The isocyanate composition according to the present embodiment may additionally contain 1.0 ppm by mass to 1.0 x 102 ppm by mass, based on the isocyanate compound, of halogen atoms that are not derived from a hydrocarbon halogenated.

[00152] The phrase “which are not derived from a halogenated hydrocarbon” means that the halogen atoms that constitute the halogenated hydrocarbon are excluded.

[00153] Although the halogen atom is not particularly limited, the halogen atom is preferably chlorine and/or bromine, and preferably at least one selected from the group consisting of chlorine ion, bromine ion, chlorine atom contained in a chlorine compound hydrolyzable and bromine atom contained in a hydrolyzable bromine compound. The halogenated hydrocarbon is distinguished from a hydrolyzable chlorine compound or a hydrolyzable bromine compound in terms of the absence of the ability to hydrolyze under conditions of normal temperature and normal pressure. Hydrolyzable chlorine compound and hydrolyzable bromine compound have a hydrolysis ability to generate halogen ion under conditions of normal temperature and normal pressure. Therefore, a halogen atom that is not derived from a halogenated hydrocarbon is preferably a hydrolyzable chlorine compound, a hydrolyzable bromine compound, a chlorine ion or a bromine ion.

[00154] Examples of the hydrolyzable chlorine compound include carbamoyl chloride compounds in which a hydrogen chloride is added to an isocyanate group. Examples of the hydrolyzable bromine compound include carbamoyl bromide compounds in which a hydrogen bromide is added to an isocyanate group.

<Sulfuric acid and/or sulfuric acid ester>

[00155] Sulfuric acid ester refers to a compound consisting of an ester bond of an alcohol and a sulfuric acid, and specific examples thereof include: benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid , monoethylsulfuric acid, and monon-propylsulfuric acid. Additionally, a sulfuric acid may be contained.

<Phosphoric acid and/or phosphoric acid ester>

[00156] Phosphoric acid ester, according to the present embodiment, refers to an ester formed by condensation by dehydration of phosphoric acid and alcohol, and can be a phosphoric acid monoester, a phosphoric acid diester or a triester of phosphoric acid. Specific examples thereof include methyl phosphate, dimethyl phosphate, butyl phosphate, dibutyl phosphate, isodecyl phosphate, diisodecyl phosphate, 2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, of lauryl, dilauryl phosphate, stearyl phosphate, distearyl phosphate and dioleyl phosphate and phenylphosphonic acid. Additionally, a phosphoric acid may be contained. Among these, C1-15 alkyl phosphate is preferred. Additionally, a phosphoric acid may be contained.

<Isocyanate composition>

[00157] The first embodiment of the isocyanate composition is an isocyanate composition containing: a trifunctional or more functional isocyanate compound; and 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being other than isocyanate.

[00158] The compound having at least one unsaturated bond excluding unsaturated bonds that constitute an aromatic ring is a compound of formula (28), a carbonic acid derivative (N-unsubstituted carbamic acid ester, carbonate ester, ester of N-substituted carbamic acid), a compound having a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum, a compound having an isocyanurate group and/or a biuret group, or a compound of formula (1).

[00159] The amount of the compound with an unsaturated bond is preferably 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the trifunctional or more functional isocyanate compound that constitutes the composition. One type of unsaturated binding compound can be used alone, or a plurality of types thereof can be used in combination.

[00160] An unsaturated bond compound as a contaminant tends to cause coloring, because an unsaturated bond of the unsaturated bond compound generally tends to be easily oxidized. However, the unsaturated binding compound, according to the present embodiment, acts effectively on the isocyanate composition, when stored, to improve the stability of the isocyanate compound without coloring the isocyanate composition.

[00161] Although the mechanism by which such effects are exhibited is not apparent, it is presumed that the effects are exhibited by selectively reacting the unsaturated binding compounds with water or oxygen, and thus suppressing the denaturation reaction of the isocyanate compound caused by water or oxygen. Furthermore, in the case of a compound having an unsaturated bond between a carbon atom and an oxygen atom, there are many cases in which the tendency to exhibit the effect becomes great.

[00162] To suppress the denaturation reaction of the isocyanate compound, the amount of the unsaturated binding compound is preferably increased. On the other hand, there is a case where an excessive amount of the unsaturated bond compound generates coloration caused by the unsaturated bond as described above, thereby deteriorating the external appearance. Thus, the amount of the unsaturated binding compounds according to the present embodiment is from 1.0 ppm by mass to 1.0x104 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, more preferably 5 .0 ppm by mass or more, and even more preferably 10 ppm by mass or more, and the upper limit of the amount is preferably 5.0x103 ppm by mass or less, more preferably 3.0x103 ppm by mass or less, and even more preferably 1.0x103 ppm by mass or less.

[00163] Among these compounds having an unsaturated bond, a compound with a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum is preferred. The compound is presumed to suppress the denaturation reaction of the isocyanate compound caused by water or oxygen, because the compound has a nylon 1 structure having a high reactivity against water or oxygen.

[00164] Additionally, among these compounds having an unsaturated bond, a compound of formula (1) is also preferably used. It is assumed that an ester group of the compound has a reactivity against water or oxygen and thereby suppresses the denaturation of the isocyanate group caused by water or oxygen.

[00165] Furthermore, a compound having an isocyanurate group and/or biuret group is also preferably used.

[00166] Thus, the first embodiment of the isocyanate composition according to the present embodiment contains: a trifunctional or more functional isocyanate compound; and 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, the compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being other than the isocyanate, and also preferably contains 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of at least one inert compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds, the inert compound not having any double bonds between carbon atoms or between a carbon atom and an oxygen atom excluding unsaturated bonds constituting an aromatic ring.

[00167] Among these, compounds having an ether bond or a sulfide bond, such as compound C, compound D, or compound E, can generate an oxide or a peroxide depending on the conditions. From the point of view of thermal stability, compounds A, B, C, D, E and G are preferred, and compounds A, B and G are more preferable. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00168] Although inert compounds generally do not have reactivity against water, oxygen or the like, and it is quite unlikely that the inert compound will act in the same way as unsaturated binding compounds, the inventors of the present invention have surprisingly found that the isocyanate composition additionally containing the inert compound also exhibits stability-enhancing effects of the isocyanate.

[00169] Although the mechanism by which such effects are exhibited is not apparent, the isocyanate compound generally reacts with water or oxygen, the isocyanate composition is stored in a storage container such as an airtight glass container, an 18 square can. liters or a drum. However, in the case of usual storage, it is assumed that the undesirable increase in viscosity of the isocyanate composition and the generation of gelatinous components are induced by the action of infinitesimally contaminated water or oxygen by leakage of an external portion or when the container of storage is filled with isocyanate composition. In contrast, a portion of the infinitesimally inert compound existing together in the isocyanate composition according to the present embodiment is assumed to vaporize in the storage container, exist as a vapor component in a vapor portion in the storage container, and thereby suppress the influences of infinitesimally existing water or oxygen, and exhibit additional favorable effects in combination with the compound having an unsaturated bond.

[00170] Although the amount of the inert compound is preferably increased in view of the above-mentioned circumstances, there is a case in which an excess amount thereof significantly alters the properties that are expected to be originally provided to the isocyanate composition, such as viscosity. Thus, the amount of the inert compound, according to the present embodiment, is from 1.0 ppm by mass to 1.0x104 ppm by mass, the lower limit thereof is preferably 3.0 ppm by mass or more, more preferably 5 .0 ppm by mass or more, and even more preferably 10 ppm by mass or more, and the upper limit thereof is preferably 5.0x103 ppm by mass or less, more preferably 3.0x103 ppm by mass or less, and even more preferably 1.0x103 ppm by mass or less. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00171] The isocyanate composition containing a trifunctional or more functional isocyanate compound and a compound having an unsaturated bond may additionally contain a sulfuric acid, a sulfuric acid ester, a phosphoric acid and/or phosphoric acid ester.

