WO2017111043A1 - Polyurethane resin-forming composition, module membrane seal material using a hollow-shaped or flat membrane-shaped fiber separation membrane using said forming composition, and allophanate group-containing polyisocyanate composition derived from mdi and production method therefor - Google Patents

Abstract

[Problem] To provide a polyurethane resin-forming composition that is well-balanced between reactivity and low viscosity, is able to impart low-temperature storage stability, and fixes a hollow-shaped or flat membrane-shaped fiber separation membrane, and to provide an MDI prepolymer not containing a metal compound and having a high allophanate group content, and a production method in which a reaction can be easily controlled in the production thereof. [Solution] The problem is solved by using a polyurethane resin-forming composition containing a specific isocyanate group-containing compound in an isocyanate component, and by reacting an MDI in the presence of at least one selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound, without containing a metal catalyst, when the MDI is allophanatized with a tertiary amine catalyst.

Description

Polyurethane resin-forming composition, membrane sealing material for module using hollow or flat membrane-like fiber separation membrane using the forming composition, allophanate group-containing polyisocyanate composition derived from MDI, and production thereof Method

The present invention relates to a polyurethane resin forming composition, a membrane sealing material for a module using a hollow or flat membrane separation membrane using the forming composition, diphenylmethane diisocyanate (hereinafter referred to as MDI) and an alcohol component. The present invention relates to a polyisocyanate composition containing derivatized allophanate groups and a method for producing the same.

Modules using hollow fibers or flat membranes as separation membranes are widely used in industrial fields such as water treatment and medical fields such as blood treatment. In particular, the demand for water purifiers, artificial kidneys, artificial lungs and the like is extremely increasing. In general, polyurethane membranes with excellent flexibility, adhesiveness, and chemical resistance at room temperature are used as membrane sealing materials for bonding and fixing the ends of converged modules using hollow or flat membrane-like fiber separation membranes. It is widely known to use.

As such a polyurethane resin, for example, as an isocyanate component, a polyurethane resin obtained by curing an isocyanate group-terminated prepolymer obtained from liquefied diphenylmethane diisocyanate and castor oil or castor oil derivative polyol with a polyol has been proposed. (For example, refer to Patent Document 1).

However, in the case of using a hollow fiber separation membrane as a separation membrane for the polyurethane resin used for such applications, in order to improve the productivity of the membrane module, an isocyanate group-terminated prepolymer or polyol is used. The demand for lower viscosity is increasing.

Furthermore, the polyurethane resin used in the conventional membrane sealing material for membrane modules has a problem that it is difficult to balance reactivity, low viscosity, and low temperature storage stability, and a solution is desired.

In addition, polyisocyanate group-terminated prepolymers containing allophanate groups derived from MDI and alcohol components have low viscosity, low precipitation of MDI monomers at low temperatures, and are easy to handle. Is useful and 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.

Catalysts that do not contain metal compounds that form allophanate groups from isocyanate and alcohol components include, 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 are also known (see, for example, Patent Document 2), but these quaternary ammonium salts are useful for aliphatic and alicyclic isocyanates. For aromatic isocyanates such as MDI, the reaction is rapid and insoluble crystals tend to precipitate, and the catalyst is easily deactivated, making it difficult to put it to practical use.

As a catalyst for generating an isocyanurate group from an isocyanate group, a tertiary amine containing a phenolic hydroxyl group such as 2,4,6-tris (dimethylaminomethyl) phenol is known (see, for example, Patent Document 3). Can produce allophanate groups in the presence of an alcohol component, but because the amount of isocyanurate groups produced is large and the compatibility with polyols is poor, the range that can be used as urethane resins for adhesives and foams is limited. It becomes.

Japanese Unexamined Patent Publication No. 53-98398 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.

The first object of the present invention is to form a polyurethane resin-forming composition for fixing a hollow or flat membrane-like fiber separation membrane capable of providing a balance between reactivity and viscosity reduction and imparting low-temperature storage stability. Is to provide.

The second object of the present invention is to provide an MDI prepolymer containing no metal compound and having a high allophanate group content and a production method capable of easily controlling the reaction in the production.

