Polyisocyanate composition, polyurethane-forming composition, adhesive agent composition, and polyurethane

Abstract

A polyisocyanate composition comprising a reaction product of an isocyanate compound and a chlorine-containing polyether polyol represented by formula (1) [in the formula, R1 represents a residue obtained by removing, from a compound having m-number of active hydrogen-containing groups, the m-number of active hydrogen-containing groups, m represents 2 or 3, and n represents the number of repeating units derived from epichlorohydrin and is an integer of 2 or more], wherein the blending ratio of the chlorine-containing polyether polyol and the isocyanate compound when setting and reacting the chlorine-containing polyether polyol and the isocyanate compound is NCO / OH=5.0 / 1 to 70.0 / 1 as indicated as the mole ratio of the total amount of NCO groups in the isocyanate compound and the total amount of OH groups in the chlorine-containing polyether polyol.

Description

Polyisocyanate composition, polyurethane-forming composition, adhesive composition, and polyurethane

[0001] The present disclosure relates to a polyisocyanate composition, a polyurethane-forming composition, an adhesive composition, and a polyurethane, and more particularly, to a polyisocyanate composition containing a reaction product of a chlorine-containing polyol and an isocyanate compound, a polyurethane-forming composition and an adhesive composition containing the polyisocyanate composition, and a polyurethane obtained from the polyurethane-forming composition.

[0002] When the chlorine-containing polyol is used as a raw material for polyurethane, it is possible to improve the adhesion of the polyurethane to a metal or resin substrate. For example, Japanese Patent Application Laid-Open No. 2020-83972 (Patent Document 1) discloses an NCO-terminated urethane prepolymer having a structural unit derived from a chlorine-containing polyol. Patent Document 1 also describes that when this urethane prepolymer is used as a raw material for polyurethane, it may be cured in one liquid or in two liquids in combination with a curing agent (active hydrogen-containing compound).

[0003] Japanese Patent Application Laid-Open No. 2020-83972

[0004] However, since the NCO-terminated urethane prepolymer described in Patent Document 1 has a high viscosity, it is not easy to mix it uniformly when mixing with a curing agent (active hydrogen-containing compound), and it has not been easy to use it as a raw material for a two-component type polyurethane-forming composition.

[0005] Therefore, one aspect of this disclosure aims to provide a polyisocyanate composition that has low viscosity, good handling properties, can be easily and uniformly mixed with a curing agent (active hydrogen-containing compound), and can form an adhesive layer with excellent reliability and durability (less prone to interfacial fracture) when used as a raw material for a polyurethane adhesive composition. Another aspect of this disclosure aims to provide a polyurethane-forming composition and a polyurethane using the polyisocyanate composition of one aspect of this disclosure. Furthermore, yet another aspect of this disclosure aims to provide an adhesive composition that can form an adhesive layer with excellent reliability and durability.

[0006] This disclosure provides the following aspects: [1] Formula (1):

[0007]

[0008] [In the above formula, R １A polyisocyanate composition containing a reaction product of a chlorine-containing polyether polyol and an isocyanate compound, wherein the mixing ratio of the chlorine-containing polyether polyol and the isocyanate compound at the time of the reaction charge is such that the molar ratio of the total amount of NCO groups of the isocyanate compound to the total amount of OH groups of the chlorine-containing polyether polyol is NCO / OH = 5.0 / 1 to 70.0 / 1. [2] The polyisocyanate composition according to [1], wherein the mixing ratio of the chlorine-containing polyether polyol to the isocyanate compound at the time of the reaction charge of the chlorine-containing polyether polyol and the isocyanate compound is chlorine-containing polyether polyol:isocyanate compound = 10:90 to 50:50 in terms of the mass ratio of the chlorine-containing polyether polyol to the isocyanate compound. [3] The polyisocyanate composition according to [1] or [2], wherein the content of NCO groups in the composition is 10 to 30% by mass. [4] The polyisocyanate composition according to any one of [1] to [3], wherein the content of free isocyanate compounds in the composition is 20 to 90% by mass. [5] A polyurethane-forming composition containing the polyisocyanate composition according to any one of [1] to [4] and an active hydrogen-containing compound. [6] A polyurethane which is the reaction product of the polyisocyanate composition and the active hydrogen-containing compound in the polyurethane-forming composition according to [5]. An adhesive composition comprising the polyisocyanate composition described in any one of items [7], [1] to [4], an active hydrogen compound, and a filler.

[0009] According to one aspect of this disclosure, a polyisocyanate composition can be obtained that has low viscosity, good handling properties, can be easily and uniformly mixed with a curing agent (active hydrogen-containing compound), and can form an adhesive layer with excellent reliability and durability (less prone to interfacial fracture) when used as a raw material for a polyurethane adhesive composition. According to another aspect of this disclosure, a polyurethane-forming composition and polyurethane can be obtained using the polyisocyanate composition of one aspect of this disclosure. Furthermore, according to yet another aspect of this disclosure, an adhesive composition can be obtained that can form an adhesive layer with excellent reliability and durability.

[0010] This graph shows the results of analyzing the polyisocyanate compositions obtained in Examples 2 to 5 by gel permeation chromatography (GPC) after sealing them with methanol.

[0011] Exemplary embodiments for carrying out each aspect of this disclosure will be described in further detail. However, this disclosure is not limited to the following embodiments.