[00172] The stability of the isocyanate composition when stored is improved by additionally containing sulfuric acid and/or sulfuric acid ester. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that sulfuric acid and sulfuric acid ester moderately suppress the formation of a nylon body structure 1 of formula (37) in the composition according to the present invention. modality, and thereby suppressing the gelation of the entire composition caused by an increase in the compound. Therefore, it is preferable that the sulfuric acid and/or sulfuric acid ester are contained in a moderate amount range, so as to further improve the stability of the isocyanate. The amount thereof, based on the isocyanate compound, is from 1.0 ppm by mass to 1.0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is preferably 1.0 x 102 ppm by mass or less.

[00173] The isocyanate composition additionally containing a phosphoric acid and/or a phosphoric acid ester also improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that phosphoric acid and phosphoric acid ester moderately suppress the formation of the nylon body structure 1 of formula (37) in the composition according to the present embodiment. in the same way as that of a sulfuric acid and a sulfuric acid ester, and thereby suppressing the gelation of the entire composition caused by the increase in the compound. Thus, to further improve the stability of the isocyanate, the phosphoric acid and/or phosphoric acid ester is preferably contained in a moderate range of the amount thereof, and the amount, based on the isocyanate compound, is 1.0 ppm by mass. at 1.0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and even more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 1, 0 x 101 mass ppm or less.

[00174] The isocyanate composition containing: a trifunctional or more functional isocyanate compound; and at least one unsaturated bond, according to the first embodiment of the isocyanate composition, preferably additionally contains a halogen atom, which is not a derivative form of a halogenated hydrocarbon (hereinafter may be referred to simply as a halogen atom). . The amount of the halogen atom is preferably 1.0 ppm by mass to 1.0 x 102 ppm by mass.

[00175] In the isocyanate composition according to the present embodiment, a halogen atom is contained in various forms. The halogen atom is preferably chlorine and/or bromine, and at least one selected from the group consisting of chlorine ion, bromine ion, chlorine atom contained in a hydrolyzable chlorine compound and bromine atom contained in a hydrolyzable bromine compound. The total amount of these chlorine atom and bromine atom can be adjusted to be within the above-mentioned range. The trifunctional or more functional isocyanate compound and a compound containing a halogen atom can be charged in such a way that the charged amount thereof is within the above-mentioned range, the amount of chlorine atom and bromine atom in the composition can be determined by inductively coupled plasma (ICP), the amount of chlorine ion and bromine ion can be determined by anion chromatography, or hydrolyzable chlorine can be measured according to a hydrolyzable chlorine test method described in appendix 3 of JIS K-1556 ( 2000).

[00176] The isocyanate composition containing a halogen atom improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that a halogen atom captures oxygen or water, which deteriorates the stability of the trifunctional or more functional isocyanate compound and thereby exhibits the effect of improving the stability of the trifunctional or more functional isocyanate compound.

[00177] Thus, the amount of halogen atom is preferably increased to further improve the stability of the isocyanate, while an excessive amount of the halogen atom generates coloration caused by the halogen atom, and may deteriorate the external appearance when used as raw material. coating, for example. Thus, the amount of halogen atom in the isocyanate composition according to the present embodiment, based on the isocyanate compound, is from 1.0 ppm by mass to 1.0 x 102 ppm by mass, the lower limit of the amount is preferably 3 .0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 5.0 x 101 ppm by mass or less.

[00178] Since the effects exhibited by containing a halogen atom that is not derived from a halogenated hydrocarbon are also exhibited when the isocyanate composition contains: a trifunctional or more functional isocyanate compound; and a compound having an unsaturated bond; and any of an inert compound, a sulfuric acid, a sulfuric acid ester, a phosphoric acid, and a phosphoric acid ester, additionally contains a halogen atom that is not derived from a halogenated hydrocarbon, the isocyanate composition containing: an trifunctional or more functional isocyanate compound; and a compound having an unsaturated bond; and any of an inert compound, a sulfuric acid, a sulfuric acid ester, a phosphoric acid and a phosphoric acid ester, and additionally containing a halogen atom that is not derived from a halogenated hydrocarbon is one of the preferred embodiments. In this case, the halogen atom is contained in the above-mentioned quantity in the isocyanate composition and exhibits the same effects.

[00179] The second embodiment of the isocyanate composition contains: a trifunctional or more functional isocyanate compound; and, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 103 ppm by mass of a sulfuric acid and/or a sulfuric acid ester, and/or 1.0 ppm by mass of a 1.0 x 103 ppm by mass of a phosphoric acid and/or a phosphoric acid ester.

[00180] The explanation of the same constitution as the first modality can be omitted.

[00181] The isocyanate composition containing sulfuric acid and sulfuric acid ester also improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that sulfuric acid and sulfuric acid ester moderately suppress the formation of the nylon body structure 1 of formula (37) in the composition according to the present embodiment. , and thereby suppressing the gelation of the entire composition caused by the increase in compound. Thus, to further improve the stability of the isocyanate, the sulfuric acid and sulfuric acid ester are preferably contained in an appropriate range of amount, and the amount thereof, based on the isocyanate compound, is from 1.0 ppm by mass to 1. .0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 1.0 x 102 mass ppm or less.

[00182] The isocyanate composition containing a phosphoric acid and a phosphoric acid ester improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that phosphoric acid and phosphoric acid ester moderately suppress the formation of the nylon body structure 1 of formula (37) in the composition according to the present embodiment. in the same way as sulfuric acid and sulfuric acid ester, and thereby suppressing the gelation of the entire composition caused by the increase in the compound. Thus, to further improve the stability of the isocyanate, the phosphoric acid and phosphoric acid ester are preferably contained in an appropriate range of amount, and the amount thereof, based on the isocyanate compound, is from 1.0 ppm by mass to 1. .0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 1.0 x 102 mass ppm or less.

[00183] The isocyanate composition containing: a trifunctional or more functional isocyanate compound; and, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 103 ppm by mass sulfuric acid and/or sulfuric acid ester, and/or 1.0 ppm by mass to 1.0 x 103 ppm by mass of phosphoric acid and/or a phosphoric acid ester, according to the second embodiment, preferably additionally contains an inert compound, and preferably additionally contains from 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of at least one inert compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds, an inert compound that does not contains neither an unsaturated bond between carbon atoms nor a double bond between a carbon atom and an oxygen atom excluding unsaturated bonds that constitute an aromatic ring. Compounds A, B, C, D, E and G are preferable from the point of view of thermal stability, and compounds A, B and G are preferable in terms that neither oxide nor peroxide is generated. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00184] The presence of the inert compound that has no reactivity against water, oxygen, or the like, further increases the stability of an isocyanate in the isocyanate composition according to one embodiment.

[00185] Such effect is presumed to be exhibited by vaporizing a portion of the infinitesimally existing inert compound together in the storage container to exist infinitesimally as a vapor component, and thus suppressing the increase in viscosity or generation of gelatinous components caused by infinitesimally existing water or oxygen.

[00186] Although the amount of the inert compound is preferably increased in view of the above-mentioned circumstances, there is a case in which an excess amount thereof significantly alters the properties originally expected to be provided to the isocyanate composition, such as viscosity. Thus, the amount of the inert compound, according to the present embodiment, is from 1.0 ppm by mass to 1.0x104 ppm by mass, the lower limit thereof is preferably 3.0 ppm by mass or more, more preferably 5 .0 ppm by mass or more, and even more preferably 10 ppm by mass or more, and the upper limit thereof is preferably 5.0x103 ppm by mass or less, more preferably 3.0x103 ppm by mass or less, and even more preferably 1.0x103 ppm by mass or less. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00187] Furthermore, it is preferred that the isocyanate compound contains: a trifunctional or more functional isocyanate compound; and, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 103 ppm by mass sulfuric acid and/or sulfuric acid ester, and/or 1.0 ppm by mass to 1.0 x 103 ppm by mass of phosphoric acid and/or a phosphoric acid ester additionally contains a halogen atom that is not derived from a halogenated hydrocarbon (hereinafter, it may be referred to simply as a halogen atom). The amount of the halogen atom is preferably 1.0 ppm by mass to 1.0 x 102 ppm by mass.