As a result of intensive studies in order to solve the above-described series of problems, the present inventors have found that in the isocyanate component (A), an isocyanate group-containing compound (a1) represented by the following general formula (1) (hereinafter referred to as (a1) It was found that the above first problem can be solved by using a polyurethane resin-forming composition containing)), which is also referred to as a structure, and a metal catalyst is included when allophanating MDI with a tertiary amine catalyst. A polyisocyanate composition containing an allophanate group reacted in the presence of at least one selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by the following general formula (2): The present inventors have found that the second problem can be solved by the manufacturing method and have completed the present invention.

(Wherein R ₁ represents a residue other than the active hydrogen group of the active hydrogen group-containing compound (b1), X represents an oxygen or sulfur atom, and R represents an unreacted isocyanate group of the isocyanate group-containing compound (a2). M represents an integer of 1 or 2. When m is 1, n represents an integer of 1 to 30, and when m is 2, n represents an integer of 1 to 15. )

(Wherein R ₂ 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 ₃ and R ₄ 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)

That is, the present invention includes the following embodiments (1) to (16).

(1) A polyurethane resin-forming composition containing an isocyanate component (A) and a polyol component (B), and an isocyanate group-containing compound represented by the following general formula (1) in the isocyanate component (A) ( An allophanate group-containing polyurethane resin-forming composition containing a1).

(Wherein R ₁ represents a residue other than the active hydrogen group of the active hydrogen group-containing compound (b1), X represents an oxygen or sulfur atom, and R represents an unreacted isocyanate group of the isocyanate group-containing compound (a2). M represents an integer of 1 or 2. When m is 1, n represents an integer of 1 to 30, and when m is 2, n represents an integer of 1 to 15. )

(2) The allophanate group-containing polyurethane resin-forming composition as described in (1) above, wherein the isocyanate component (A) is liquid at normal temperature.

(3) The content of the isocyanate group-containing compound (a1) represented by the general formula (1) in the isocyanate component (A) is 20 to 90 peak area% in gel permeation chromatography measurement. The allophanate group-containing polyurethane resin-forming composition as described in (1) or (2) above.

(4) The isocyanate group-containing compound (a1) is an allophanate group-containing polyisocyanate composition which is a reaction product of diphenylmethane diisocyanate and an alcohol, and the molar ratio of allophanate groups to isocyanurate groups is 80:20 to 100: 0, comprising at least one selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by formula (2), and a tertiary amine catalyst as an allophanatization reaction aid, and a metal catalyst The allophanate group-containing polyurethane resin-forming composition according to any one of (1) to (3) above, wherein the allophanate group-containing polyisocyanate composition does not contain any of the above.

(Wherein R ₂ 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 ₃ and R ₄ 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)

(5) The allophanate group-containing polyurethane resin-forming property according to any one of (1) to (4) above, wherein the isocyanate group-containing compound (a2) is an aromatic isocyanate having two or more isocyanate groups. Composition.

(6) The allophanate group-containing polyurethane resin-forming composition as described in any one of (1) to (5) above, wherein the isocyanate group-containing compound (a2) is diphenylmethane diisocyanate.

(7) The allophanate group-containing polyurethane resin according to any one of (1) to (6) above, wherein the active hydrogen group-containing compound (b1) is a monool or diol having 1 to 70 carbon atoms Formable composition.

(8) Use of the allophanate group-containing polyurethane resin-forming composition according to any one of (1) to (7) as a sealing material for a membrane module.

(9) A method for producing an allophanate group-containing polyurethane resin comprising reacting the isocyanate component (A) according to any one of (1) to (7) and a polyol component (B).

(10) A sealing material comprising a cured product of the allophanate group-containing polyurethane resin-forming composition according to any one of (1) to (7) above.

(11) A membrane module that is sealed with the sealing material described in (10) above.

(12) An allophanate group-containing polyisocyanate composition, which is a reaction product of diphenylmethane diisocyanate and alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0, and the carboxylic acid amide, sulfone It contains at least one selected from the group consisting of an acid amide and an active methylene compound represented by the general formula (2), and a tertiary amine catalyst as an allophanatization reaction aid, and does not contain a metal catalyst. An allophanate group-containing polyisocyanate composition.

