JP6946699B2 - Polyisocyanate composition containing an allophanate modified product derived from MDI and a method for producing the same. - Google Patents

Description

The present invention relates to a polyisocyanate composition containing diphenylmethane diisocyanate (hereinafter, also referred to as MDI) and an allophanate group derived from an alcohol component, and a method for producing the composition.

A polyisocyanate prepolymer containing an allophanate group derived from MDI and an alcohol component is useful in fields such as adhesives and foams because it has a low viscosity, less precipitation of MDI monomers at low temperatures, and is easy to handle. Widely applied.

As a catalyst for generating an allophanate group from MDI and an alcohol component, zinc acetylacetone, metal carboxylates such as zinc, lead, tin, copper and cobalt, and hydrates thereof are known, but all of them are metals. It is a compound and is not preferable for medical and food applications.

Examples of catalysts free of metal compounds that generate allophanate groups from isocyanates and alcohol components include N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide and N, N, N-trimethyl-N-2-. Tertiary ammonium salts such as hydroxypropylammonium-2-ethylhexanoate (see, for example, Patent Document 1) and tertiary amines containing phenolic hydroxyl groups such as 2,4,6-tris (dimethylaminomethyl) phenol Although it is known (see, for example, Patent Document 2), these catalysts are not practical because a large amount of isocyanurate is produced and the prepolymer itself becomes turbid.

Japanese Unexamined Patent Publication No. 2011-99119 Japanese Unexamined Patent Publication No. 2004-250662

The present invention has been made in view of the background art described above, and an object of the present invention is an MDI-derived allophanate group-containing polyisocyanate composition containing no metal compound and having no turbidity, and a method for producing the composition. Is to provide.

As a result of diligent studies to solve the above problems, the present inventor uses a certain range of 2,4'-MDI when alofanating MDI with a tertiary amine catalyst. It was found that the above-mentioned problems could be solved, and the present invention was completed.

That is, the present invention includes the following embodiments [1] to [3].

[1] A polyisocyanate composition containing an allophanate modified product obtained from a diphenylmethane diisocyanate (A), an alcohol component (B), and a catalyst (C).
In diphenylmethane diisocyanate (A),
10,90% by weight of 2,4'-diphenylmethane diisocyanate (a-1),
4,4'-Diphenylmethane diisocyanate (a-2) in an amount of 10 to 90% by weight,
0 to 10% by weight of 2,2'-diphenylmethane diisocyanate (a-3)
To include,
The catalyst (C) is at least one selected from the group consisting of tertiary amines and quaternary ammonium salts.
The polyisocyanate composition does not contain a metal compound, and
The turbidity of the polyisocyanate composition is 3 or less.
A polyisocyanate composition comprising an allophanate modified product.

[2] A polyurethane resin-forming composition obtained from a polyisocyanate composition containing the allophanate modified product according to the above [1] and a polyol.

[3] A sealing material made of a cured product of the polyurethane resin-forming composition according to the above [2].

[4] A membrane module sealed with the sealing material according to the above [3].

[5] A modified allophanate obtained by reacting a diphenylmethane diisocyanate (A) with an alcohol component (B) in the presence of a catalyst (C) and terminating the reaction with a catalyst poison (D). A method for producing a polyisocyanate composition.
In diphenylmethane diisocyanate (A),
10,90% by weight of 2,4'-diphenylmethane diisocyanate (a-1),
4,4'-Diphenylmethane diisocyanate (a-2) in an amount of 10 to 90% by weight,
2,2'-Diphenylmethane diisocyanate (a-3) in an amount of 0 to 10% by weight,
To include,
The catalyst (C) is at least one selected from the group consisting of tertiary amines and quaternary ammonium salts.
The polyisocyanate composition does not contain a metal compound, and
The turbidity of the polyisocyanate composition is 3 or less.
A method for producing a polyisocyanate composition containing an allophanate modified product.

INDUSTRIAL APPLICABILITY According to the present invention, a polyisocyanate composition containing an allophanate modified product, which is free from metal compounds and is extremely useful in industry, can be obtained.