[00188] In the isocyanate composition according to the present embodiment, a halogen atom is contained in various forms. The halogen atom is preferably chlorine and/or bromine, and at least one selected from the group consisting of chlorine ion, bromine ion, chlorine atom contained in a hydrolyzable chlorine compound and bromine atom contained in a hydrolyzable bromine compound. The total amount of these chlorine atom and bromine atom can be adjusted to be within the above-mentioned range. The trifunctional or more functional isocyanate compound and a compound containing a halogen atom can be charged in such a way that the charged amount thereof is within the above-mentioned range, the amount of chlorine atom and bromine atom in the composition can be determined by inductively coupled plasma (ICP), the amount of chlorine ion and bromine ion can be determined by anion chromatography, or hydrolyzable chlorine can be measured according to a hydrolyzable chlorine test method described in appendix 3 of JIS K-1556 ( 2000).

[00189] The isocyanate composition containing a halogen atom improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that a halogen atom captures oxygen or water, which deteriorates the stability of the trifunctional or more functional isocyanate compound and thereby exhibits the effect of improving the stability of the trifunctional or more functional isocyanate compound.

[00190] Thus, the amount of halogen atoms is preferably increased to further improve the stability of the isocyanate, while an excessive amount of halogen atoms generates coloration caused by the halogen atom, and may deteriorate the external appearance when used as a raw material. coating, for example. Thus, the amount of halogen atoms in the isocyanate composition according to the present embodiment, based on the isocyanate compound, is from 1.0 ppm by mass to 1.0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 5.0 x 101 ppm by mass or less.

[00191] The third embodiment of the isocyanate composition contains: a difunctional or more functional isocyanate compound; and 1.0 ppm by mass to 1.0 x 104 ppm, based on the isocyanate compound, of a compound having at least one unsaturated bond, and the compound having at least one unsaturated bond is a compound having a UV absorption in an area of decamer or higher isocyanates in a gel permeation chromatography measurement spectrum.

[00192] The explanation of the same constitution of the first or second modality can be omitted.

[00193] Although oxidation of an unsaturated bond readily causes coloration in general, the unsaturated bond compound in the isocyanate composition, according to the present embodiment, acts effectively in the isocyanate composition, when stored, to improve the stability of the isocyanate compound. isocyanate without coloring the isocyanate composition.

[00194] Such effects are presumed to be exhibited by selective reaction of the unsaturated bond compounds with water or oxygen, and thus suppressing the denaturation reaction of the isocyanate compound caused by water or oxygen. Furthermore, in the case of a compound having an unsaturated bond between a carbon atom and an oxygen atom, there are many cases in which the tendency to exhibit the effect becomes great.

[00195] To suppress the denaturation reaction of the isocyanate compound, the amount of the unsaturated binding compound is preferably increased. On the other hand, there is a case where an excessive amount of the unsaturated bond compound generates coloration caused by the unsaturated bond as described above, thereby deteriorating the external appearance. Thus, the amount of the unsaturated binding compound according to the present embodiment is from 1.0 ppm by mass to 1.0x104 ppm, the lower limit of the amount is preferably 3.0 ppm by mass or more, more preferably 5.0 ppm by mass or more, and even more preferably 10 ppm by mass or more, and the upper limit of the amount is preferably 5.0x103 ppm by mass or less, more preferably 3.0x103 ppm by mass or less, and even more preferably 1 .0x103 mass ppm or less.

[00196] Thus, the isocyanate composition, according to the present embodiment, contains: a difunctional or more functional isocyanate compound; and 1.0 ppm by mass to 1.0 x 104 ppm, based on the isocyanate compound, of a compound having at least one unsaturated bond, and the compound having at least one unsaturated bond is a compound having a UV absorption in an area of decamer or higher isocyanates in a gel permeation chromatography measurement spectrum. The isocyanate composition preferably also contains 1.0 ppm by mass to 1.0 x 104 ppm, based on the isocyanate compound, of at least one inert compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds and silicon-containing sulfide compounds, the inert compound having no unsaturated bonds between carbon atoms and double bonds between a carbon atom and an oxygen atom, excluding unsaturated bonds constituting an aromatic ring. Among these, compounds A, B, C, D, E and G are preferable from the point of view of thermal stability, and compounds A, B and G are preferable in terms that neither oxide nor peroxide are generated. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00197] Although the inert compound generally has no reactivity against water, oxygen, or the like, the presence of the inert compound further improves the stability of an isocyanate in the isocyanate composition according to one embodiment.

[00198] Such an effect is presumed to be exhibited by vaporizing a portion of the infinitesimally existing inert compound together in the storage container to exist as a vapor component, and thus suppressing the effects of the infinitesimally existing water or oxygen to suppress the increase viscosity or the generation of gelatinous components.

[00199] Although the amount of the inert compound is preferably increased in view of the above-mentioned circumstances, there is a case in which an excess amount thereof significantly alters the properties originally expected to be provided to the isocyanate composition, such as viscosity. Thus, the amount of the inert compound, according to the present embodiment, is from 1.0 ppm by mass to 1.0x104 ppm by mass, the lower limit thereof is preferably 3.0 ppm by mass or more, more preferably 5 .0 ppm by mass or more, and even more preferably 10 ppm by mass or more, and the upper limit thereof is preferably 5.0x103 ppm by mass or less, more preferably 3.0x103 ppm by mass or less, and even more preferably 1.0x103 ppm by mass or less. One type of inert compound may be used alone, or a plurality of types thereof may be used in combination.

[00200] Furthermore, the isocyanate composition containing: a difunctional or more functional isocyanate compound; and a compound having an unsaturated bond preferably additionally contains a sulfuric acid, a sulfuric acid ester, a phosphoric acid and/or a phosphoric acid ester.

[00201] The stability of the isocyanate composition when stored is improved by additionally containing sulfuric acid and/or sulfuric acid ester. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that sulfuric acid and sulfuric acid ester moderately suppress the formation of a nylon body structure 1 of formula (37) in the composition according to the present invention. modality, and thereby suppressing the gelation of the entire composition caused by an increase in the compound. Therefore, it is preferable that the sulfuric acid and/or sulfuric acid ester are contained in a moderate amount range, so as to further improve the stability of the isocyanate. The amount thereof, based on the isocyanate compound, is from 1.0 ppm by mass to 1.0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is preferably 1.0 x 102 ppm by mass or less.

[00202] The isocyanate composition additionally containing a phosphoric acid and/or a phosphoric acid ester also further improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that phosphoric acid and phosphoric acid ester moderately suppress the formation of the nylon body structure 1 of formula (37) in the composition according to the present embodiment. in the same way as that of a sulfuric acid and a sulfuric acid ester, and thereby suppressing the gelation of the entire composition caused by the increase in the compound. Thus, to further improve the stability of the isocyanate, the phosphoric acid and/or phosphoric acid ester is preferably contained in a moderate range of the amount thereof, and the amount, based on the isocyanate compound, is 1.0 ppm by mass. at 1.0 x 103 ppm by mass, the lower limit of the amount is preferably 3.0 ppm by mass or more, and even more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 1, 0 x 101 mass ppm or less.

[00203] The isocyanate composition, according to the present embodiment, also preferably contains a halogen atom, which is not derived from a halogenated hydrocarbon (hereinafter it can be referred to as a halogen atom, simply). The amount of the halogen atom is preferably 1.0 ppm by mass to 1.0 x 102 ppm by mass.

[00204] In the isocyanate composition according to the present embodiment, a halogen atom is contained in various forms, as described above. The halogen atom is preferably chlorine and/or bromine, and at least one selected from the group consisting of chlorine ion, bromine ion, chlorine atom contained in a hydrolyzable chlorine compound and bromine atom contained in a hydrolyzable bromine compound. The total amount of these chlorine atom and bromine atom can be adjusted to be within the above-mentioned range. The difunctional or more functional isocyanate compound and a compound containing a halogen atom can be charged such that the charged amount thereof is within the above-mentioned range, the amount of chlorine atom and bromine atom in the composition can be determined by inductively coupled plasma (ICP), the amount of chlorine ion and bromine ion can be determined by anion chromatography, or hydrolyzable chlorine can be measured according to a hydrolyzable chlorine test method described in appendix 3 of JIS K-1556 ( 2000).