[0012] In this specification, numerical ranges indicated using "~" represent a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. Furthermore, the upper and lower limits described individually can be combined in any way.

[0013] The polyisocyanate compositions, polyurethane-forming compositions, adhesive compositions, and polyurethanes of this disclosure will be described in detail below in accordance with their preferred embodiments.

[0014] [Polyisocyanate Composition] A polyisocyanate composition according to one aspect of the present disclosure contains a reaction product obtained by reacting a chlorine-containing polyether polyol with an isocyanate compound in a specific ratio.

[0015] (Chlorine-containing polyether polyol) Chlorine-containing polyether polyol is given by the following formula (1):

[0016]

[0017] It is represented by [this].

[0018] In formula (1), R １ represents the residue obtained by removing m active hydrogen-containing groups from a compound having m active hydrogen-containing groups, where m is 2 or 3.

[0019] Examples of active hydrogen-containing groups include hydroxyl groups, amino groups, carboxylic acid groups, and thiol groups. There are no particular restrictions on compounds having m active hydrogen-containing groups (m-functional active hydrogen-containing compounds) as long as they have m of these active hydrogen-containing groups, and examples include hydroxyl compounds, amine compounds, carboxylic acid compounds, and thiol compounds. Examples of residues obtained by removing m active hydrogen-containing groups from an m-functional active hydrogen-containing compound include hydroxyl residues, amine residues, carboxylic acid residues, and thiol residues.

[0020] Examples of hydroxy compounds include low molecular weight diols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,6-hexanediol, 1,9-nonanediol, 2,5-hexanediol, 1,3-cyclohexanediol, 2-methylpentane-2,4-diol, 2,5-dimethyl-2,5-hexanediol, bisphenol, and 1,5-naphthalenediol; low molecular weight triols such as glycerin, trimethylolpropane, and hexanetriol; polyether diols such as polypropylene glycol with a molecular weight of 200 to 1000; and polyether triols with a molecular weight of 200 to 1000 obtained by addition polymerization of propylene glycol to glycerin.

[0021] Examples of amine compounds include ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,2-butylenediamine.

[0022] Examples of carboxylic acid compounds include phthalic acid and adipic acid.

[0023] Examples of thiol compounds include ethanedithiol and butanedithiol.

[0024] Among these m-functional active hydrogen-containing compounds, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,9-nonanediol, 2,5-hexanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, ethylenediamine, and polyetherdiols with molecular weights of 200 to 1000 are preferred from the viewpoint of being able to efficiently produce chlorine-containing polyetherdiols, and tripropylene glycol, 2,5-hexanediol, 1,9-nonanediol, and polyetherdiols with molecular weights of 200 to 1000 are particularly preferred.

[0025] In formula (1), n ​​represents the number of repeating units derived from epichlorohydrin. There are no particular restrictions as long as n is an integer of 2 or more, but from the viewpoint of viscosity, handling properties, and production efficiency of polyurethane, an integer between 2 and 50 is preferred, and an integer between 2 and 30 is more preferred.

[0026] The number-average molecular weight of the chlorine-containing polyether polyol is preferably 400 to 5000, and more preferably 1000 to 3000, from the viewpoint of viscosity, handling properties, and production efficiency of the polyisocyanate composition and polyurethane.

[0027] Chlorine-containing polyether polyols can be obtained by polymerizing epichlorohydrin using an m-functional active hydrogen-containing compound as an initiator. There are no particular restrictions on the polymerization method, and conventionally known methods can be employed.

[0028] For example, a method of addition polymerization of epichlorohydrin using an m-functional active hydrogen-containing compound as an initiator in the presence of a Lewis acid catalyst or a complex metal cyanide catalyst; and a method of ring-opening polymerization of epichlorohydrin using an m-functional active hydrogen-containing compound as an initiator in the presence of a phosphazenium salt or onium salt catalyst and a Lewis acid catalyst.

[0029] The Lewis acid catalyst, phosphazenium salt, and onium salt catalyst are not particularly limited as long as they can be used in the addition polymerization or ring-opening polymerization of epichlorohydrin. For example, the Lewis acid catalyst, phosphazenium salt, and onium salt catalyst described in Japanese Patent Application Publication No. 2020-83972 can be cited.

[0030] While there are no particular restrictions on the polymerization temperature, a temperature of 70 to 150°C is preferred, and 90 to 110°C is more preferred, from the viewpoint that epichlorohydrin does not easily decompose and the molecular weight distribution does not spread, and catalytic activity is easily expressed.

[0031] Polymerization reactions are preferably carried out without a solvent, but may also be carried out in a solvent. Examples of solvents include benzene, toluene, xylene, cyclohexane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 1,4-dioxane, and 1,2-dimethoxyethane.

[0032] (Isocyanate Compounds) There are no particular restrictions on the isocyanate compounds, and examples include aromatic isocyanate compounds, aliphatic isocyanate compounds, alicyclic isocyanate compounds (monocyclic alicyclic isocyanate compounds, crosslinked cyclic alicyclic isocyanate compounds), and polyisocyanate derivatives thereof.

[0033] Examples of aromatic isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or mixtures thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or mixtures thereof), 4,4'-diphenyl diisocyanate, diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate, or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), and tetramethylxylylene Examples include isocyanates (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, naphthalene diisocyanates (1,5-, 1,4- or 1,8-naphthalene diisocyanate, or mixtures thereof) (NDI), triphenylmethane triisocyanate, tris(isocyanatephenyl)thiophosphate, polymethylene polyphenylene polyisocyanate, nitrodiphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

[0034] Examples of aliphatic isocyanate compounds include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate, pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, and the like.