The polyisocyanate composition containing an allophanate modified product of the present invention is a polyisocyanate composition containing an allophanate modified product obtained from MDI (A), an alcohol component (B), and a catalyst (C), and is an MDI (. In A), 2,4'-MDI (a-1) is 10 to 90% by weight, 4,4'-MDI (a-2) is 10 to 90% by weight, and 2,2'-MDI (a-). 3) is contained in an amount of 0 to 10% by weight, and the catalyst (C) is at least one selected from the group consisting of a tertiary amine and a quaternary ammonium salt, and the polyisocyanate composition does not contain a metal compound and is turbid. It is a polyisocyanate composition containing an allophanate modified product having a degree of 3 or less.

The isomer ratio of MDI (A) (hereinafter, also referred to as "A component") used in the present invention is 10 to 90% by weight for 2,4'-MDI (a-1) and 4,4'-MDI (a). -2) is 10 to 90% by weight, and 2,2'-MDI (a-3) is 0 to 10% by weight.

Further, (a-1) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight. (A-2) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight. Since the reaction of (a-3) is slow, it is preferable that the reaction is as small as possible.

If (a-1) is below the lower limit, the prepolymer becomes turbid, and if it exceeds the upper limit, the reaction is slowed down. Further, it is preferable that the total of (a-1), (a-2) and (a-3) is 100% by weight.

The component A in the present invention preferably has a lower viscosity, but if a certain degree of high viscosity is allowed, a polymeric MDI, polymethylene polyphenylene polyisocyanate, can also be used. In that case, the content of polymethylene polyphenylene polyisocyanate is preferably 0 to 30% by weight in the isocyanate component used. If it exceeds 30% by weight, the viscosity becomes too high, and insoluble matter is likely to be produced.

As the alcohol component (B) (hereinafter, also referred to as “B component”) in the present invention, a compound containing a hydroxyl group having one or two number average functional groups, that is, monool or diol can be used, but it contains a phenolic hydroxyl group. This compound is not preferable because the production ratio of isocyanurate groups is high and the viscosity is high. Further, a polyol having a triol or higher viscosity is also not preferable because it has a high viscosity.

Examples of the B component monool that can be used in the present invention include methanol, ethanol, propanol, 1- and 2-butanol, 1-pentanol, 1-hexanol, 2-methyl-1-pentanol, 4-. Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl- 1-pentanol, 1-nonanol, 2,6-dimethyl-4-heptanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentanol, 1-hexa Aliphatic products such as decanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol, 1-hexacosanol, 1-heptatricontanol, 1-oleyl alcohol, 2-octyldodecanol, etc. Alcohol and mixtures thereof and the like can be mentioned. Further, in addition to these aliphatic alcohols, polyalkylene glycol monoalkyl / aryl ether which is an oxyalkylene adduct using a compound containing a phenolic hydroxyl group such as phenol, cresol, xylenol, nonylphenol as an initiator, and a mixture thereof and the like. Can be mentioned. Examples thereof include monocarboxylic acid esters of polyalkylene glycols and mixtures thereof. Furthermore, a dehydrated condensate of castor oil fatty acid and monool can also be used.

Of these, an aliphatic monoalcohol having 8 or more carbon atoms is preferable in order to reduce the number of eluted components.

Examples of the B component diol that can be used in the present invention include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, and 2-methyl-1,3-propanediol. , 1,5-Pentanediol, 2,2'-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-2-butyl-1,3-propanediol and other aliphatic glycols and these. Examples thereof include polyalkylene glycol which is an oxyalkylene adduct using glycol as an initiator, bifunctional castor oil derivatives such as partially dehydrated castor oil and acylated castor oil, esterified products of diol and castor oil fatty acid, and mixtures thereof. ..

Of these, bifunctional castor oil derivatives such as aliphatic glycols, partially dehydrated castor oil, and acylated castor oil are preferable in order to reduce the amount of eluted components.

The catalyst (C) in the present invention (hereinafter, also referred to as “C component”) is at least one selected from the group consisting of tertiary amines and quaternary ammonium salts.

As the tertiary amine in the present invention, for example, trialkylamine, polymethylpolyalkylenepolyamine, tertiary aminoalcohol and the like can be used.

Examples of the trialkylamine include N, N, N-benzyldimethylamine, N, N, N-dibenzylmethylamine, N, N, N-cyclohexyldimethylamine, N-methylmorpholine, N, N, N-to. Examples thereof include rebenzylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine.