[00205] The isocyanate composition containing a halogen atom improves stability when stored. Although the mechanism by which such an effect is exhibited is not apparent, it is assumed that a halogen atom captures oxygen or water, which deteriorates the stability of the difunctional or more functional isocyanate compound and thereby exhibits the effect of improving the stability of the difunctional or more functional isocyanate compound.

[00206] Thus, the amount of halogen atom is preferably increased to further improve the stability of the isocyanate, while an excessive amount of the halogen atom generates coloration caused by the halogen atom, and may deteriorate the external appearance when used as a raw material. coating, for example. Thus, the amount of halogen atom in the isocyanate composition according to the present embodiment, based on the isocyanate compound, is from 1.0 ppm by mass to 1.0 x 102 ppm by mass, the lower limit of the amount is preferably 3 .0 ppm by mass or more, and more preferably 5.0 ppm by mass or more, and the upper limit of the amount is more preferably 5.0 x 101 ppm by mass or less.

[00207] Since the effects exhibited by containing a halogen atom that is not derived from a halogenated hydrocarbon are also exhibited when the isocyanate composition contains: a trifunctional or more functional isocyanate compound; and a compound having an unsaturated bond; and any of an inert compound, a sulfuric acid, a sulfuric acid ester, a phosphoric acid, and a phosphoric acid ester, additionally contains a halogen atom that is not derived from a halogenated hydrocarbon, the isocyanate composition containing: an trifunctional or more functional isocyanate compound; and a compound having an unsaturated bond; and any of an inert compound, a sulfuric acid, a sulfuric acid ester, a phosphoric acid and a phosphoric acid ester, and additionally containing a halogen atom that is not derived from a halogenated hydrocarbon, is one of the preferable embodiments. In this case, the halogen atom is contained in the above-mentioned quantity in the isocyanate composition and exhibits the same effects.

<Method for producing isocyanate composition>

[00208] The isocyanate composition, according to the present embodiment, can be produced by appropriately mixing an isocyanate compound, a compound having an unsaturated bond, an inert compound, a halogen atom, which is not derived from a halogenated hydrocarbon , sulfuric acid, sulfuric acid ester, a phosphoric acid and a phosphoric acid ester.

[00209] The isocyanate compound can be produced by a conventionally known method. For example, a corresponding organic primary amine and a phosgene are reacted and hydrogen chloride is eliminated to produce an isocyanate compound. The reaction of organic primary amine and phosgene can be carried out in a solvent or in a vapor phase.

[00210] The isocyanate composition, according to the present embodiment, can be produced by appropriately mixing the isocyanate compound obtained by subjecting the isocyanate compound obtained by the conventionally known method, as described above, to a purification step by a method conventionally known, with a compound having an unsaturated bond, an inert compound, a halogen atom that is not derived from a halogenated hydrocarbon, a sulfuric acid, a sulfuric acid ester, a phosphoric acid and a phosphoric acid ester. The compound having an unsaturated bond, the inert compound, the halogen atom that is not derived from a halogenated hydrocarbon, sulfuric acid, sulfuric acid ester, phosphoric acid and phosphoric acid ester, can be pre-added to obtain The isocyanate composition according to the present embodiment, in the step of producing the isocyanate compound, or can be added to obtain the isocyanate composition, according to the present embodiment, after the isocyanate compound is obtained.

[00211] A compound having a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum is produced, for example, by reacting an isocyanate compound having at least one isocyanate group in a molecule of the even in the presence of a catalyst, followed by the addition of a terminating agent to it to stop the polymerization reaction. As a catalyst, the same catalyst used in the isocyanurate formation reaction described below can be used. Although the amount of catalyst to be used depends on the type of compound used, the amount can be from 1.0 x 10-4 parts by mass to 1.0 parts by mass, relative to 100 parts by mass of the isocyanate compound. The upper limit of the amount of catalyst to be used is preferably 5.0x10-1 parts by mass or less, more preferably 1.0x10-1 parts by mass or less, and even more preferably 2.0x10-2 parts by mass or less, from the point of view of suppressing coloration or discoloration of the resulting products and reaction control. The lower limit of the amount of catalyst to be used is, preferably, 1.0x10-3 parts by mass or more and, preferably, 2.0x10-3 parts by mass or more, from the point of view of reactivity.

[00212] As a terminating agent, the same terminating agent as that used in the isocyanurate formation reaction described below can be used. Although the amount of the terminating agent to be used can be appropriately selected depending on the amount of catalyst used or the type of compound used, the amount is preferably at least 1 equivalent, relative to the amount of catalyst used.

[00213] The temperature at which the polymerization reaction of the isocyanate compound is carried out in the presence of a catalyst is preferably from -20 to 60°C. There is a tendency for the isocyanurate formation reaction to proceed easily in association with increasing the reaction temperature and therefore the reaction temperature is preferably low so as to obtain a nylon 1 body structure. The polymerization reaction of the isocyanate compound proceeds excessively slowly at an excessively low reaction temperature, and therefore the reaction temperature is most preferably -10::C to 50°C, and even more preferably from 0°C to 40°C.

[00214] Although the polymerization of the isocyanate compound is carried out in the presence or absence of a solvent, the polymerization is preferably carried out in the presence of a solvent from the point of view of ease in controlling and operating the reaction.

[00215] As a solvent, a solvent that is inert to the isocyanate compound to be used, and can dissolve both a crude isocyanate compound and a resulting polymer: Specifically, as the solvent, acetate esters, such as ethyl acetate, acetate butyl or amyl acetate; aromatic hydrocarbons, such as benzene, toluene, xylene or monochlorobenzene, or the like, can be used alone or in combination.

[00216] The progress of polymerization can be tracked by appropriately sampling the reaction liquid and then performing gel permeation chromatography measurement, and the reaction can be stopped by adding a terminating agent to the reaction liquid, when a peak is confirmed in an area of desired molecular weight. In the case where the isocyanurate formation reaction is carried out in the absence of the solvent, an unreacted isocyanate compound serves as the solvent causing the conversion rate to be 50% or less to dissolve the resulting polymer therein.

[00217] The compound thus produced having a UV absorption in an isocyanate decamer area in a gel permeation chromatography measurement spectrum can be collected by removing the unreacted isocyanate compound and the solvent from the reaction liquid after the end of reaction, or the reaction liquid can be used directly to produce an isocyanate composition in accordance with the present embodiment. The method for collecting the isocyanurate compound is not particularly limited, and examples of this include a method in which an unreacted polyisocyanate and a solvent are removed by carrying out distillation purification. Removal from the process is preferably carried out at a low temperature, and using, for example, an apparatus, which has a large evaporation area for the liquid and presents a favorable evaporation efficiency, such as the reducing falling thin film evaporator. , thin film evaporation apparatus, or molecular distillation apparatus.

[00218] In relation to the compound containing an isocyanurate group and/or a biuret group, a compound containing an isocyanurate group can be produced by the same method as described in <method for producing an isocyanate polymer> described below.

[00219] The compound having a biuret group can be produced by allowing the reaction to proceed using, for example, water, monovalent tertiary alcohol, formic acid, hydrogen sulfide, organic primary monoamine, or organic primary diamine, as a formation agent. biuret, at a reaction temperature of 70C to 200C, for 10 minutes to 24 hours, followed by, after the end of the reaction, separating unreacted polyisocyanates and a solvent from a composition containing an isocyanate polymer by carrying out a treatment such as such as a thin film distillation method or a solvent extraction method. The same solvent as that in the <method for producing isocyanate polymer> described below can be used in the biuret formation reaction.

<Method for producing isocyanate polymer>

[00220] In one embodiment, the present invention provides a method for producing an isocyanate polymer, containing a step in which the isocyanate compound contained in the isocyanate composition is reacted. Hereinafter, the production method, according to the present embodiment, will be explained. Although the isocyanurate formation reaction is mainly explained, conventionally known reactions, such as imino-oxadiazinedione formation reaction or uretdione formation reaction, may be used, depending on the catalysts or reaction conditions used, as described below.

[00221] The isocyanurate formation reaction is preferably carried out in the presence of an isocyanurate formation catalyst. As the isocyanurate formation catalyst, basic catalysts are generally preferred, for example, and specific examples thereof include the following compounds (i) to (viii).

