JP2018172598A - Polyisocyanate composition containing modified allophanate derived from MDI and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an MDI prepolymer containing an allophanate modified product which does not contain a metal compound and has no turbidity. An allophanate group-containing polyisocyanate composition obtained from an MDI (A), an alcohol component (B), and a catalyst (C), wherein 2,4'-MDI ( It contains 10 to 90% by weight of a-1), 10 to 90% by weight of 4,4'-MDI (a-2), 0 to 10% by weight of 2,2'-MDI (a-3), and It is solved by a polyisocyanate composition containing an allophanate modified product, wherein the catalyst (C) is at least one selected from the group consisting of a tertiary amine and a quaternary ammonium salt. [Selection diagram] None

Description

  The present invention relates to a polyisocyanate composition containing an allophanate group derived from diphenylmethane diisocyanate (hereinafter also referred to as MDI) and 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 the fields of adhesives and foams because of low viscosity, low precipitation of MDI monomer at low temperature, and easy handling. Widely applied.

  Known catalysts for generating allophanate groups from MDI and alcohol components include zinc acetylacetone, metal carboxylates such as zinc, lead, tin, copper, and cobalt, and hydrates thereof. It is a compound and is not preferred for medical and food applications.

  As a catalyst not containing a metal compound that generates an allophanate group from an isocyanate and an alcohol component, for example, N, N, N-trimethyl-N-2-hydroxypropylammonium hydroxide and N, N, N-trimethyl-N-2- Quaternary 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 It is known (see, for example, Patent Document 2), but these catalysts are not practical because a large amount of isocyanurate is produced and the prepolymer itself becomes cloudy.

JP 2011-99119 A JP 2004-250662 A

  The present invention has been made in view of the above-described background art, and an object thereof is an allophanate group-containing polyisocyanate composition derived from MDI that does not contain a metal compound and is not turbid, and a method for producing the composition. Is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor, when MDI is allophanatized with a tertiary amine catalyst, contains MDI used in a certain range of 2,4′-MDI. Thus, the inventors have found that the above problems can be solved, and have completed the present invention.

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

[1] A polyisocyanate composition containing a modified allophanate obtained from diphenylmethane diisocyanate (A), an alcohol component (B), and a catalyst (C),
In diphenylmethane diisocyanate (A),
10 to 90% by weight of 2,4′-diphenylmethane diisocyanate (a-1),
10 to 90% by weight of 4,4′-diphenylmethane diisocyanate (a-2),
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;
Not containing a metal compound in the polyisocyanate composition; and
The turbidity of the polyisocyanate composition is 3 or less,
A polyisocyanate composition comprising an allophanate-modified product characterized by the above.

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

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

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

[5] An allophanate modified product obtained by reacting diphenylmethane diisocyanate (A) with an alcohol component (B) in the presence of a catalyst (C) and stopping the reaction with a catalyst poison (D) is included. A method for producing a polyisocyanate composition, comprising:
In diphenylmethane diisocyanate (A),
10 to 90% by weight of 2,4′-diphenylmethane diisocyanate (a-1),
10 to 90% by weight of 4,4′-diphenylmethane diisocyanate (a-2),
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;
Not containing a metal compound in the polyisocyanate composition; and
The turbidity of the polyisocyanate composition is 3 or less,
The manufacturing method of the polyisocyanate composition containing the allophanate modified body characterized by these.

  INDUSTRIAL APPLICABILITY According to the present invention, a polyisocyanate composition containing an allophanate-modified product which does not contain a metal compound and has no turbidity and is industrially extremely useful can be obtained.

  The polyisocyanate composition containing the modified allophanate 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), In A), 2,4′-MDI (a-1) is 10 to 90% by weight, 4,4′-MDI (a-2) is 10 to 90% by weight, 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 tertiary amines and quaternary ammonium salts, does not contain a metal compound in the polyisocyanate composition, and is turbid. 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 “component A”) used in the present invention is 10 to 90% by weight of 2,4′-MDI (a-1), 4,4′-MDI (a -2) is 10 to 90% by weight, and 2,2′-MDI (a-3) is 0 to 10% by weight.

  Moreover, (a-1) is preferably 20 to 80% by weight, and more preferably 30 to 70%. (A-2) is preferably 20 to 80% by weight, and more preferably 30 to 70%. Since (a-3) has a slow reaction, it is preferable to have as little as possible.