[0035] Examples of monocyclic alicyclic isocyanate compounds include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), methylenebis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis(cyclohexyl isocyanate)), or mixtures thereof. Examples include hydrogenated MDI (compound), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis(isocyanate methyl)cyclohexane (1,3- or 1,4-bis(isocyanate methyl)cyclohexane, or mixtures thereof) (hydrogenated XDI), dimer acid diisocyanate, transcyclohexane 1,4-diisocyanate, hydrogenated tolylene diisocyanate (hydrogenated TDI), hydrogenated tetramethylxylylene diisocyanate (hydrogenated TMXDI), etc.

[0036] Examples of cross-linked cyclic alicyclic isocyanate compounds include norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, diisocyanate methyl bicycloheptane, and di(diisocyanate methyl)tricyclodecane.

[0037] Examples of derivatives of these polyisocyanates include polymers of the above-mentioned isocyanate compounds (dimers, trimers, pentamers, heptamers, uretidinedione, ureitonimine, isosynurate modified, polycarbodiimide, etc.), urethane modified (e.g., urethane modified in which a portion of the isocyanate groups in the above-mentioned isocyanate compound or polymer is modified or reacted with a monool or polyol), biuret modified (e.g., biuret modified produced by the reaction of the above-mentioned isocyanate compound with water), allophanate modified (e.g., allophanate modified produced by the reaction of the above-mentioned isocyanate compound with a monool or polyol component), urea modified (e.g., urea modified produced by the reaction of the above-mentioned isocyanate compound with a diamine), oxadiazinetrione (e.g., oxadiazinetrione produced by the reaction of the above-mentioned isocyanate compound with carbon dioxide, etc.).

[0038] The above-mentioned isocyanate compounds or their derivatives may be used individually or in combination of two or more.

[0039] (Polyisocyanate composition) The polyisocyanate composition contains a reaction product obtained by mixing a chlorine-containing polyether polyol and an isocyanate compound in a specific ratio and reacting them.

[0040] When charging the chlorine-containing polyether polyol and the isocyanate compound for reaction, the mixing ratio of the chlorine-containing polyether polyol and the isocyanate compound is required to be 5.0 / 1 to 70.0 / 1 in terms of the molar ratio (NCO / OH) of the total amount of NCO groups of the isocyanate compound and the total amount of OH groups of the chlorine-containing polyether polyol, preferably 8.0 / 1 to 55.0 / 1, and more preferably 10.0 / 1 to 50.0 / 1. When NCO / OH is at or above the lower limit, the viscosity of the resulting polyisocyanate composition tends to be low and the handling property tends to improve. On the other hand, when NCO / OH is at or below the upper limit, when the polyisocyanate composition is used as a raw material for a polyurethane adhesive composition, the reliability and durability of the adhesive layer tend to improve (interface failure is less likely to occur).

[0041] Further, as the mixing ratio of the chlorine-containing polyether polyol and the isocyanate compound when charging the chlorine-containing polyether polyol and the isocyanate compound for reaction, the mass ratio of the chlorine-containing polyether polyol and the isocyanate compound (chlorine-containing polyether polyol: isocyanate compound) is preferably 10:90 to 50:50, more preferably 10:90 to 45:55, and even more preferably 10:90 to 40:60. When the chlorine-containing polyether polyol: isocyanate compound is at or above the lower limit, the viscosity of the resulting polyisocyanate composition tends to be low and the handling property tends to improve. On the other hand, when the chlorine-containing polyether polyol: isocyanate compound is at or below the upper limit, when the polyisocyanate composition is used as a raw material for a polyurethane adhesive composition, the reliability and durability of the adhesive layer tend to improve (interface failure is less likely to occur).

[0042] The temperature at which the chlorine-containing polyether polyol and the isocyanate compound are reacted may be set as appropriate. For example, 60 to 90 °C is preferable.

[0043] The reaction product of chlorine-containing polyether polyol and isocyanate compound is obtained by reacting the chlorine-containing polyether polyol and isocyanate compound at the above-mentioned mixing ratio during the reaction phase, that is, under conditions of a large excess of isocyanate compound. It is believed that the reaction occurs when the terminal hydroxyl groups of the chlorine-containing polyether polyol react with the isocyanate groups of the isocyanate compound, resulting in a compound having terminal isocyanate groups, with m isocyanate compound molecules bonded to the terminals of one molecule of chlorine-containing polyether polyol. Furthermore, because of the large excess of isocyanate compound, the polyisocyanate composition contains unreacted isocyanate compound (free isocyanate compound) in addition to the above-mentioned reaction product.

[0044] Thus, in the polyisocyanate composition according to one embodiment of the present disclosure, the reaction product of the chlorine-containing polyether polyol and the isocyanate compound has a low molecular weight, and free isocyanate compounds remain, which is thought to result in low viscosity and excellent handling properties.

[0045] The NCO group content in the polyisocyanate composition is preferably 10 to 30% by mass, more preferably 15 to 30% by mass, and even more preferably 18 to 30% by mass. When the NCO group content in the polyisocyanate composition is above the lower limit, the viscosity of the resulting polyisocyanate composition tends to decrease, improving handling properties. On the other hand, when the NCO group content in the polyisocyanate composition is below the upper limit, when the polyisocyanate composition is used as a raw material for a polyurethane adhesive composition, the reliability and durability of the adhesive layer tend to improve (interfacial fracture is less likely to occur).