(Wherein R ₂ 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 ₃ and R ₄ 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)

(13) In the presence of (E) diphenylmethane diisocyanate and (F) at least one alcohol component selected from the group consisting of (G) a carboxylic acid amide and a sulfonic acid amide and an active methylene compound represented by formula (2) (H) A method for producing an allophanate group-containing polyisocyanate composition, characterized in that allophanatization is carried out with a tertiary amine as a catalyst, and (J) the reaction is stopped by a catalyst poison.

(Wherein R ₂ 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 ₃ and R ₄ 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)

(14) The method for producing an allophanate group-containing polyisocyanate composition according to the above (13), wherein a tertiary amine and a quaternary ammonium salt are used in combination as the catalyst (F) to form an allophanate.

(15) The method for producing an allophanate group-containing polyisocyanate composition according to (13) or (14) above, wherein the catalyst does not contain a metal catalyst as the (F) catalyst.

(16) The allophanate group-containing polyisocyanate composition according to any one of (13) to (15) above, wherein the molar ratio of allophanate groups to isocyanurate groups is 80:20 to 100: 0. Production method.

In addition, the normal temperature in the present invention means −5 ° C. to 45 ° C.

In the present invention, means for solving the first problem is referred to as Embodiment 1, and means for solving the second problem is referred to as Embodiment 2.

As a first effect, the use of the polyurethane resin-forming composition of the present invention makes it possible in particular to improve reactivity, viscosity reduction, and low-temperature storage stability. In addition, the polyurethane resin-forming composition according to the present invention is liquid at room temperature (for example, 25 ° C.). This excellent effect is very suitable for use as a binding material for medical and industrial fluid separation devices (ie, sealing materials for membrane modules) using the desired hollow fiber separation membrane or flat membrane separation membrane. can do.

As a second effect, according to the present invention, it is possible to obtain a polyisocyanate composition containing an allophanate group which does not contain a metal compound and has a small amount of isocyanurate causing turbidity. It can be used suitably. Moreover, when obtaining the polyisocyanate composition containing the said allophanate group, since reaction can be controlled easily, it is very useful industrially.

It is a figure which shows transition of NCO content in the middle of reaction in an Example and a comparative example. It is a figure which shows transition of NCO content in the middle of reaction in an Example.

Hereinafter, the present invention will be described in more detail.

The polyurethane resin-forming composition that solves the first problem of the present invention comprises an isocyanate component (A) and a polyol component (B). As the isocyanate component (A), an isocyanate group-containing compound (a2) And an isocyanate group-containing compound (a1) represented by the general formula (1) obtained by reacting an active hydrogen group-containing compound (b1) in the presence of a catalyst (C). .

<Isocyanate component (A)>
In the present invention, the isocyanate component (A) is represented by the general formula (1) obtained by reacting the isocyanate group-containing compound (a2) and the active hydrogen group-containing compound (b1) in the presence of the catalyst (C). Containing the isocyanate group-containing compound (a1).

The isocyanate group-containing compound (a2) in the present invention is not particularly limited, and any compound that contains two or more isocyanate groups in one molecule can be used. Examples of the compound containing two or more isocyanate groups in one molecule include toluene diisocyanate, MDI, paraphenylene diisocyanate, metaphenylene diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″. -Aromatic isocyanates such as triisocyanate, polyphenylene polymethylene polyisocyanate, hexamethylene diisocyanate, 1,10-decane diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1, 4-diisocyanate, isophorone diisocyanate, 2,4- and 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- and -1,4-phenylene Isocyanurate-modified, biuret-modified, allophanate-modified, uretdione from aliphatic or alicyclic isocyanates such as isocyanate, perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate, or a part of a series of these isocyanates Modification, uretoimine modification, carbodiimide modification, oxazolidone modification, amide modification, imide modification, etc. can be mentioned, and these can be used alone or in combination of two or more.

Of these, aromatic isocyanates are preferred from the viewpoints of being able to form a cured resin that is excellent in the working environment at the time of molding and has good physical properties (for example, mechanical strength such as hardness) required for a sealing material. MDI is more preferable.