  When (a-1) is below the lower limit, the prepolymer becomes turbid, and when it exceeds the upper limit, the reaction is delayed. Moreover, it is preferable that the sum total of (a-1), (a-2), and (a-3) is 100 weight%.

  The component A in the present invention preferably has a lower viscosity. However, when a certain degree of increase in viscosity is permitted, polymethylene polyphenylene polyisocyanate, which is a polymeric MDI, can also be used. In this 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 easily generated.

  As the alcohol component (B) in the present invention (hereinafter also referred to as “B component”), a compound containing a hydroxyl group having 1 to 2 number-average functional groups, that is, a monool or a diol can be used, but a phenolic hydroxyl group is contained. The compound to be used is not preferable because the generation ratio of isocyanurate groups is increased and the viscosity is increased. Also, triol or higher polyol is not preferable because of its 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-pentadecanol, 1-hexa Decanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, - eicosanol, 1-hexacosanol, 1-hepta Tricon pentanol, 1-oleyl alcohol, 2-aliphatic monoalcohols, such as octyldodecanol, and mixtures thereof. In addition to these aliphatic alcohols, for example, polyalkylene glycol monoalkyl / aryl ethers, which are oxyalkylene adducts using compounds containing phenolic hydroxyl groups such as phenol, cresol, xylenol, and nonylphenol as initiators, and mixtures thereof Is mentioned. Moreover, the monocarboxylic acid ester of polyalkylene glycol, a mixture thereof, etc. are mentioned. Furthermore, a dehydration condensate of castor oil fatty acid and monool can be used.

  Of these, aliphatic monoalcohols having 8 or more carbon atoms are preferred in order to reduce the 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. Aliphatic glycols such as 1,5-pentanediol, 2,2′-dimethyl-1,3-propanediol, 1,6-hexanediol, 2-methyl-2-butyl-1,3-propanediol, and the like Examples include polyalkylene glycols, which are oxyalkylene adducts 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 preferred in order to reduce the amount of eluted components.

  The catalyst (C) (hereinafter also referred to as “C component”) in the present invention 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-toe. Examples include rebenzylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine.

  Examples of the polymethyl polyalkylene 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.

  Of these tertiary amines, tertiary amino alcohols are preferred because they volatilize during the reaction and are less soluble when they become final resins, and are more active to reduce the amount of catalyst used as much as possible. High 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 component C, for example, tetraalkylammonium, a compound in which a hydroxyalkyltrialkylammonium and a counter ion are combined, or the like can be used.

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

  Examples of hydroxyalkyltrialkylammonium include N- (2-hydroxyethyl) -N, N, N-trimethylammonium and N- (2-hydroxypropyl) -N, N, N, -trimethylammonium.

  Examples of the counter ion combined with ammonium include chloride, bromide, hydroxide, formate, caproate, hexanoate, 2-ethylhexanoate, monoalkyl carbonate, and the like.

  Among these, as tetraalkylammonium, all are suitable, but as a counter ion to be combined, carboxylate and monoalkyl carbonate are 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 starts (hereinafter also referred to as “induction period”) becomes long. Quaternary ammonium salts are useful for shortening the production time because the reaction starts within a few minutes after addition.

  In general, the amount of component C added in the present invention is preferably 0.1 to 100 ppm based on the total amount of component A and component B, and particularly preferably 1 to 50 ppm, although it depends on the catalytic activity. If it is less than 0.1 ppm, the reaction may not proceed, and if it exceeds 100 ppm, the reaction may be fast and difficult to control.

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

(Wherein R ₁ is selected from any _one of H, an alkyl group, an alkenyl group, a cycloalkyl group, an arylalkyl group and an aryl group, wherein R ₂ and R ₃ are each independently an OH group, an alkyl group, , An alkenyl group, a cycloalkyl group, an arylalkyl group, an aryl group, an oxyalkyl group, an oxyalkenyl group, an oxycycloalkyl group, an oxyarylalkyl group, and an 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, 2- Examples include phenylacetamide, 4-methylbenzamide, 2-aminobenzamide, 3-aminobenzamide, 4-aminobenzamide, and mixtures thereof.

  Examples of the sulfonic acid amide include methylsulfonamide, butylsulfonamide, t-butylsulfonamide, phenylsulfonamide, benzylsulfonamide, o-toluylsulfonamide, p-toluylsulfonamide, 3-aminophenylsulfonamide, 4- Examples thereof include aminophenylsulfonamide and a mixture thereof.