Examples of the polymethylpolyalkylene polyamine include N, N, N', N'-tetramethylethylenediamine, N, N, N', N', N "-pentamethyldiethylenetriamine and the like.

Examples of the tertiary amino alcohol include 2- (dimethylamino) ethanol, 3- (dimethylamino) propanol, 2- (dimethylamino) -1-methylpropanol, 2- {2- (dimethylamino) ethoxy} ethanol, 2 − {2- (Diethylamino) ethoxy} ethanol, 2-[{2- (dimethylamino) ethyl} methylamino] ethanol and the like can be mentioned.

Of these tertiary amines, tertiary amino alcohol is preferable because it volatilizes during the reaction and elution itself is small when it becomes the final resin, and it is more active in order to reduce the amount of catalyst used as much as possible. Higher 2- {2- (dimethylamino) ethoxy} ethanol, 2- {2- (diethylamino) ethoxy} ethanol, 2-[{2- (dimethylamino) ethyl} methylamino] ethanol are more preferred.

As the quaternary ammonium salt in the C component, for example, tetraalkylammonium, a compound in which hydroxyalkyltrialkylammonium and a counterion are combined, and the like can be used.

Examples of tetraalkylammonium include N, N, N, N, -tetramethylammonium, N, N, N-trimethyl-N-octylammonium and the like.

Examples of the hydroxyalkyl trialkylammonium include N- (2-hydroxyethyl) -N, N, N-trimethylammonium, N- (2-hydroxypropyl) -N, N, N, -trimethylammonium and the like.

Examples of the counterion to be combined with the above ammonium include chloride, bromide, hydroxide, formate, caproate, hexanoate, 2-ethylhexanoate, monoalkyl carbonate and the like.

Of these, all of them are suitable as tetraalkylammonium, but as the counterion to be combined, carboxylate or monoalkyl carbonate is preferable from the viewpoint of compatibility with MDI.

When the reaction is carried out only with a tertiary amine, the combined use of a quaternary ammonium salt is effective when the time until the reaction is started (hereinafter, also referred to as “induction period”) becomes long. Since the reaction of the quaternary ammonium salt starts within a few minutes after the addition, it is useful for shortening the production time.

The amount of the C component added in the present invention is generally preferably 0.1 to 100 ppm with respect to the total amount of the A component and the B component, and is particularly preferably 1 to 50 ppm, although it depends on the catalytic activity thereof. If it is less than 0.1 ppm, the reaction may not proceed, and if it is added in excess of 100 ppm, the reaction may be rapid and control may be difficult.

In the allophanation with a tertiary amine or a quaternary ammonium salt in the present invention, when the reaction is rapid and difficult to control, the group consisting of the carboxylic acid amide and the sulfonic acid amide and the active methylene compound represented by the following formula (1) is selected. It is effective to add at least one selected.

(R ₁ in the formula is selected from any of H, alkyl group, alkenyl group, cycloalkyl group, arylalkyl group and aryl group, and R _{2 and R 3} in the formula are independently OH group and alkyl group, respectively. , Alkenyl group, cycloalkyl group, arylalkyl group, aryl group, oxyalkyl group, oxyalkenyl group, oxycycloalkyl group, oxyarylalkyl group and oxyaryl group).

Examples of the carboxylic acid amide include formamide, acetamide, propionic acid amide, butanoic acid amide, isobutanoic acid amide, hexanoic acid amide, octanoic acid amide, 2-ethylhexanoic acid amide, oleic acid amide, stearic acid amide, benzamide and 2-. Examples thereof include phenylacetamide, 4-methylbenzamide, 2-aminobenzamide, 3-aminobenzamide, 4-aminobenzamide and mixtures thereof.

Examples of the sulfonic acid amide include methyl sulfonamide, butyl sulfonamide, t-butyl sulfonamide, phenyl sulfonamide, benzyl sulfonamide, o-toluyl sulfonamide, p-toluyl sulfonamide, 3-aminophenyl sulfonamide, 4- Examples thereof include aminophenyl sulfonamide and mixtures thereof.