[00222] (i) Hydroxides or salts of organic acids (such as acetic acid salts, butyric acid salts, decanoic acid salts) of tetraalkylammonium (such as tetramethylammonium or tetraethylammonium).

[00223] (ii) Hydroxide or salts of organic acids (such as acetic acid salts, butyric acid salts, or decanoic acid salts) of trialkylhydroxyalkyl ammonium (such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium , or triethylhydroxyethylammonium).

[00224] (iii) Metal salts (such as tin salts, zinc salts, lead salts, sodium salts or potassium salts) of alkylcarboxylic acids such as acetic acid, capric acid, octyl acid or myristic acid.

[00225] (iv) Metal alkoxides such as sodium or potassium.

[00226] (v) Compounds containing aminosilyl groups (such as hexamethyldisilazane).

[00227] (vi) Phosphorus-based compounds, such as tributylphosphine.

[00228] (vii) Fluorine compounds or polyhydrogen fluoride compounds (such as tetraalkylammonium fluorides such as tetramethylammonium fluoride hydrate or tetraethylammonium fluoride).

[00229] (viii) Compounds consisting of compounds having a structure of the following formula (40) or formula (41) (such as 3,3,3-trifluoropropionic acid; 3,3,4,4,4-pentafluorobutanoic acid); 3,3,4,4,5,5,5-heptafluoropentanoic acid or 3,3-difluoroprop-2-enoic acid) and quaternary ammonium ions or quaternary phosphonium ions.

[00230] In formulas (40) and (41), R22 and R23 each independently represent a C1-30 perfluoroalkyl group, R' each independently represents a group selected from the group consisting of an atom of hydrogen, a C1-20 alkyl group, and an aromatic group, and R22, R23, and R' may contain a heteroatom.

[00231] In formulas (40) and (41), R22 and R23 can each independently represent a linear, branched or cyclic saturated perfluoroalkyl group or an unsaturated perfluoroalkyl group.

[00232] Among these, catalyst (i) or (ii) is preferable as the isocyanurate formation catalyst from the point of view of the efficiency of the catalyst and the selectivity of the isocyanurate formation reaction. Furthermore, the catalyst (vi) is preferably used to form a uretdione structure (the structure of formula (7)) at a high rate. Furthermore, the catalyst (vii) or the catalyst (viii) is preferably used to form an imino-oxadiazinedione structure (the structure of formula (5)) at a high ratio.

[00233] Although the amount of the isocyanurate formation catalyst to be added to the reaction system of the isocyanurate formation reaction can be appropriately varied depending on the type of catalyst used or the concentration of other components in the reaction system, the amount, in relative to 100 parts by mass of the isocyanate compound, it may be 1.0 x 10-4 parts by mass to 1.0 parts by mass. The upper limit of the amount used of the isocyanurate-forming catalyst is preferably 5.0x10-1 parts by mass or less, more preferably 1.0x10-1 parts by mass or less, and even more preferably 2.0x10-2 parts by mass mass or less, from the standpoint of suppression of coloring or discoloration or resulting products and reaction control. The lower limit of the amount used of the isocyanurate-forming catalyst is more preferably 1.0x10-3 parts by mass or more, and even more preferably 2.0x10-3 parts by mass or more, from the point of view of reactivity.

[00234] The aforementioned isocyanurate formation catalyst can simultaneously serve as an allophanate formation catalyst. In this way, it is possible to allow the isocyanurate-forming reaction and the allophanate-forming reaction to proceed simultaneously by adding a compound containing a hydroxy group before or during the isocyanurate-forming reaction.

[00235] The hydroxy group-containing compound is, preferably, a compound having one or two hydroxy groups in a molecule consisting only of carbon, hydrogen and oxygen, and even more preferably, a compound having only one hydroxy group. a hydroxy group include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, examples of the compound having two hydroxy groups include ethylene glycol, 1,3-butanediol, 1 ,4-butanediol, neopentylglycol and 2-ethylhexanediol, and two types or more can be used together.

[00236] Although the reaction temperature of the isocyanurate formation reaction is not particularly limited, the reaction temperature is preferably 0C to 200°C. In the case where the reaction temperature is lower than 0C, the reaction rate is small, which is not practical. In the case where the reaction temperature exceeds 200C, secondary reaction or excessive coloring of the resulting product tends to occur easily. Among the range, the lower limit of the reaction temperature is more preferably 40C, even more preferably 50C, and particularly preferably 60C, from the point of view of the reaction rate. The upper limit of the reaction temperature is more preferably 150C or less, even more preferably 120C, and particularly preferably 110C, from the point of view of the color of the resulting product.

[00237] The reaction time of the isocyanurate formation reaction is not particularly limited, and the reaction time can be within a range of 10 seconds to 24 hours.

[00238] Examples of a method of confirming the endpoint of the isocyanurate formation reaction include: a method for measuring the rate of isocyanate group content in the reaction mixture (% NCO; a method for measuring an index of refraction; and a method in which the reaction mixture is subjected to measurement by gel permeation chromatography.The method for measuring the amount of isocyanate groups (%NCO) in the reaction mixture will be described below.

[00239] In the case where the isocyanurate formation reaction proceeds excessively, the viscosity of the resulting product is increased, the proportion of the amount of the isocyanurate compound is increased, and a manufactured article having desired physical properties cannot be obtained, and, therefore, the reaction conversion rate (mass proportion of the resulting isocyanate polymer, relative to the initial mass of isocyanate compound as a feedstock) is preferably limited to 50% or less (more preferably 40% or less, and further more preferably 25% or less). Furthermore, from the point of view of sufficiently obtaining the yield of the isocyanurate compound, the reaction conversion rate is preferably 5% or more, more preferably 10% or more, and most preferably 15% or more.

[00240] In the production method, according to the present embodiment, when the isocyanurate formation reaction reaches the desired conversion rate, a catalyst terminating agent is added to the resultant to deactivate the isocyanurate formation catalyst so until the isocyanurate formation reaction is completed. If the catalyst terminating agent is not added, the isocyanurate formation reaction proceeds further in a step where remaining monomers or solvents are removed by distillation of the isocyanate polymer or when the manufactured article is stored, thus causing cases where the its viscosity increases and gelatinous components are generated. Therefore, it is preferable that the isocyanurate forming catalyst is deactivated by adding the catalyst terminating agent to the resultant when the desired conversion rate is obtained.

[00241] As the catalyst terminating agent, for example, compounds of sulfuric acid, phosphoric acid, acidic phosphate esters, hydrochloric acid, sulfonic acid and the like can be used. In the case where a reaction product of the catalyst terminating agent and the catalyst are precipitated as a solid, the reaction product is preferably separated by a method such as filtration using a filter or Celite.

[00242] Although the isocyanurate formation reaction can be carried out in the presence or absence of a solvent, the isocyanurate formation reaction is preferably carried out in the presence of a solvent from the point of view of ease in controlling and operating the reaction.

[00243] As a solvent available in the isocyanurate formation reaction, a solvent that is inactive with respect to an isocyanate compound to be used and can dissolve an isocyanate compound used as a raw material and a resulting isocyanurate compound is selected . Specifically, as the solvent, acetate esters such as ethyl acetate, butyl acetate and amyl acetate; and aromatic hydrocarbons such as benzene, toluene, xylene and monochlorobenzene can be used alone or in combination.

[00244] Furthermore, in the case where the isocyanurate formation reaction is carried out in the absence of a solvent, the unreacted polyisocyanate functions as a solvent and can dissolve the resulting isocyanurate compound when the conversion rate is limited to 50% or less. Thus, the conversion rate of the isocyanurate formation reaction in the absence of a solvent is preferably 5% to 50%, and more preferably 10% to 40%.

[00245] After completion of the isocyanurate formation reaction, the isocyanurate compound can be collected by removing the unreacted isocyanate compound and the solvent from the reaction system, for example. A removal method is not particularly limited, and the unreacted isocyanate compound and solvent can be removed by distillation purification, for example. Furthermore, the removal process is desirably carried out at a low temperature, and is preferably carried out using a device that has a large evaporating surface relative to the liquid and good evaporation efficiency, such as a falling thin film evaporator, a thin film evaporation apparatus, or a molecular distillation apparatus.