[0046] The content of the free isocyanate compound (unreacted isocyanate compound) in the polyisocyanate composition is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, and still more preferably 35 to 80% by mass. When the content of the free isocyanate compound in the polyisocyanate composition is at least the above lower limit, the viscosity of the resulting polyisocyanate composition tends to be low and the handling property tends to be improved. On the other hand, when the content of the free isocyanate compound in the polyisocyanate composition is at most the above upper limit, when the polyisocyanate composition is used as a raw material for the polyurethane adhesive composition, the reliability and durability of the adhesive layer tend to be improved (interface failure is less likely to occur).

[0047] [Polyurethane-forming composition and adhesive composition] The polyurethane-forming composition of another aspect of the present disclosure contains a polyisocyanate composition and an active hydrogen-containing compound. Further, the adhesive composition of another aspect of the present disclosure contains a polyisocyanate composition, an active hydrogen-containing compound, and a filler.

[0048] (Active hydrogen-containing compounds) There are no particular restrictions on active hydrogen-containing compounds as long as they play a role as a curing agent for the polyisocyanate composition, and any compound having one or more active hydrogen-containing groups is acceptable, for example, water, polypropylene glycol, polyethylene propylene glycol, ethylene glycol (EG), diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripylene glycol, 1,4-butanediol (1,4-BD), 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane and other diols; polypropylene triol, polyethylene propylene Examples include triols such as triols, glycerin, trimethylolpropane (TMP), and triethanolamine; polyols with four or more functions such as polypropylenetetraol, polyethylenepropylenetetraol, castor oil, sucrose, and sorbitol; modified polyamines such as 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA) and modified MOCA modified with aniline, etc.; aromatic amines such as toluenediamine, diphenylmethanediamine, and diethyltoluenediamine; aliphatic amines such as ethylenediamine; polyamines such as Jefamine ED; amino alcohols such as ethanolamine and diethanolamine; and mixtures of two or more of these.

[0049] (Fillers) Examples of fillers include inorganic fillers and organic fillers.

[0050] Examples of inorganic fillers include silica, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, ferrites, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, talc, clay, mica, montmorillonite, bentonite, sepiolite, imogolite, sericite, glass fibers, glass beads, silica balloons, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, carbon fibers, carbon balloons, zinc borate, and various magnetic powders.

[0051] Examples of organic fillers include synthetic organic fine particles such as polystyrene, polyacrylonitrile, polymethyl methacrylate, polypropylene, polyethylene, polyvinyl chloride, and polyurethane, as well as natural organic fine particles such as wood powder, bamboo powder, sawdust, paper pulp, and wood-based refined cellulose powder obtained from paper pulp.

[0052] (Other components) Polyurethane-forming compositions and adhesive compositions may contain various additives such as urethane catalysts, foam stabilizers, antioxidants, and plasticizers, as needed, as well as other polyols.

[0053] Examples of urethane catalysts include known urethane catalysts such as tertiary amine compounds and organometallic compounds.

[0054] Examples of tertiary amine compounds include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, and diazabicycloundecene (also known as DBU).

[0055] Examples of organometallic compounds include tin compounds and non-tin compounds.

[0056] Examples of tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (also known as DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, dioctyltin dilaurylate (also known as DOTDL), and tin 2-ethylhexanoate.

[0057] Examples of non-tin compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium naphthenate.

[0058] These urethane catalysts may be used individually or in combination of two or more. Among these urethane catalysts, dibutyltin dilaurate (also known as DBTDL), dioctyltin dilaurate (also known as DOTDL), and tin 2-ethylhexanoate are preferred from the viewpoint of reactivity and hygiene.

[0059] Examples of foam stabilizers include silicone compounds.

[0060] Examples of antioxidants include compounds that have the effect of suppressing the oxidation of polymer chains, such as thioether compounds, phosphorus-based antioxidants, and hindered phenol compounds.

[0061] Examples of plasticizers include phthalates, non-aromatic dibasic acid esters, aliphatic esters, polyalkylene glycol esters, phosphate esters, trimellitic acid esters, chlorinated paraffins, hydrocarbon oils, process oils, polyethers, epoxy plasticizers, and polyester plasticizers, with phthalates being preferred. Specifically, examples include dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, isodecyl succinate, tricresyl phosphate, tributyl phosphate, epoxidized soybean oil, and benzyl epoxy stearate.

[0062] Other polyols include, for example, polyether polyols obtained by ring-opening polymerization of alkylene oxides, polymer polyols obtained by radical polymerization of vinyl monomers in polyether polyols, polyester polyols obtained by polycondensation of polyhydric alcohols and polyhydric carboxylic acids, polyesteramide polyols obtained by polycondensation of polyhydric alcohols, polyhydric carboxylic acids and amino alcohols, polylactone polyols obtained by ring-opening polymerization of lactones, polycarbonate polyols obtained by polycondensation of polyhydric alcohols and carbonates, acrylic polyols, polybutadiene polyols and their hydrogenated products, polyisoprene polyols and their hydrogenated products, partially saponified ethylene-vinyl acetate copolymers, and natural oil-based polyols such as soybean oil and castor oil.