In the present invention, as the active hydrogen group-containing compound (b1), a compound containing one or more active hydrogen groups in one molecule can be used. Monovalent or divalent ones are preferred from the standpoints of excellent workability, suitable physical properties required for the obtained membrane sealing material, and excellent membrane sealing material productivity. Trivalent or higher compounds are not preferred because the viscosity of the resulting isocyanate component (A) increases. The active hydrogen group-containing compound (b1) preferably has 1 to 70 carbon atoms, and more preferably 3 to 30 carbon atoms.

Examples of the compound (b1) having a monovalent or divalent active hydrogen group include aliphatic, aromatic, and alicyclic alcohols, diols, and thiols.

Examples of the aliphatic alcohol include methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol, stearyl alcohol and the like.

Examples of the aliphatic diol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, 3-methyl-1,5-pentanediol and the like.

Examples of the aromatic alcohol include benzyl alcohol, phenethyl alcohol, hydroxybenzyl alcohol, hydroxyphenethyl alcohol, methoxyphenylmethanol and the like.

Examples of the aromatic diol include 1,4-benzenedimethanol and 2,3-naphthalenediethanol.

Examples of the alicyclic alcohol include cyclohexanol, methylcyclohexanol, dimethylcyclohexanol and the like.

Examples of the alicyclic diol include 1,2-cyclopentanediol, 1,3-cyclopentanediol, 3-methyl-1,2-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Examples include 1,4-cyclohexanediol, 4,4′-bicyclohexanol, 1,4-cyclohexanedimethanol and the like.

Examples of the thiols include tridecyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, 3-mercaptobutyrate derivatives, 1,4-bis (mercaptomethyl) benzene, and the like.

Of these, aliphatic alcohols and aliphatic diols are preferable, and 2-propanol, 2-ethylhexanol, and tridecanol are particularly preferable from the viewpoint of obtaining more suitable physical properties required for the obtained membrane sealing material.

The monomer isocyanate content present in the isocyanate component (A) was determined from the peak area% (hereinafter also referred to as PA%) obtained by GPC measurement. The monomer isocyanate content is preferably 10.0 to 70.0 PA% in the sample to be measured, more preferably 20.0 to 60.0 PA%, and the viewpoint that the molding processability is excellent in the production of the membrane sealing material Most preferably, it is present in the range of 30.0 to 50.0 PA%.

The isocyanate group content of the isocyanate component (A) is preferably 3 to 30% by mass, more preferably 5 to 28% by mass, and 10 to 26% by mass from the viewpoint of excellent molding processability in the production of the membrane sealing material. Most preferably.

The presence of the (a1) structure represented by the general formula (1) contained in the isocyanate component (A) was confirmed using ¹³ C-NMR.
(1) Measuring device: ECX400M (manufactured by JEOL Ltd.)
(2) Measurement temperature: 23 ° C
(3) Sample concentration: 0.1 g / ml
(4) Solvent: Chloroform-d
(5) Evaluation method: (a1) The presence of the (a1) structure was confirmed from the signal derived from the structure (120 ppm, 152 ppm, 156 ppm).

The content of the (a1) structure in the isocyanate component (A) is determined from PA% obtained by GPC measurement, and is preferably 20 to 90 PA%, more preferably 30 to 80 PA%, and more preferably 50 to 70 PA% in the sample to be measured. Is most preferred.

Further, the viscosity of the isocyanate component (A) is preferably 250 to 1500 mPa · s at 25 ° C. from the viewpoint of obtaining low viscosity and good moldability.

<Polyol component (B)>
In the present invention, the polyol component (B) is not particularly limited, but any compound containing an active hydrogen group can be used. For example, a low molecular polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a castor oil polyol, a polyolefin polyol, a hydroxyl group-containing amine compound, and the like can be given. These can be used alone or in combination of two or more. Among these, castor oil-based polyol is preferable because it is excellent in chemical resistance and elution resistance.

Examples of the low molecular polyol include divalent ones such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-, 1,3- or 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexaneglycol, 1,8-octanediol, 1,10-decandiol, neopentylglycol, hydrogenated bisphenol A, etc. Examples include methylolpropane, hexanetriol, pentaerythritol, and sorbitol. The molecular weight of the low molecular polyol is preferably 50 to 200.