  Specific examples of the active methylene compound represented by the above formula (1) include acetylacetone, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3,5-heptanedione, 3 , 5-heptanedione, 6-methyl-2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, methyl 3-oxopentanoate, malonic 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 immediately before the addition of the catalyst and 30 minutes after the addition of the catalyst. Is preferred.

  The higher the temperature at which allophanation of component A and component B is carried out using component C, the higher the production rate of allophanate groups and the lower the viscosity, but side reactions such as uretdioneization and carbodiimidization occur. It becomes easy. In addition, since the amount of isocyanurate groups produced increases and the viscosity increases in the reaction at low temperatures, the reaction temperature is preferably 20 ° C. or higher and 200 ° C. or lower, and the production ratio of isocyanurate groups is suppressed to 20 mol% or less. In order to make it low viscosity, 60 degreeC or more and 160 degrees C or less are preferable.

  Moreover, the polyisocyanate composition containing the modified allophanate of the present invention is characterized by not containing a metal compound. By not containing a metal compound, it can be suitably used for medical purposes.

  Moreover, since the polyisocyanate composition containing the modified allophanate of the present invention has very little turbidity, the appearance of a cured product using the composition becomes transparent and excellent, and should be suitably used for a sealing material or the like. Can do.

  Next, the manufacturing method of the polyisocyanate composition containing the allophanate modified body of this invention is demonstrated.

  Using the above-mentioned components of MDI (A), alcohol component (B), catalyst (C), and catalyst poison (D) described above for production, the following steps are obtained from the first step to the third step. Can do.

First step: A step of charging MDI (A) with a predetermined isomer ratio Second step: Add alcohol component (B) to MDI (A) prepared in the first step, and mix by stirring. Step of adding (C) and causing allophanatization reaction Third step: Stopping the allophanatization reaction with catalyst poison (D) so as to achieve the target isocyanate content.

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

  The polyisocyanate composition containing the modified allophanate thus obtained can be made into a polyurethane resin-forming composition by reacting with a polyol. Moreover, 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.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is limited to these Examples and is not interpreted. In the following, “%” means “% by weight” unless otherwise specified.

The following components were used in the examples and comparative examples.
-Iso A1; Millionate MT (manufactured by Tosoh Corporation, isomer 1.0%)
・ Iso A2: Millionate NM (Tosoh Corporation, 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 Chemical Industry Co., Ltd.)
Active methylene compound: diethyl malonate (manufactured by Tokyo Chemical Industry Co., Ltd.).

  In the examples and comparative examples, the predetermined amount refers to each composition amount described in Table 1.

<Examples 1-3>
Predetermined amounts of iso A1 and iso A2 were added to a 1 liter four-necked flask to obtain an isocyanate mixture, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly B was added with stirring, and the internal solution was heated to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. Next, a predetermined amount of active methylene compound and catalyst C were added in this order to initiate the allophanatization reaction. The reaction is followed while sampling the internal solution and measuring the NCO content, and when the NCO content is predicted to be 16.1%, a predetermined amount of catalyst poison D is added to stop the reaction, and polyphenols containing various allophanate modified products 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 isoA1 was added to a 1-liter four-necked flask to obtain an isocyanate mixture, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly B was added with stirring, and the internal solution was heated to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. Next, a predetermined amount of active methylene compound and catalyst C were added in this order to initiate the allophanatization reaction. Polyisocyanate containing allophanate-modified product by sampling the internal solution and pursuing the reaction while measuring the NCO content and stopping the reaction by adding a predetermined amount of catalyst poison D when the NCO content is predicted to be 16.1% A composition (AP-4) was obtained. AP-4 was cloudy at room temperature, and the polyisocyanate composition containing the allophanate-modified product, which was the object of the present invention, was not obtained. This indicates that when the isomer ratio before the reaction is low, the resulting composition becomes turbid. The composition and properties are shown in Table 1.