[0063] In polyurethane-forming compositions, from the viewpoint of superior tensile strength of the resulting polyurethane, and in adhesive compositions, from the viewpoint of superior adhesion, in the polyisocyanate compositions used as raw materials for these compositions, the mixing ratio of chlorine-containing polyether polyol to isocyanate compound during the reaction charge of chlorine-containing polyether polyol to isocyanate compound is preferably 11.0 / 1 to 70.0 / 1 in terms of the molar ratio (NCO / OH) of the total amount of NCO groups of the isocyanate compound to the total amount of OH groups of the chlorine-containing polyether polyol, more preferably 12.0 / 1 to 55.0 / 1, and even more preferably 13.0 / 1 to 50.0 / 1. Furthermore, the mass ratio (chlorine-containing polyether polyol: isocyanate compound) of chlorine-containing polyether polyol to isocyanate compound is preferably 10:90 to 35:65, more preferably 10:90 to 32:68, and even more preferably 10:90 to 30:70.

[0064] In polyurethane-forming compositions and adhesive compositions, from the viewpoint of superior adhesion to metals, the molar ratio (NCO groups / active hydrogen-containing groups) of the total amount of NCO groups to the total amount of active hydrogen-containing groups in the composition is preferably 1.0 / 1 to 15.0 / 1, more preferably 1.0 / 1 to 12.0 / 1, and even more preferably 1.0 / 1 to 10.0 / 1.

[0065] Furthermore, in the adhesive composition, from the viewpoint of superior adhesion to metals, the amount of filler added is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the total amount of the polyisocyanate composition and the active hydrogen-containing compound.

[0066] Furthermore, when incorporating the above-mentioned additives or other polyols into polyurethane-forming compositions and adhesive compositions, there are no particular restrictions on the amount to be added; it can be set appropriately according to the desired physical properties.

[0067] [Polyurethane] A polyurethane in another aspect of the present disclosure is a reaction product of a polyisocyanate composition and an active hydrogen-containing compound in a polyurethane-forming composition.

[0068] The temperature and time for reacting the polyisocyanate composition with the active hydrogen-containing compound can be appropriately set according to the purpose, but for example, a reaction temperature of 20 to 220°C and a reaction time of 0.1 minutes to 24 hours are preferred.

[0069] Polyurethane can be molded into desired shapes by conventionally known methods. For example, when producing polyurethane sheets or polyurethane films, molding methods include manual coating using spatulas, combs, rollers, trowels, rakes, etc., and mechanical coating using sealing guns, sprays, etc.

[0070] Specific applications of polyurethane are not limited to these, but include, for example, waterproof coatings for balconies and rooftops of buildings, waterproof sheets, waterproof coatings for vehicles, flooring for condominiums, houses, and hospitals, elastic paving materials for sports facilities, sealing materials for civil engineering and construction, sealing materials for vehicles such as direct glazing and body sealers, potting agents for medical use, and caulking for siding joints.

[0071] The following describes examples of the present disclosure, but the present disclosure is not limited to these examples. The chlorine-containing polyether polyols used in the examples and comparative examples were synthesized by the following method. The molecular weight of the synthesized chlorine-containing polyether polyols was determined by the following method.

[0072] (Molecular weight of chlorine-containing polyether polyol) The hydroxyl value d (unit: mgKOH / g) of the chlorine-containing polyether polyol was measured according to the method described in JIS K-1557. The number of functional groups of the obtained chlorine-containing polyether polyol was denoted as e, and the molecular weight (unit: g / mol) of the chlorine-containing polyether polyol was calculated using the following formula.

[0073] Molecular weight = (56100 / d) x e

[0074] (Synthesis Example 1) Synthesis of Chlorine-Containing Polyether Polyol (A-1) First, 566.4 g of polypropylene glycol with a molecular weight of 400 (manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix PP-400) and 6.85 g of tetrabutylammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged into a 2 L four-necked flask equipped with a stirring blade. After replacing the atmosphere inside the flask with a nitrogen atmosphere, dehydration treatment was carried out under reduced pressure at 0.5 kPa at a temperature of 100°C for 2 hours. Then, 13.02 g of triisopropoxyaluminum (manufactured by Kawaken Fine Chemicals, Ltd., trade name: PADM) was added, and dehydration treatment was carried out under reduced pressure at 0.5 kPa at a temperature of 100°C for 2 hours to prepare the initiator composition.

[0075] Next, the obtained initiator composition was heated to 98°C, and then 720 ml of epichlorohydrin (ECH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was continuously supplied over 4 hours. After that, an aging treatment was carried out for 2 hours while maintaining the internal temperature at 90-100°C, and then residual epichlorohydrin was removed by depressurization treatment at 100°C and a pressure of 0.5 kPa to obtain 1498 g of crude chlorine-containing polyether polyol. After cooling this crude chlorine-containing polyether polyol to 80°C, 74.89 g of epoxidized soybean oil (manufactured by ADEKA Corporation, trade name: ADEKA Sizer O-130P) was added, and then 1 part by mass of diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., trade name: Radiolite #3000) and 5 parts by mass of ion-exchanged water were added to 100 parts by mass of the obtained crude liquid, and the mixture was stirred at atmospheric pressure and 80°C for 2 hours. Subsequently, dehydration was initiated by increasing the temperature while reducing the pressure, and finally, dehydration was carried out under reduced pressure at a temperature of 100°C and a pressure of 0.2 kPa for 3 hours. The obtained liquid was subjected to pressure filtration at a temperature of 90°C and a pressure of 0.3 MPa using a stainless steel holder with a tank fitted with a 120-mesh stainless steel mesh (Advantec Toyo Co., Ltd., product name: KST-142) to obtain a pale yellow chlorine-containing polyether polyol (A-1) with a molecular weight of 1000.