Examples of polyether polyols include adducts of the above low molecular polyols with alkylene oxides (alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, etc.), and ring-opening polymers of alkylene oxides. Specific examples include polypropylene glycol, polyethylene glycol, polytetramethylene ether glycol, and chipped ether that is a copolymer of ethylene oxide and propylene oxide. The molecular weight of the polyether polyol is preferably 200 to 7000. The molecular weight is more preferably 500 to 5,000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.

Polyester acids include polycarboxylic acids (aliphatic saturated or unsaturated polycarboxylic acids such as azelaic acid, dodecanoic acid, maleic acid, fumaric acid, itaconic acid, ricinoleic acid, dimerized linoleic acid, and aromatic polycarboxylic acids. Examples thereof include a polyol obtained by condensation polymerization of phthalic acid, isophthalic acid, terephthalic acid) and a polyol (at least one selected from the group consisting of the above low-molecular polyol and polyether polyol). The molecular weight of the polyester polyol is preferably 200 to 5,000. The molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.

Polylactone-based polyols include polymerization initiators such as glycols and triols, ε-caprolactone, α-methyl-ε-caprolactone, ε-methyl-ε-caprolactone, and β-methyl-σ-valerolactone. Examples include polyols obtained by addition polymerization of at least one selected from the group consisting of organic metal compounds, metal chelate compounds, fatty acid metal acyl compounds and the like in the presence of a catalyst. The molecular weight of the polylactone polyol is preferably 200 to 5,000. The molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.

As the castor oil-based polyol, a linear or branched polyester obtained by a reaction between a castor oil fatty acid and a polyol (at least one selected from the group consisting of the above low-molecular polyol and polyether polyol), for example, a diglyceride of castor oil fatty acid. Monoglyceride, mono-, di- or triester of castor oil fatty acid and trimethylol alkane, mono-, di-, or triester of castor oil fatty acid and polypropylene glycol. The molecular weight of the castor oil-based polyol is preferably 300 to 4000. The molecular weight is more preferably 500 to 3000 from the viewpoint of excellent molding processability during the production of the membrane sealing material.

Examples of the polyolefin-based polyol include polybutadiene-based polyol in which a hydroxyl group is introduced at the end of a copolymer of polybutadiene or butadiene and styrene or acrylonitrile.

Other examples include polyether ester polyols obtained by addition reaction of an alkylene oxide such as ethylene oxide or propylene oxide with a polyester having at least one selected from the group consisting of a carboxyl group and a hydroxyl group at the terminal.

Examples of the hydroxyl group-containing amine compound include amino alcohols as oxyalkylated derivatives of amino compounds.

Examples of amino alcohols include N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, N, N, N ′, N, which are propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine. Examples include '-tetrakis [2-hydroxyethyl] ethylenediamine, mono-, di- and triethanolamine, N-methyl-N, N'-diethanolamine, and the like. Of these, propylene oxide or ethylene oxide adducts of amino compounds such as ethylenediamine are preferred, and N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is more preferred. Use of N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine is effective in improving processability during molding and lowering the eluate.

The amount of the hydroxyl group-containing amine compound used is preferably in the range of 1 to 30% by mass, particularly preferably in the range of 5 to 25% by mass with respect to 100% by mass of the polyol component (B). . If the proportion in the polyol (B) is less than 1% by mass, the effect of the hydroxyl group-containing amine compound cannot be obtained, and if it exceeds 30% by mass, the reactivity becomes too high, the workability deteriorates and the filling property is impaired. Moreover, there is a possibility that the problem that the hardness of the obtained sealing material becomes too high may occur.

<Catalyst (C)>
As the catalyst (C), for example, any known catalyst that can promote the allophanatization reaction of the isocyanate group-containing compound (a2) and the active hydrogen group-containing compound (b1) is included. For example, metal salts, quaternary ammonium salts, and tertiary amines.

Examples of the metal salt include metal salts such as zinc acetylacetonate (ZnAcAc), stannous octoate, and zinc octoate.