Specific examples of the active methylene compound represented by the above formula (1) include acetylacetone, 3-methyl-2,4-pentandione, 3-ethyl-2,4-pentandione, 3,5-heptandione, 3 , 5-Heptandione, 6-Methyl-2,4-Heptandione, Methyl acetoacetate, Ethyl acetoacetate, Methyl 3-oxopentate, Maronic acid, Dimethyl malonate, Diethyl malonate and mixtures thereof. ..

Further, at least one selected from the group consisting of the above-mentioned carboxylic acid amide and sulfonic acid amide and the active methylene compound represented by the above formula (1) should be added from immediately before the addition of the catalyst to 30 minutes after the addition of the catalyst. Is preferable.

The higher the temperature at which the A component and the B component are allophanated using the C component, the higher the rate of allophanate group formation and the lower the viscosity, but side reactions such as uretdione formation and carbodiimide formation occur. It will be easier. Further, since the amount of isocyanurate groups produced increases and the viscosity increases in the reaction at a low temperature, the reaction temperature is preferably 20 ° C. or higher and 200 ° C. or lower, and the isocyanurate group formation ratio is suppressed to 20 mol% or less. In order to reduce the viscosity, it is preferably 60 ° C. or higher and 160 ° C. or lower.

Further, the polyisocyanate composition containing the modified allophanate of the present invention is characterized by not containing a metal compound. Since it does not contain a metal compound, it can be suitably used for medical applications and the like.

Further, since the polyisocyanate composition containing the allophanate modified product of the present invention has very little turbidity, the appearance of the cured product using the composition is transparent and excellent, and it is preferably used as a sealing material or the like. Can be done.

Next, a method for producing a polyisocyanate composition containing the modified allophanate of the present invention will be described.

For production, each component of MDI (A), alcohol component (B), catalyst (C), and catalyst poison (D) described above is used, and the mixture is obtained by going through the following first to third steps. Can be done.

First step: Step of charging MDI (A) having a predetermined isomer ratio Second step: Add alcohol component (B) to MDI (A) prepared in the first step, stir and mix, and after becoming uniform, catalyst Step of adding (C) and causing an allophanation reaction Third step: A step of stopping the allophanation reaction with a catalytic poison (D) so as to have a target isocyanate content.

As the catalytic poison (D) (hereinafter, also referred to as “D component”) used in the present invention, an acidic substance is suitable, for example, anhydrous hydrogen chloride, sulfuric acid, phosphoric acid, monoalkyl sulfate ester, alkyl sulfonic acid, alkyl benzene sulfone. Also included are acids, mono or dialkyl phosphoric acid esters, benzoyl chloride and Lewis acids. The amount to be added is preferably equal to or more than the number of moles of the tertiary amine or quaternary ammonium salt of the C component as a catalyst, and is preferably 1.0 to 1.5 times the molar equivalent.

The polyisocyanate composition containing the allophanate modified product thus obtained can be made into a polyurethane resin-forming composition by reacting with the polyol. Further, a sealing material can be obtained by curing the forming composition, and the obtained sealing material can be suitably used as a member of a membrane module.

Hereinafter, the present invention will be described based on examples, but the present invention is not construed as being limited to these examples. In the following, "%" means "% by weight" unless otherwise specified.

The following components were used in Examples and Comparative Examples.
-Iso A1; Millionate MT (manufactured by Tosoh, Isomer 1.0%)
-Iso A2; Millionate NM (manufactured by Tosoh, Isomer 55.0%)
-Poly B; Tridecanol (manufactured by KH Neochem)
-Catalyst C; 2-[{2- (dimethylamino) ethyl} methylamino] ethanol (trade name RX-5, 1% tridecanol solution manufactured by Tosoh Corporation)
-Catalyst poison D; Benzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.)
-Active methylene compound; diethyl malonate (manufactured by Tokyo Kasei Co., Ltd.).

In addition, in Examples and Comparative Examples, the predetermined amount means each composition amount shown in Table 1.