[0076] (Synthesis Example 2) - Synthesis of chlorine-containing polyether polyol (A-2) The synthesis was carried out in the same manner as in Synthesis Example 1, except that the amount of polypropylene glycol with a molecular weight of 400 was changed to 308.95 g, the amount of tetrabutylammonium bromide to 3.73 g, the amount of triisopropoxyaluminum to 7.10 g, and the amount of epoxidized soybean oil to 61.17 g. A pale yellow chlorine-containing polyether polyol (A-2) with a molecular weight of 1500 was obtained.

[0077] (Synthesis Example 3) - Synthesis of chlorine-containing polyether polyol (A-3) The synthesis was carried out in the same manner as in Synthesis Example 1, except that the amount of polypropylene glycol with a molecular weight of 400 was changed to 130.71 g, the amount of tetrabutylammonium bromide was changed to 1.58 g, the amount of triisopropoxyaluminum was changed to 3.00 g, and the amount of epoxidized soybean oil was changed to 51.68 g. A pale yellow chlorine-containing polyether polyol (A-3) with a molecular weight of 3000 was obtained.

[0078] (Example 1) 150 g of the chlorine-containing polyether polyol (A-1) obtained in Synthesis Example 1 and 350 g of isocyanate compound (B-1) (a mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate (manufactured by Tosoh Corporation, product name: Millionate NM)) were charged into a 1 L four-necked flask equipped with a stirring blade. The molar ratio of the total amount of NCO groups in isocyanate compound (B-1) to the total amount of OH groups in chlorine-containing polyether polyol (A-1), calculated from the amount charged, was NCO / OH = 9.3 / 1.

[0079] After replacing the atmosphere inside the flask with a nitrogen atmosphere, the chlorine-containing polyether polyol (A-1) and isocyanate compound (B-1) were reacted by stirring at a temperature of 75°C. The content of NCO groups in the reaction solution was measured and monitored according to the method described in JIS K7301, and the reaction was continued until the decrease in the NCO group content stopped, yielding a polyisocyanate composition (C-1) containing the reaction product of chlorine-containing polyether polyol (A-1) and isocyanate compound (B-1).

[0080] (Example 2) A polyisocyanate composition (C-2) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 1, except that 70 g of chlorine-containing polyether polyol (A-2) obtained in Synthesis Example 2 was used instead of chlorine-containing polyether polyol (A-1), and the amount of isocyanate compound (B-1) was changed to 430 g. The molar ratio of the total amount of NCO groups in isocyanate compound (B-1) to the total amount of OH groups in chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 36.2 / 1.

[0081] (Example 3) A polyisocyanate composition (C-3) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 2, except that the amount of chlorine-containing polyether polyol (A-2) was changed to 145 g and the amount of isocyanate compound (B-1) was changed to 355 g. The molar ratio of the total amount of NCO groups of isocyanate compound (B-1) to the total amount of OH groups of chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 14.3 / 1.

[0082] (Example 4) A polyisocyanate composition (C-4) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 2, except that the amount of chlorine-containing polyether polyol (A-2) was changed to 185 g and the amount of isocyanate compound (B-1) was changed to 315 g. The molar ratio of the total amount of NCO groups of isocyanate compound (B-1) to the total amount of OH groups of chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 10.2 / 1.

[0083] (Example 5) A polyisocyanate composition (C-5) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 2, except that the amount of chlorine-containing polyether polyol (A-2) was changed to 225 g and the amount of isocyanate compound (B-1) was changed to 275 g. The molar ratio of the total amount of NCO groups of isocyanate compound (B-1) to the total amount of OH groups of chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 7.3 / 1.

[0084] (Example 6) A polyisocyanate composition (C-6) containing the reaction product of chlorine-containing polyether polyol (A-3) and isocyanate compound (B-1) was obtained in the same manner as in Example 1, except that 250 g of chlorine-containing polyether polyol (A-3) obtained in Synthesis Example 3 was used instead of chlorine-containing polyether polyol (A-1), and the amount of isocyanate compound (B-1) was changed to 250 g. The molar ratio of the total amount of NCO groups in isocyanate compound (B-1) to the total amount of OH groups in chlorine-containing polyether polyol (A-3), calculated from the amount charged, was NCO / OH = 12.0 / 1.

[0085] (Comparative Example 1) A polyisocyanate composition (D-1) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 2, except that the amount of chlorine-containing polyether polyol (A-2) was changed to 25 g and the amount of isocyanate compound (B-1) was changed to 475 g. The molar ratio of the total amount of NCO groups in isocyanate compound (B-1) to the total amount of OH groups in chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 114 / 1.

[0086] (Comparative Example 2) A polyisocyanate composition (D-2) containing the reaction product of chlorine-containing polyether polyol (A-2) and isocyanate compound (B-1) was obtained in the same manner as in Example 2, except that the amount of chlorine-containing polyether polyol (A-2) was changed to 350 g and the amount of isocyanate compound (B-1) was changed to 150 g. The molar ratio of the total amount of NCO groups of isocyanate compound (B-1) to the total amount of OH groups of chlorine-containing polyether polyol (A-2), calculated from the amount charged, was NCO / OH = 2.6 / 1.