Quaternary ammonium salts include tetraalkylammonium such as N, N, N, N, -tetramethylammonium, N, N, N-trimethyl-N-octylammonium, and N- (2-hydroxyethyl) -N, N. , N, -trimethylammonium, N- (2-hydroxypropyl) -N, N, N, -trimethylammonium and other hydroxyalkyltrialkylammonium and chloride, bromide, hydroxide, formate, caproate, hexanoate, 2-ethyl This compound is a combination of counter ions such as hexanoate and monoalkyl carbonate.

Tertiary amines include N, N, N-benzyldimethylamine, N, N, N-dibenzylmethylamine, N, N, N-cyclohexyldimethylamine, N-methylmorpholine, N, N, N-tribenzyl Trialkylamines such as ruamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine and N, N, Polymethylpolyalkylenepolyamines such as N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine and 2- (N, N-dimethylamino) ethanol, 3- ( N, N-dimethylamino) propanol, 2- (N, N-dimethylamino) -1-methylpropanol, {2- (N, N-dimethyl) Mino) ethoxy} ethanol, {2- (N, 3 amino alcohol such as N- diethylamino) ethoxy} ethanol.

The catalyst (C) is preferably 1 to 100 ppm, more preferably 10 to 50 ppm based on the mass of the isocyanate component (A). If it is less than 1 ppm, the reaction may not proceed. If it exceeds 100 ppm, the reaction may be fast and difficult to control.

<Stopper (D)>
In the present invention, the terminator (D) is used as a terminator for the allophanatization reaction. The terminator (D) includes any known one that deactivates the catalyst (C). For example, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid and other phosphoric acid compounds, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, monoalkyl or dialkyl ester of polyphosphoric acid, halogenated acetic acid such as monochloroacetic acid, benzoyl chloride Hydrochloric acid, sulfuric acid, sulfuric ester, ion exchange resin, chelating agent and the like. The terminator (D) is preferably added in an amount equal to or greater than the number of moles of the catalyst (C), and is preferably added in an amount of 1.0 to 1.5 times.

The polyisocyanate composition containing an allophanate group that solves the second problem of the present invention is a reaction product of MDI and an alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0. And an allophanate group-containing polyisocyanate composition characterized by not containing a metal catalyst.

When the (H) tertiary amine catalyst is used as the allophanatization catalyst, the reaction is rapid and difficult to control, and even if the reaction can be stopped at the desired reaction rate, the amount of isocyanurate produced is low. Because there are many, prepolymer tends to become cloudy.

Therefore, it is useful to perform the reaction in the presence of at least one selected from the group consisting of (G) carboxylic acid amides, sulfonic acid amides and active methylene compounds represented by the above formula (2).

(G) The reaction proceeds slowly by reacting with a tertiary amine catalyst in the presence of at least one selected from the group consisting of carboxylic acid amides, sulfonic acid amides and active methylene compounds represented by formula (2). In addition, since allophanatization proceeds selectively, a prepolymer with a low isocyanurate group content can be obtained, and the reaction control is facilitated.

(E) MDI (hereinafter also referred to as “E component”) used in the present invention may be any generally available MDI monomer. The isomer of the MDI monomer is usually 0 to 5% by weight of 2,2'-MDI, 0 to 95% by weight of 2,4'-MDI, and 5 to 100% by weight of 4,4'-MDI.

In order to obtain a prepolymer having a lower viscosity, the E component used in the present invention is preferably the above-mentioned MDI monomer. However, if a certain degree of increase in viscosity is allowed, polymethylene polyphenylene polyisocyanate, which is polymeric MDI, is also used. Can be used.

In this case, the content of polymethylene polyphenylene polyisocyanate is preferably 0 to 50% by weight in the isocyanate component used. When it exceeds 50% by weight, the viscosity becomes too high, and insoluble matter is easily generated.

As the (F) at least one alcohol component (hereinafter also referred to as “F component”) used in the present invention, a compound containing a hydroxyl group having 1 to 2 number average functional groups, that is, a monool or a diol can be used. A compound containing a phenolic hydroxyl group is not preferred because the isocyanurate group generation rate is increased and the viscosity is increased. Also, triol or higher polyol is not preferable because of its high viscosity.