<Examples 1 to 3>
A predetermined amount of Iso A1 and Iso A2 was added to a 1-liter four-necked flask to prepare an isocyanate mixture, and the temperature was adjusted to 50 ° C. while stirring under a nitrogen stream. Next, a predetermined amount of Poly B was added with stirring, and after the heat generation of the urethanization reaction had subsided, the internal liquid was heated to 110 ° C. Next, a predetermined amount of the active methylene compound and the catalyst C were added in this order, and the allophanate reaction was started. The reaction was followed while measuring the NCO content by sampling the internal solution, and when the NCO content was predicted to reach 16.1%, a predetermined amount of catalytic poison D was added to stop the reaction, and poly containing various allophanate modified products was added. An isocyanate composition (AP-1 to 3) was obtained. AP-1 to 3 were pale yellow transparent liquids. The composition and properties are shown in Table 1.

<Comparative example 1>
A predetermined amount of Iso A1 was added to a 1-liter four-necked flask to prepare an isocyanate mixture, and the temperature was adjusted to 50 ° C. while stirring under a nitrogen stream. Next, a predetermined amount of Poly B was added with stirring, and after the heat generation of the urethanization reaction had subsided, the internal liquid was heated to 110 ° C. Next, a predetermined amount of the active methylene compound and the catalyst C were added in this order, and the allophanate reaction was started. The reaction was followed while measuring the NCO content by sampling the internal solution, and when the NCO content was predicted to reach 16.1%, a predetermined amount of catalytic poison D was added to stop the reaction, and the polyisocyanate containing the allophanate modified product was added. The composition (AP-4) was obtained. AP-4 was turbid at room temperature, and the polyisocyanate composition containing the allophanate modified product, which was the object of the present invention, could not be obtained. This indicates that the resulting composition becomes turbid when the isomer ratio before the reaction is low. The composition and properties are shown in Table 1.

<Comparative example 2>
A predetermined amount of Iso A1 was added to a 1-liter four-necked flask to prepare an isocyanate mixture, and the temperature was adjusted to 50 ° C. while stirring under a nitrogen stream. Next, a predetermined amount of Poly B was added with stirring, and after the heat generation of the urethanization reaction had subsided, the internal liquid was heated to 110 ° C. Next, a predetermined amount of the active methylene compound and the catalyst C were added in this order, and the allophanate reaction was started. The reaction is followed while sampling the internal solution and measuring the NCO content. When the NCO content is predicted to reach 10.8%, a predetermined amount of catalytic poison D is added to stop the reaction, and a predetermined amount of isocyanate A2 is further added. Mixing at 50 ° C. for 30 minutes gave a polyisocyanate composition (AP-5) containing an allophanate modified product. AP-5 was turbid at room temperature, and the polyisocyanate composition containing the allophanate modified product, which was the object of the present invention, could not be obtained. This indicates that controlling the isomer ratio after the reaction does not eliminate the turbidity. The composition and properties are shown in Table 1.

<Appearance evaluation>
The appearance was evaluated using the method of kaolin turbidity (visual method) shown in JIS K 0101. When the turbidity was 3 or less, it was considered good.

<Polycarbonate preparation example 1>
750 g of castor oil (manufactured by Itoh Oil Chemicals, trade name castor oil LAV) and N, N, N', N'-tetrakis (isopropanol) ethylenediamine (manufactured by ADEKA, trade name EDP-300) in a 1-liter four-necked flask. 250 g was added, and the mixture was stirred at 50 ° C. for 30 minutes under a nitrogen stream to obtain polyol BP-1.

<Examples 4 to 6>
A cured product was obtained from the prepolymers (AP1 to 3) obtained in Examples 1 to 3 and the BP-1 obtained in polyol preparation example 1 by the formulation shown in Table 2. Table 2 shows the physical characteristics of the cured product.

The measurement method of each physical property value is as follows.

<Pot life>
The temperature of each of the prepolymer and the polyol is adjusted to 45 ° C., and 30 g of the prepolymer and then 20 g of the polyol are quickly weighed in a 200 ml poly cup. Mix with a spatula for 30 seconds and transfer 30 g to a 30 ml plastic cup. The viscosity is measured with a B-type viscometer No. 4 rotor, and the pot life is defined as the time when 50,000 mPa · s is reached.