[0087] (Comparative Example 3) A polyisocyanate composition (D-3) containing the reaction product of PPG and isocyanate compound (B-1) was obtained in the same manner as in Example 1, except that 145 g of general-purpose polypropylene glycol (PPG, manufactured by Sanyo Chemical Industries, Ltd., trade name: Sannix PP-1000) was used instead of chlorine-containing polyether polyol (A-1), and the amount of isocyanate compound (B-1) was changed to 355 g. The molar ratio of the total amount of NCO groups in isocyanate compound (B-1) to the total amount of OH groups in PPG, calculated from the amount charged, was NCO / OH = 9.6 / 1.

[0088] [Properties of the Polyisocyanate Composition] The content of NCO groups and free diphenylmethane diisocyanate (MDI) in the obtained polyisocyanate composition, as well as the viscosity of the polyisocyanate composition, were measured by the following method. These results are shown in Table 1.

[0089] <NCO group content> The NCO group content [mass%] was measured according to the method described in JIS K7301.

[0090] <Free MDI Content> A sample with a concentration of 0.1% by mass was prepared by dissolving the polyisocyanate composition in chloroform. Gas chromatography (GC) analysis was performed on this sample under the following measurement conditions, and the free MDI content [by mass] was determined from the peak area ratio of free MDI to the standard sample, based on a calibration curve previously prepared using the standard sample.

[0091] (Measurement conditions) GC instrument: Shimadzu GC-2025. Column: Agilent Technologies HP-50+ (0.25 mm I.D. × 30 m, df = 0.25 μm). Column temperature: 150°C for 2 minutes → increase temperature at 10°C / min → 280°C for 5 minutes. Detector temperature: 280°C. Standard sample: Mixture of 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate (Tosoh Corporation, product name: Millionate NM).

[0092] <Viscosity> The viscosity of the polyisocyanate composition at 25°C was measured using a Brookfield viscometer and evaluated according to the following criteria: A (Excellent handling): Less than 10,000 mPa·s. B (Good handling): 10,000 mPa·s or more and less than 30,000 mPa·s. C (Poor handling): 30,000 mPa·s or more.

[0093]

[0094] <GPC Measurement> The obtained polyisocyanate compositions were reacted with methanol to encapsulate the isocyanate groups, and the results were analyzed using gel permeation chromatography. The results are shown in Figure 1. From the results shown in Figure 1, it was confirmed that the polyisocyanate compositions (C-2) to (C-5) are mixtures of reaction products between chlorine-containing polyether polyols and isocyanate compounds, and free isocyanate compounds (unreacted isocyanate compounds).

[0095] (Example 7) In a 150 ml container for stirring and defoaming mixer, 22.6 g of the polyisocyanate composition (C-2) obtained in Example 2, 23.4 g of general-purpose PPG (manufactured by Sanyo Chemical Industries, Ltd., product name: Sannix PP-1000), 3.1 g of 1,4-butanediol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 1.6 g of trimethylolpropane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed. Using a stirring and defoaming mixer (manufactured by THINKY, product name: Awatori Rentaro ARE-310), the mixture was stirred for 15 minutes at 23°C and 2000 rpm, and then defoamed at 2200 rpm to prepare a polyurethane-forming composition.

[0096] The obtained polyurethane-forming composition was coated onto a release polyethylene terephthalate (PET) film (manufactured by Teijin DuPont, trade name: Purex) with a 0.5 mm thick spacer using a coater, and then left to stand for 24 hours at room temperature under a nitrogen atmosphere. Subsequently, the polyurethane-forming composition on the PET film was cured by leaving it in a gear oven at 80°C for 3 days to produce a polyurethane sheet.

[0097] Similarly, in the same manner as above, 22.6 g of polyisocyanate composition (C-2), 23.4 g of general-purpose PPG, 3.1 g of 1,4-butanediol, and 1.6 g of trimethylolpropane were placed in a 150 ml container for a stirring and defoaming mixer. Furthermore, 4.7 g of talc (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 4.7 g of zeolite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred for 15 minutes at 23°C and 2000 rpm using a stirring and defoaming mixer (manufactured by THINKY, product name: Awatori Rentaro ARE-310), followed by defoaming at 2200 rpm to prepare the adhesive composition.

[0098] The obtained adhesive composition was applied to an aluminum substrate (Al-Mg alloy, A5052P, untreated surface, 25 mm wide, 100 mm long, 3 mm thick) to a width of 25 mm and a length of 10 mm. A similar aluminum substrate was then placed on top of the applied portion, and the resulting laminate was left to stand in a 90°C gear oven for 3 days to cure the adhesive composition, thereby creating an adhesive test specimen in which the aluminum substrates were bonded together. When placing the aluminum substrates on top of the applied portion, glass beads were used to adjust the thickness of the adhesive layer to 0.25 mm.

[0099] (Example 8) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 27.0 g of the polyisocyanate composition (C-3) obtained in Example 3 was used instead of the polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 18.9 g. A polyurethane sheet was then produced.

[0100] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 27.0 g of polyisocyanate composition (C-3) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 18.9 g. Adhesion test specimens were then prepared.

[0101] (Example 9) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 30.1 g of the polyisocyanate composition (C-4) obtained in Example 4 was used instead of the polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 15.7 g. A polyurethane sheet was then produced.