Preferred monools for the F component used in the present invention include, for example, methanol, ethanol, propanol, 1- and 2-butanol, 1-pentanol, 1-hexanol, 2-methyl-1-pentanol, and 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-hexadecane 1-heptadecanol, 1-octadecanol, 1-nonadecanol 1-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.

Preferred diols for the F component used in the present invention include, for example, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 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 these glycols And polyalkylene glycols, which are oxyalkylene adducts having an initiator as the initiator, and mixtures thereof.

As the (G) carboxylic acid amide used in the present invention, at least one (hereinafter also referred to as “G component”) carboxylic acid amide selected from the group consisting of a carboxylic acid amide, a sulfonic acid amide, and an active methylene compound represented by the above formula (2) For example, 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-phenylacetamide, 4- Examples thereof include methylbenzamide, 2-aminobenzamide, 3-aminobenzamide, 4-aminobenzamide, and mixtures thereof.

Examples of the G sulfonic acid amide used in the present invention include methylsulfonamide, butylsulfonamide, t-butylsulfonamide, phenylsulfonamide, benzylsulfonamide, o-toluylsulfonamide, p-toluylsulfonamide, 3 -Aminophenylsulfonamide, 4-aminophenylsulfonamide and mixtures thereof.

Examples of the active methylene compound of G component used in the present invention include acetylacetone, 3-methyl-2,4-pentanedione, 3-ethyl-2,4-pentanedione, 3,5-heptanedione, 3,5- Examples include heptanedione, 6-methyl-2,4-heptanedione, methyl acetoacetate, ethyl acetoacetate, methyl 3-oxopentanoate, malonic acid, dimethyl malonate, diethyl malonate, and mixtures thereof.

As the (H) tertiary amine (hereinafter also referred to as “H component”) used 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-tone. Examples include rebenzylamine, N, N, N-tripropylamine, N, N, N-tributylamine, N, N, N-tripentylamine or N, N, N-trihexylamine.

Examples of the polymethylpolyalkylenepolyamine include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine and the like.

Examples of tertiary amino alcohols 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 amino alcohols are particularly preferred because of volatilization during the reaction and less elution when they become final resins.

When the reaction is carried out using only the H component, 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.

As the quaternary ammonium salt used in combination with the H component, for example, a tetraalkylammonium, a compound in which a hydroxyalkyltrialkylammonium is combined with a counter ion, or 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 hydroxyalkyltrialkylammonium include N- (2-hydroxyethyl) -N, N, N-trimethylammonium, N- (2-hydroxypropyl) -N, N, N, -trimethylammonium and the like.

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

Of these, tetraalkylammonium is suitable as the counter ion, but as the counter ion to be combined, carboxylate and monoalkyl carbonate are preferable from the viewpoint of compatibility with MDI.

It should be noted that the reaction is not controlled by the G component without using a tertiary amine and the quaternary ammonium salt alone is not effective because it deactivates during the reaction.

The G component used in the present invention can be added at any time from immediately before the urethanization reaction by the E component and the F component to immediately after the start of the allophanatization reaction. If the H component is added, the effect cannot be exerted, so the G component is added immediately before the urethanization reaction and after the completion of the urethanization reaction, immediately before the addition of the H component and until the allophanatization starts. Or it is preferable to add G component and H component simultaneously.

In general, the amount of addition of the H component in the present invention is preferably 0.1 to 100 ppm with respect to the total amount of the E component and the F component, and particularly preferably 1 to 50 ppm, depending on its 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.

Further, the amount of G component used in the present invention is preferably about 0.1 to 50 times mol of H component, and if it is less than 0.1 times mol, the reaction becomes abrupt and cannot be controlled, and exceeds 50 times mol. If added, the reaction may hardly proceed.

The temperature at which the E component and the F component are allophanatized with the G component and the H component, the higher the temperature, the more the allophanate group is produced and the lower the viscosity, but side reactions such as uretdioneization and carbodiimidization occur. In the reaction at a low temperature, the amount of isocyanurate groups produced is increased and the viscosity is increased. Therefore, the reaction temperature is preferably 20 ° C. or more and 200 ° C. or less, and the production ratio of isocyanurate groups is suppressed to 20 mol% or less. In order to make it lower viscosity, 60 degreeC or more and 160 degrees C or less are preferable.