<Isocyanate polymer>

[00246] The above-mentioned production method is preferably used to produce an isocyanate polymer by polymerizing isocyanate compounds. The isocyanate polymer has: one unit of the following formula (A) or (B); and at least one unit of the following formulas (2) to (8). Nitrogen atoms that constitute an isocyanate polymer bond with carbon atoms.

[00247] In formulas (A), (B) and (2) to (8), each R3 independently represents a residual group obtained by removing two isocyanate groups from the isocyanate compound, and each R4 independently represents a monovalent organic group.

[00248] In formulas (6) and (8), R4 depends on a compound used to produce an isocyanate polymer and often represents a residual group obtained by removing a hydroxy group (OH group) from the aforementioned alcohol when the alcohol is used, for example.

[00249] Although the structure of the isocyanate polymer according to the present embodiment depends on the isocyanate compounds used, the composition of the isocyanate composition, the reaction conditions, or the like, the structure of the following formula (46), (47) , (48) or (49) is preferably contained.

[00250] In the formulas, R3 formulas (A), (B) and (2) to (8), and R4 represents the same group as R4 in formulas (6) and (8).

[00251] The isocyanate compound is not particularly limited and can be suitably modified depending on the intended isocyanurate. For example, an aliphatic and/or alicyclic isocyanate is preferably used from the point of view of obtaining an isocyanurate polymer preferably available in the application in which weather resistance is required. Furthermore, an aromatic isocyanate can be selected for the purpose of applying the resultant in the field where weather resistance is not required.

<Use of isocyanate polymer>

[00252] A block isocyanate polymer can be produced using a composition including several isocyanate polymers obtained by the method described above and blocking part or all of the isocyanate groups of the isocyanate polymers by a blocking agent.

[00253] Furthermore, with the aim of improving water dispersibility, a composition containing an isocyanate polymer modified by a hydrophilic group can also be obtained, in which a part of the isocyanate groups of various isocyanate polymers obtained by the previous method is modified by a hydrophilic compound containing active hydrogen.

[00254] Furthermore, the isocyanate polymer obtained by the above-mentioned production method can be reacted with a blocking agent and an active hydrogen-containing hydrophilic compound, respectively, when it is being used as a coating material for a liquid or an agent. crosslinking of a coating agent.

[00255] As described above, the isocyanate composition exhibits a stability-enhancing effect when stored. Furthermore, an isocyanate polymer can be prepared using the isocyanate composition according to the above-mentioned embodiment. The isocyanate composition or isocyanate polymer may suitably be used preferably as a raw material of a coating material, an adhesive agent, or the like.

<Method for storing a difunctional or more functional isocyanate compound>

[00256] In one embodiment, the present invention provides a method for storing the difunctional or more functional isocyanate compound. The storage method according to the present embodiment contains: formulation, in the difunctional or more functional isocyanate compound, from 1.0 ppm by mass to 1.0 x 104 ppm, based on the isocyanate compound, of the compound having at least an unsaturated bond other than unsaturated bonds constituting an aromatic ring, the compound being other than an isocyanate, a sulfuric acid, an ester of sulfuric acid, a phosphoric acid, and/or, an ester of phosphoric acid.

[00257] The storage method according to the present embodiment makes it possible to prevent the isocyanate compound from increasing viscosity, generating gelatinous components, or increasing chromaticity, even when the trifunctional or more functional isocyanate compound is stored for a long period , such as, for 100 days or more, 200 days or more, 300 days or more, or 500 days or more.

EXAMPLES

[00258] Although the present invention is described in greater detail below by the Examples, the present invention is not limited to the following Examples. The terms “%” and “ppm” described in the Examples mean “% by mass” and “ppm by mass”, respectively.

<NCO Quantity (%NCO)>

[00259] The amount of NCO (% by mass) was determined by neutralizing the isocyanate group in the test portion with an excessive amount of 2N amine and then performing the back-titration with 1N hydrochloric acid.

<Gel Permeation Chromatography (GPC)>

[00260] The GPC measurement method is described below.

[00261] Apparatus used: HLC-8120 (manufactured by Tosoh Corporation) Column used: TSK GEL Super H1000, TSK GEL Super H2000, TSK GEL Super H3000 (all of them are manufactured by Tosoh Corporation.) Test portion concentration: 5% wt/vol (50 mg of a test portion was dissolved in 1 mL of tetrahydrofuran (THF)).

[00262] Vehicle: THF Detection method: Differential refractometer Outflow flow: 0.6 mL/min Column temperature: 30° C

[00263] In producing the calibration curve, polystyrene having a molecular weight of 1,000 to 20,000 was used.

<Liquid chromatography (LC)>

[00264] The LC measurement method is described below.

[00265] Apparatus used: HLC-8120 (manufactured by Tosoh Corporation) Column used: TSK GEL ODS-5 (manufactured by Tosoh Corporation.) Vehicle: acetonitrile/water = 50/50 (vol) Detection method: UV: Flow of output: 1.0 mL/min, Column temperature: 40° C

<Gas chromatography (GC)>

[00266] Column: The inner diameter was 0.32 mm, the length was 30 m, and the liquid phase film thickness was 1.0 μm (DB-1 manufactured by J&W Scientific, Inc.)

[00267] Column temperature: The initial temperature was 50 C and then the temperature was increased at a rate of 10 C/minute to the final temperature of 300 C (maintained for 15 minutes at the final temperature).

[00268] Injection temperature: 300°C Detector temperature: 300°C.

[00269] Detector: Flame ionization detector Carrier gas: Helium Carrier gas output flow (column): 1.2 mL/minute

<NMR analysis method>

[00270] Equipment: JNM-A400 FT-NMR System (manufactured by JEOL LTD.)

[00271] Analysis sample: Approximately 0.3 g of a sample solution was accurately weighed, and approximately 0.7 g of deuterochloroform or deuterodimethylsulfoxide and approximately 0.05 g of tetramethyltin, as an internal standard substance, were added to the same and mixed evenly to obtain a sample for NMR analysis.

<Hazen color number (APHA)>

[00272] The numerical values obtained by measurement by a Hazen meter are described as the Hazen color number.

<Measurement of chlorine concentration and bromine concentration>

[00273] A weighed sample was placed on a sample plate of a combustion pretreatment apparatus, the sample plate was moved to a combustion part, the sample was burned by an automatic combustion controller, and the vaporized component was absorbed by an absorbent liquid. The absorbent liquid was injected into an ion chromatograph to determine the amount of the intended component.

[00274] Combustion pretreatment apparatus: AQF-100 automatic combustion controller (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) Furnace temperature: Inlet 900°C, Outlet 1000°C Output gas flow: Air/ O2 400 mL/minute, O2 200 mL/minute Ion chromatograph: ICS-1500 (manufactured by DIONEX) Pre-column: AG 12a Separation column: AG 12a Suppressor: ASRS-300 Suppressor current: 50 mA Eluent: 2.7 mM Na2CO3, 0.3 mM NaHCO3

A1 purification example

[00275] A sample was supplied to a multi-stage distillation column (selected from the structured packing distillation column, random packing distillation column and plate distillation column). Pressure was controlled at the top of the distillation column (absolute pressure), and the amount of heat required for distillation was supplied by a reboiler. After the temperature distribution in the column became stable, a fraction of the distillate was removed from a side cutting line equipped below the upper portion of the column in a height direction. The resulting fraction was analyzed.

A2 purification example

[00276] An isocyanate liquid to be purified was supplied to a fine falling film type molecular distillation device (such as type MS-300 manufactured by SHIBATA SCIENTIFIC TECHNOLOGY LTD.), and a vaporized composition component was captured on the surface from a cooling device and then extracted to a collection device. An inert gas such as nitrogen, argon or helium was accompanied with this as necessary.

A3 purification example

[00277] The amount of heat required for distillation was supplied to a falling film type evaporator by a jacket or medium heat heater, an isocyanate composition to be purified was supplied from an upper portion of the falling film type evaporator and a vapor gas was extracted by countercurrent flow or concurrent flow. An inert gas such as nitrogen, argon or helium was accompanied with this as necessary.