[0102] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 30.1 g of polyisocyanate composition (C-4) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 15.7 g. Adhesion test specimens were then prepared.

[0103] (Example 10) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 34.1 g of the polyisocyanate composition (C-5) obtained in Example 5 was used instead of the polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 11.2 g. A polyurethane sheet was then produced.

[0104] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 34.1 g of polyisocyanate composition (C-5) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 11.2 g. Adhesion test specimens were then prepared.

[0105] (Comparative Example 4) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 20.6 g of the polyisocyanate composition (D-1) obtained in Comparative Example 1 was used instead of the polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 25.4 g. A polyurethane sheet was then produced.

[0106] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 20.6 g of polyisocyanate composition (D-1) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 25.4 g. Adhesion test specimens were then prepared.

[0107] (Comparative Example 5) An attempt was made to prepare a polyurethane-forming composition in the same manner as in Example 7, except that 50.1 g of the polyisocyanate composition (D-2) obtained in Comparative Example 2 was used instead of the polyisocyanate composition (C-2), the amount of 1,4-butanediol was changed to 2.1 g and the amount of trimethylolpropane was changed to 1.2 g, and general-purpose PPG was not used. However, the viscosity was high and it was not possible to mix it uniformly, making it difficult to produce a polyurethane sheet.

[0108] Furthermore, an attempt was made to prepare an adhesive composition in the same manner as in Example 7, except that 50.1 g of polyisocyanate composition (D-2) was used instead of polyisocyanate composition (C-2), the amount of 1,4-butanediol was changed to 2.1 g, the amount of trimethylolpropane to 1.2 g, the amount of talc to 3.3 g, and the amount of zeolite to 3.3 g, and general-purpose PPG was not used. However, the viscosity was high, it could not be mixed uniformly, and it was difficult to prepare adhesive test specimens.

[0109] (Comparative Example 6) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 27.6 g of the polyisocyanate composition (D-3) obtained in Comparative Example 3 was used instead of the polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 18.4 g. A polyurethane sheet was then produced.

[0110] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 27.6 g of polyisocyanate composition (D-3) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 18.4 g. Adhesion test specimens were then prepared.

[0111] (Comparative Example 7) A polyurethane-forming composition was prepared in the same manner as in Example 7, except that 19.6 g of isocyanate compound (B-1) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 26.4 g. A polyurethane sheet was then produced.

[0112] Furthermore, an adhesive composition was prepared in the same manner as in Example 7, except that 19.6 g of isocyanate compound (B-1) was used instead of polyisocyanate composition (C-2), and the amount of general-purpose PPG was changed to 26.4 g. Adhesion test specimens were then prepared.

[0113] [Physical Properties of Polyurethane] The tensile strength and tensile elongation of the obtained polyurethane sheets, and the adhesive strength and fracture state of the adhesive test specimens were measured by the following methods. These results are shown in Table 2.

[0114] <Tensile Strength and Tensile Elongation> The obtained polyurethane sheet was punched out into the shape of an AS-1822 dumbbell to prepare tensile test specimens. Tensile tests were performed on these specimens using a tensile testing machine (manufactured by TSE Corporation, product name: Autocom type universal testing machine AC-10KN-CM-PL) at a tensile speed of 10 mm / min, and the breaking strength and elongation were measured and evaluated as tensile strength and tensile elongation.

[0115] <Adhesive Strength and Failure State> Tensile tests were performed on the obtained adhesive test specimens using a tensile testing machine (manufactured by TSE Corporation, product name: Autocom type universal tester AC-10KN-CM-PL) at a tensile speed of 50 mm / min, and the shear peel strength was measured and evaluated as the adhesive strength. In addition, the failure state of the adhesive portion of the adhesive test specimen after the shear peel strength measurement (cohesive failure (CF) or interfacial failure (AF), and the percentage of cohesive failure (CF) in the case of cohesive failure) was observed and evaluated visually.

[0116]

Claims

1. The following formula (1): [In the above formula, R １ A polyisocyanate composition containing a reaction product of a chlorine-containing polyether polyol and an isocyanate compound, wherein the mixing ratio of the chlorine-containing polyether polyol and the isocyanate compound at the time of the reaction charge is such that the molar ratio of the total amount of NCO groups of the isocyanate compound to the total amount of OH groups of the chlorine-containing polyether polyol is NCO / OH = 5.0 / 1 to 70.0 / 1.

2. The polyisocyanate composition according to claim 1, wherein the mixing ratio of the chlorine-containing polyether polyol to the isocyanate compound at the time of the reaction between the chlorine-containing polyether polyol and the isocyanate compound is such that the mass ratio of the chlorine-containing polyether polyol to the isocyanate compound is 10:90 to 50:

50.

3. The polyisocyanate composition according to claim 1, wherein the content of NCO groups in the composition is 10 to 30% by mass.

4. The polyisocyanate composition according to claim 1, wherein the content of free isocyanate compounds in the composition is 20 to 90% by mass.

5. A polyurethane-forming composition comprising the polyisocyanate composition according to any one of claims 1 to 4 and an active hydrogen-containing compound.

6. A polyurethane which is a reaction product of a polyisocyanate composition and an active hydrogen-containing compound in the polyurethane-forming composition according to claim 5.

7. An adhesive composition comprising the polyisocyanate composition according to any one of claims 1 to 4, an active hydrogen compound, and a filler.

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