<Hardness (10 seconds value)>
The temperature of each of the prepolymer and the polyol is adjusted to 45 ° C., and 60 g of the prepolymer and then 40 g of the polyol are quickly weighed in a 500 ml poly cup. Mix with a spatula for 30 seconds and vacuum defoam at 50 mmHg for 60 seconds. After defoaming, transfer 80 g to a 300 ml plastic cup and cure at 45 ° C. for 48 hours. The cured product is taken out from the polycup, left to stand in an environment of 25 ° C. for 4 hours, and the hardness is measured with a Durometer D hardness tester. The reading value 10 seconds after pressing the hardness tester is defined as the hardness (10 second value).

<Methanol extraction rate>
The temperature of each of the prepolymer and the polyol is adjusted to 45 ° C., and 60 g of the prepolymer and then 40 g of the polyol are quickly weighed in a 500 ml poly cup. Mix with a spatula for 30 seconds and vacuum defoam at 50 mmHg for 60 seconds. After defoaming, the mixed solution is developed on a paper pattern to form a sheet having a thickness of 1 mm. After curing at 45 ° C. for 48 hours, cut into 10 mm squares. 20 g of the cut sample and 200 g of methanol are placed in a 500 ml sample bottle, sealed tightly, and shaken at 25 ° C. for 24 hours. After shaking, the mixture is filtered, and the extract is collected in a 300 ml eggplant flask and evaporated to dryness. The methanol extraction rate is calculated by the following formula.

Methanol extraction rate (%) = {Eggplant flask weight (g) after evaporation to dryness-Eggplant flask empty weight (g)} / Sample weight (g) x 100.

According to Examples 4 to 6, it can be seen that a cured product having good physical properties can be obtained by using the polyisocyanate composition containing the modified allophanate of the present invention.

Claims (8)

A polyisocyanate composition used in a polyurethane resin-forming composition for a sealing material used in a membrane module.
A polyisocyanate composition containing an allophanate modified product obtained from a diphenylmethane diisocyanate (A), an alcohol component (B), and a catalyst (C).
In diphenylmethane diisocyanate (A),
10,90% by weight of 2,4'-diphenylmethane diisocyanate (a-1),
4,4'-Diphenylmethane diisocyanate (a-2) in an amount of 10 to 90% by weight,
0 to 10% by weight of 2,2'-diphenylmethane diisocyanate (a-3)
Including
The catalyst (C) is at least one selected from the group consisting of tertiary amines and quaternary ammonium salts.
The polyisocyanate composition does not contain a metal compound, and
Ri Der turbidity of 3 or less of the polyisocyanate composition,
A polyisocyanate composition containing an allophanate modified product, wherein the polyisocyanate composition is a pale yellow transparent liquid. The polyisocyanate composition according to claim 1, wherein the proportion of isocyanurate groups is 20 mol% or less. The polyisocyanate composition according to claim 1 or 2, wherein the membrane sealing material is used for a membrane module for medical use. A polyurethane resin-forming composition obtained from a polyisocyanate composition containing the allophanate modified product according to any one of claims 1 to 3 and a polyol. A sealing material made of a cured product of the polyurethane resin-forming composition according to claim 4. A membrane module sealed by the sealing material according to claim 5. A method for producing a polyisocyanate composition used in a polyurethane resin-forming composition for a sealing material used in a membrane module.
A polyisocyanate composition containing a modified allophanate is prepared by reacting a diphenylmethane diisocyanate (A) with an alcohol component (B) in the presence of a catalyst (C) and terminating the reaction with a catalyst poison (D). Be prepared to get
In diphenylmethane diisocyanate (A),
10,90% by weight of 2,4'-diphenylmethane diisocyanate (a-1),
4,4'-Diphenylmethane diisocyanate (a-2) in an amount of 10 to 90% by weight,
2,2'-Diphenylmethane diisocyanate (a-3) in an amount of 0 to 10% by weight,
Including
The catalyst (C) is at least one selected from the group consisting of tertiary amines and quaternary ammonium salts.
The polyisocyanate composition does not contain a metal compound, and
Turbidity of the polyisocyanate composition Ri der 1 or less,
A method for producing a polyisocyanate composition containing an allophanate modified product, wherein the polyisocyanate composition is a pale yellow transparent liquid. The method for producing a polyisocyanate composition according to claim 7 , wherein the reaction temperature of the allophanate reaction is 20 ° C. or higher and 200 ° C. or lower.