Example 1 Preparation of isocyanate composition

[00278] 200 g of 1,3,6-triaminohexane was mixed with 1000 g of o-dichlorobenzene and phosgene gas was bubbled for 12 hours, heating the mixture to 130°C. Furthermore, a nitrogen gas was additionally bubbled into the resultant to remove the phosgene and the o-dichlorobenzene was removed by distillation at 1 kPa and 120°C to obtain 190 g of a 1,3,6-triisocyanate-hexane ( TTI) crude (with a purity of 90%). The resulting 1,3,6-triisocyanate-hexane was subjected to purification by distillation using a falling thin film type molecular distillation device (type MS 300 manufactured by SHIBATA SCIENTIFIC TECHNOLOGY LTD.) at a jacket temperature of 160 ::C and at a pressure of 0.5 kPa to obtain 1,3,6-triisocyanate-hexane. Methyl-phenyl-carbonate was added to the resultant such that its amount, relative to isocyanate, became 13 ppm, to prepare an isocyanate composition. The amount of 1,3,6-triisocyanate-hexane in the composition, measured by GC, was 98.7% by mass, and the composition was a mixture composed of 1,3,6-tri-isocyanate-hexane and methyl-phenyl-carbonate. APHA was 10.

Storage of isocyanate composition

[00279] 300 g of the resulting isocyanate composition obtained above was placed in a 500 mL storage container made of SUS, nitrogen exchange was performed, and the resultant was stored for 300 days in a storage environment in the Kojima area of Kurashiki City, Okayama Prefecture, Japan. After storage, the molecular weight of the resultant was analyzed by GPC, a peak area (referred to as peak 2) confirmed on the one side of higher molecular weight than the peak of 1,3,6 -triisocyanate-hexane (referred to as peak 1) was approximately 10%, relative to peak 1. APHA was 20.

Example 2 Preparation of isocyanate composition

[00280] 1,3,6-Triisocyanate-hexane was prepared in the same way as in Example 1 and then a dibutyl phosphate was added in such a way that the amount of dibutyl phosphate, in relation to the isocyanate, was became 7 ppm, to prepare an isocyanate composition. The amount of 1,3,6-triisocyanatohexane in the composition, measured by GC, was 97% by mass and APHA was 21.

Storage of isocyanate composition

[00281] The isocyanate composition prepared above was stored in the same way as that in Example 1. The result is shown in Table 1. Synthesis Example B1

[00282] 100 g (321 mmol) of a compound of the following formula (40) and 90.6 g (969 mmol) of phenol reacted by heating the mixture under a nitrogen atmosphere at 100°C. When the reagent was analyzed by liquid chromatography to confirm the amount of phenol remaining, the amount of phenol was at or below the limit of detection. The reagent was used as a compound of formula (1) or (33) in the present embodiment.

Example 3 Preparation of isocyanate composition

[00283] 100 g of the compound of formula (40) and 9 g of the compound prepared in Synthesis Example B1 were mixed to prepare an isocyanate composition. The amount of the compound of formula (1) or (33), relative to the isocyanate compound, was 90 ppm. Dimethyl carbonate and pentadecane were added such that their amounts, relative to the isocyanate compound, became 14 ppm and 1700 ppm, respectively, to prepare an isocyanate composition.

Storage of isocyanate composition

[00284] The isocyanate composition prepared above was stored in the same way as that in Example 1. The result is shown in Table 1. Synthesis Example B2

[00285] 100 g (495 mmol) of the compound of the following formula (44) and 73.4 g (990 mmol) of 1-butanol reacted by heating the mixture under a nitrogen atmosphere at 100°C. When the reagent was analyzed by liquid chromatography to confirm the amount of butanol remaining, the amount was at or below the limit of detection. The reagent was used as a compound of formula (1) or (33) in the present embodiment.

Example 4 Preparation of isocyanate composition

[00286] 55 g of the compound of formula (44) and 1.5 mg of the compound obtained in Synthesis Example B2 were mixed to prepare an isocyanate composition. The amount of the compound of formula (1) or (33), relative to the isocyanate compound, was 3 ppm.

Storage of isocyanate composition

[00287] The isocyanate composition prepared above was stored in the same way as that in Example 1. The result is shown in Table 1. Synthesis Example B3

[00288] 1,8-Diisocyanate-4-isocyanatomethyloctane (hereinafter may be referred to as TTI) was prepared in the same way as in Example 1, except that 4-aminomethyloctane-1,8-diamine was used instead of 1,3,6-triaminohexane.

[00289] 10.5 mg (4.6x10-2 mmol) of a titanium catalyst of the following formula (45) and TTI were reacted under a nitrogen atmosphere for 24 hours at 25°C. The obtained reagent was a compound with a UV absorption in a decamer area or higher isocyanates in a gel permeation chromatography measurement spectrum as shown in Fig.1.

[00290] In Fig. 1, a horizontal axis indicates the retention time in gel permeation chromatography and the vertical axis indicates the absorption measured by the UV detector (at a wavelength of 254 nm). The retention time indicated as TTI decamer shows the retention time of the molecular weight corresponding to the TTI decamer, and the retention time indicated as TTI shows the retention time of the molecular weight corresponding to the TTI. The compound having a UV absorption in a decamer or higher isocyanate area in a gel permeation chromatography measurement spectrum obtained in Synthesis Example B3 was a compound having a peak at the 8.778 minute retention time of the gel permeation chromatogram. gel in Fig. 1.

Example 5 Preparation of isocyanate composition

[00291] 500 g of TTI and 7.5 mg of a compound obtained in Synthesis Example B3 were mixed to prepare an isocyanate composition. The amount of a compound with a UV absorption in an area of decamer or higher isocyanates, relative to the isocyanate compound, was 15 ppm.

Storage of isocyanate composition

[00292] The isocyanate composition prepared above was stored in the same way as that in Example 1. The result is shown in Table 1.

Example 6 Preparation of isocyanate composition

[00293] To a purified TTI liquid obtained in a similar manner to Example 1, dibutyl phosphate and DURANATE (TLA-100 manufactured by Asahi Kasei Corporation), which was a mixture of uretdione and dibutyl isocyanurate, were added. hexamethylene isocyanate, so that their respective amounts, in relation to the isocyanate compound, were 20 ppm.

Storage of isocyanate composition

[00294] The isocyanate composition prepared above was stored in the same way as that in Example 1. The result is shown in Table 1. Examples 7-74, Comparative Examples 1-18

[00295] Isocyanates obtained in the same way as those in Example 1 were used, except that the corresponding raw materials were used and the amounts of a “crude amine” and a stabilizer were changed as described in the tables. After the isocyanates were purified by any of purification examples A1 to A3, isocyanate compositions were prepared using the isocyanates and stored in the same manner as those in Example 1. The results are shown in the tables below. In Comparative Examples 1, 3, 5, 7, 9, 11, 13, 15 and 17, gel was generated in the isocyanate after storage and therefore GPC measurement could not be performed.

[00296] In the following tables, the term “crude amine” means an amine used as a raw material to synthesize an isocyanate. For example, the case in which a compound obtained by reaction of isocyanate and phenol was used as a compound of formula (1) or (33) as in Synthesis Example B1 was indicated as “isocyanate and phenol reagent”. In the synthesis of the compound corresponding to the compound of formula (1) or (33), an isocyanate contained in the isocyanate composition, and two equivalents of a hydroxyl compound (aromatic hydroxy compound or alcohol) were used, in relation to isocyanate groups of the isocyanate , were used. As a “compound having a UV absorption in an area of decamer or higher isocyanates”, a compound synthesized in a manner similar to that in Synthesis Example B2, except that an isocyanate contained in the isocyanate composition was used instead of 1,3 ,6-triisocyanate-hexane. As a compound having an isocyanurate group and/or a biuret group, DURANATE TPA-100, TKA-100 and TLA-100, manufactured by Asahi Kasei Corporation, were used.

[00297] In the following tables, the amount of a compound contained in the composition represents an amount relative to an isocyanate compound.

Example C1 Isocyanate polymer synthesis

[00298] 100 g of the isocyanate composition after storage in Example 1 was placed in a four-neck glass flask and equipped with a thermometer, a stirrer and a sealed nitrogen tube, the air in the flask was replaced by nitrogen, and the composition was heated to 70C while stirring was carried out. The refractive index of the reaction liquid was measured to gradually add a catalyst (tetramethylammonium hydroxide) to the composition until the isocyanate conversion rate became 20%, and when the conversion rate became 20%, 0.5 g of an 85% aqueous phosphoric acid solution was added to terminate the reaction.