<Comparative example 2>
A predetermined amount of isoA1 was added to a 1-liter four-necked flask to obtain an isocyanate mixture, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly B was added with stirring, and the internal solution was heated to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. Next, a predetermined amount of active methylene compound and catalyst C were added in order, and the allophanatization reaction was started. The internal solution is sampled and the reaction is followed while measuring the NCO content. When the NCO content is predicted to be 10.8%, a predetermined amount of catalyst poison D is added to stop the reaction, and a predetermined amount of isoA2 is added. It mixed at 50 degreeC for 30 minutes, and obtained the polyisocyanate composition (AP-5) containing an allophanate modified body. AP-5 was turbid at room temperature, and the polyisocyanate composition containing the allophanate-modified product, which was the object of the present invention, was not obtained. This indicates that turbidity is not eliminated even if the isomer ratio is controlled after the reaction. The composition and properties are shown in Table 1.

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

<Polyol Preparation Example 1>
750 g of castor oil (trade name castor oil LAV, manufactured by Ito Oil Co., Ltd.) and N, N, N ′, N′-tetrakis (isopropanol) ethylenediamine (trade name EDP-300, manufactured by ADEKA) in a 1-liter four-necked flask 250g was added and it stirred at 50 degreeC under nitrogen stream for 30 minutes, and obtained polyol BP-1.

<Examples 4 to 6>
A cured product was obtained from the prepolymers (AP1 to AP3) obtained in Examples 1 to 3 and BP-1 obtained in Polyol Preparation Example 1 according to the formulation shown in Table 2. Table 2 shows the physical properties of the cured product.

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

<Pot life>
Each temperature 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 polycup. Mix for 30 seconds with a spatula and transfer 30 g into a 30 ml polycup. Viscosity is measured with a B-type viscometer No. 4 rotor, and the point at which 50,000 mPa · s is reached is defined as the pot life.

<Hardness (10-second value)>
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 polycup. Mix for 30 seconds with a spatula and vacuum degas for 60 seconds at 50 mmHg. After defoaming, 80 g is transferred to a 300 ml polycup and cured at 45 ° C. for 48 hours. The cured product is taken out from the polycup, left in an environment at 25 ° C. for 4 hours, and the hardness is measured with a durometer D hardness meter. The reading value 10 seconds after pressing the hardness meter is taken as the hardness (10-second value).

<Methanol extraction rate>
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 polycup. Mix for 30 seconds with a spatula and vacuum degas for 60 seconds at 50 mmHg. After defoaming, the mixed solution is developed on a release paper to form a sheet having a thickness of 1 mm. After curing at 45 ° C. for 48 hours, cut into 10 mm squares. Put 20 g of the cut sample and 200 g of methanol in a 500 ml sample bottle, seal tightly, and shake at 25 ° C. for 24 hours. Filter after shaking and collect the extract in a 300 ml eggplant flask and evaporate to dryness. The methanol extraction rate is obtained from the following formula.

  Methanol extraction rate (%) = {weight of eggplant flask after evaporation to dryness (g) −empty weight of eggplant flask (g)} / sample weight (g) × 100.

  According to Examples 4-6, it turns out that the hardened | cured material with a favorable physical property can be obtained by using the polyisocyanate composition containing the allophanate modified body of this invention.

Claims (5)

A polyisocyanate composition comprising a modified allophanate obtained from diphenylmethane diisocyanate (A), an alcohol component (B), and a catalyst (C),
In diphenylmethane diisocyanate (A),
10 to 90% by weight of 2,4′-diphenylmethane diisocyanate (a-1),
10 to 90% by weight of 4,4′-diphenylmethane diisocyanate (a-2),
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,
Not containing a metal compound in the polyisocyanate composition; and
The turbidity of the polyisocyanate composition is 3 or less,
A polyisocyanate composition comprising an allophanate-modified product characterized by the above.   A polyurethane resin-forming composition obtained from a polyisocyanate composition comprising the allophanate-modified product according to claim 1 and a polyol.   A sealing material comprising a cured product of the polyurethane resin-forming composition according to claim 2.   A membrane module sealed with the sealing material according to claim 3. Polyisocyanate composition comprising an allophanate modified product obtained by reacting diphenylmethane diisocyanate (A) with alcohol component (B) in the presence of catalyst (C) and terminating the reaction with catalyst poison (D) A method for manufacturing a product,
In diphenylmethane diisocyanate (A),
10 to 90% by weight of 2,4′-diphenylmethane diisocyanate (a-1),
10 to 90% by weight of 4,4′-diphenylmethane diisocyanate (a-2),
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;
Not containing a metal compound in the polyisocyanate composition; and
The turbidity of the polyisocyanate composition is 1 or less,
The manufacturing method of the polyisocyanate composition containing the allophanate modified body characterized by these.