[00299] After the reaction, the reacting liquid was subjected to filtration and the unreacted isocyanates were removed at 160°C (0.5 Pa) for the first time and at 180°C (0.5 Pa) for the second time using a falling thin film type molecular distillation device to obtain an isocyanate polymer. As a result of FT-IR measurement and 1H NMR measurement of the resulting isocyanate polymer, it was confirmed that the resulting isocyanate polymer had an isocyanurate structure (structure of formula (2) and a terminal isocyanate structure (structure of formula (A) or (B)), and was a medium isocyanate of 3.5 mer.

[00300] The conversion rate was determined by measuring the change in the refractive index of a reactant liquid as a sample at 30C using a refractometer (trade name of RA-520 manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD). weather resistance of isocyanate polymer

[00301] The isocyanurate polymer and polyester polyol (manufactured by Nuplex Resin under the trade name Setal 166) were formulated in such a way that the equivalent ratio of isocyanate groups/hydroxy groups became 1.0 and then a mixture composed of ethyl acetate, toluene, butyl acetate, xylene and propylene glycol monomethyl ether acetate (mass ratio of 30/30/20/15/5) so that the mass of the solid content including the isocyanurate polymer and the polyol is became 50% to obtain a coating material solution. The coating material solution was applied to a plate coated with white enamel, coating with an applicator so that the thickness of the film after drying was 40 μm, and then the coated film was cured at a temperature of 20C and a humidity of 63% for 1 week, followed by evaluating the weather resistance of the coated board. Weather resistance was evaluated using a weather resistance meter with dew point indicator panel (manufactured by Suga Test Instruments Co., Ltd.). The evaluation was carried out according to JIS D 0205 under the conditions where the irradiance was 30 W/m2, the panel temperature was 60C and the irradiation time and condensation time were repeated every 4 hours.

[00302] When the exposure time reached 1200 hours, the gloss retention rate of the coated plate was 80% or more.

Example D1

[00303] An inner portion of a four-necked flask equipped with a stirrer, a thermometer, a cooling tube and an FT-IR probe (manufactured by METTLER TOLEDO, React-IR, AgX probe) was replaced with nitrogen, 120 g of the isocyanate composition after storage in Example 2 and 130 g of polyester polyol “PLACCEL 305” (trade name manufactured by DAICEL CORPORATION) derived from trivalent alcohol and ε-caprolactone were placed therein and then the mixture was heated to 130°C while the mixture was stirred. The reaction progressed while the amount of urethane groups produced by FT-IR was confirmed.

[00304] Then, 0.5 g of an octanol solution containing 20% zirconyl 2-ethylhexanoate was added to the resultant to allow an allophanate formation reaction to proceed. When the increase in refractive index became 0.0051, a solution of 2-ethyl-1-hexanol containing a pyrophosphoric acid at a solids content of 10% (the trade name “phosphoric acid (105%)” manufactured by Taihei Chemical Industrial Co. Ltd., diluted with 2-ethyl-1-hexanol) was added to the resultant to stop the reaction.

[00305] After the filtrate was filtered, distillation was carried out at 180°C and 0.3 kPa using a falling thin film evaporator to collect the residue. The residue was further subjected to distillation using a thin film distillation apparatus at 160°C and 0.3 kPa to obtain an isocyanate polymer.

[00306] The resulting isocyanate polymer was used to evaluate in terms of weather resistance in a similar way to Example C1. When the exposure time reached 1200 hours, the gloss retention rate was 80% or more.

Example E1

[00307] 400 g of TTI and 200 g of the composition in Example 1 were weighed in a four-neck glass flask and equipped with a thermometer, a stirrer and a tube sealed with nitrogen, nitrogen replacement was carried out in the reactor and then the mixture was heated to 65°C. Then, 140 g of 2-ethylhexanol were added to the resultant and then the mixture was stirred for 10 minutes. Then, 50 g of a 5% isobutanol solution of tetrabutylammonium acetate was added to the resultant for 60 minutes. The temperature was maintained at 65 ± 2 C during the reaction. 5 g of an 85% aqueous phosphoric acid solution was added as a reaction termination agent, the mixture was heated to 100°C and then stirred for 1 hour after the temperature reached 100°C. The reaction liquid was colorless and transparent. The reaction liquid was filtered with a membrane filter with a fine pore size of 1 μm to separate a residue from the reaction, and then an unreacted TTI was removed by distillation with a thin film distillation apparatus to obtain a polypropylene composition. -isocyanate. The resulting polyisocyanate composition was approximately colorless and transparent.

[00308] As a result of FT-IR and 1H NMR measurement of the resulting isocyanate polymer, it was confirmed that the resulting isocyanate polymer had an isocyanurate structure (structure of formula (2)), an allophanate structure (structure of formula (6)), a urethane group (structure of formula (8) in which R4 represents the 2-ethylhexyl group), and a terminal isocyanate structure (structure of formula (A) and (B)), and was an isocyanate of 3.3 mer.

INDUSTRIAL APPLICABILITY

[00309] According to the present invention, an isocyanate composition containing a difunctional diisocyanate and/or a trifunctional or more functional isocyanate is provided, the storage stability of which is improved. Furthermore, in accordance with the present invention, a method for producing a polyisocyanate composition by polymerizing the isocyanate composition is provided.

Claims (5)

1. Isocyanate composition, characterized by the fact that it comprises: a trifunctional isocyanate compound of formula (24): wherein a plurality of Y1 each independently represents a single bond, or a bivalent C120 hydrocarbon group which may contain an ester structure and/or an ether structure, and R24 represents a hydrogen atom or an monovalent C1-12 hydrocarbon; and 1.0 ppm by mass to 1.0 x 104 ppm by mass, based on the isocyanate compound, of a compound having at least one unsaturated bond excluding unsaturated bonds constituting an aromatic ring, the compound being other than the isocyanate compound and from formula (1) wherein R1 represents a C2-10 aliphatic group or a C6-10 aromatic group, which may have an isocyanate group, R2 represents a C2-10 aliphatic group or a C2-25 aromatic group, which does not have an isocyanate group, and the represents an integer of 1 or 2. 2. Isocyanate composition according to claim 1, characterized in that it further comprises, based on the isocyanate compound, 1.0 ppm by mass to 1.0 x 104 ppm by mass of at least one inert compound selected from the group consisting of hydrocarbon compounds, ether compounds, sulfide compounds, halogenated hydrocarbon compounds, silicon-containing hydrocarbon compounds, silicon-containing ether compounds, and silicon-containing sulfide compounds, the inert compound being free of unsaturated bonds between atoms of carbon and unsaturated bonds between a carbon atom and an oxygen atom, excluding unsaturated bonds constituting an aromatic ring, and/or, 1.0 ppm by mass to 1.0x103 ppm by mass of a sulfuric acid and/or an ester of sulfuric acid, and/or, 1.0 ppm by mass to 1.0x103 ppm by mass of a phosphoric acid and/or a phosphoric acid ester. 3. Isocyanate composition according to claim 1 or 2, characterized in that it further comprises 1.0 ppm by mass to 1.0 x 102 ppm by mass, based on the isocyanate compound, of a halogen atom that is not derived from a halogenated hydrocarbon compound. 4. Isocyanate composition according to any one of claims 1 to 3, characterized in that an amount of the isocyanate compound is 97% by mass or more, based on a total of the isocyanate composition. 5. Method for producing an isocyanate polymer, characterized in that it comprises reacting a comprised isocyanate compound into an isocyanate composition as defined in any one of claims 1 to 4, wherein the isocyanate polymer comprises: a unit of formula (A); and at least one unit selected from the group consisting of units of formulas (2), (3), (4), (5), (6), (7) and (8), and a nitrogen atom constituting the bonds of isocyanate polymer with one carbon atom: wherein each R3 independently represents a residual group obtained by removing two isocyanate groups from the isocyanate compound, and each R4 independently represents a monovalent organic group.