As the (J) catalyst poison (hereinafter also referred to as “J component”) 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 amount added is preferably equivalent to or more, and preferably 1.0 to 1.5 times the molar equivalent of the number of moles of the tertiary amine or quaternary ammonium salt of the H component as the catalyst.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not construed as being limited to these examples. In the following, “%” means “% by weight” unless otherwise specified.

[Embodiment 1]
The following components were used in the examples and comparative examples.
<Isocyanate (a11)>
4,4′-MDI, trade name “Millionate MT (manufactured by Tosoh Corporation)”, isocyanate group content = 33.6 (mass%)
<Isocyanate (a12)>
Mixture of 2,4′-MDI and 4,4′-MDI, trade name “Millionate NM (manufactured by Tosoh Corporation)”, isocyanate group content = 33.6 (mass%)
<Isocyanate (a13)>
Modified carbodiimide of 4,4′-MDI, trade name “Coronate MX (manufactured by Tosoh Corporation)”, isocyanate group content = 29.1 (mass%)
<Isocyanate (a14)>
Modified carbodiimide of 4,4′-MDI, trade name “Millionate MTL-C (manufactured by Tosoh Corporation)”, isocyanate group content = 28.6 (mass%)
<Polyol (b11)>
2-ethylhexanol, number of functional groups = 1.0, molecular weight = 130
<Polyol (b12)>
Isotridecanol, functional group number = 1.0, molecular weight = 200, hydroxyl value = 275 (mgKOH / g)
<Polyol (b13)>
Castor oil, trade name “castor oil LAV (manufactured by Ito Oil Co., Ltd.)”, average functional group number = 2.7, hydroxyl value = 160 (mgKOH / g), number average molecular weight: 1000
<Polyol (b14)>
Polypropylene glycol, average number of functional groups = 2, hydroxyl value = 110 (mgKOH / g), number average molecular weight: 1000
<Polyol (b15)>
N, N, N ′, N′-tetrakis [2-hydroxypropyl] ethylenediamine, functional group number = 4.0, hydroxyl value = 760 (mgKOH / g)
<Catalyst (C)>
Acetylacetone zinc <stopper (D)>
2-ethylhexyl phosphate (monoester: diester = 1: 1 mol)

[Production Example 1: Production of isocyanate component (A-1)]
The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. Into this flask, 871.9 g of isocyanate (a11) was charged, and heating and stirring were started. When the temperature reached 70 ° C., 128.1 g of polyol (b11) was added and reacted by stirring and mixing at 90 ° C. for 1 hour under a nitrogen atmosphere to obtain an isocyanate group-terminated prepolymer. The catalyst (C) was added to this, heated to 90 ° C., the reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to reach 21.0%, the terminator (D) was placed. The reaction was stopped by adding a fixed amount to obtain an isocyanate component (A-1). The isocyanate component (A-1) was light yellow and transparent, and its viscosity at 25 ° C. was 550 mPa · s.

[Production Examples 2 to 4, 13, and 14: Production of isocyanate components (A-2) to (A-4), (A-13), and (A-14)]
Isocyanate components (A-2) to (A-4), (A-13), (A-14) shown in Table 1 in the same manner as in Production Example 1, except that the composition of the raw material was changed to the composition shown in Table 1. )

[Production Example 5: Production of isocyanate component (A-5)]
The inside of a 2 L four-necked flask equipped with a thermometer, a stirrer, a nitrogen seal tube, and a cooling tube was purged with nitrogen. Into this flask, 724.2 g of isocyanate (a11) was charged, and heating and stirring were started. When the temperature reached 50 ° C., 275.8 g of polyol (b13) was added and reacted by stirring and mixing at 70 ° C. for 5 hours under a nitrogen atmosphere, whereby the isocyanate group-terminated prepolymer (A-5) was reacted. Obtained. The isocyanate component (A-5) was pale yellow and transparent, had an NCO content of 21.0% and a viscosity at 25 ° C. of 480 mPa · s.

[Production Examples 6 to 12: Production of isocyanate components (A-6) to (A-12)]
Isocyanate components (A-6) to (A-12) shown in Table 2 were obtained in the same manner as in Production Example 5 except that the composition of the raw material was changed to the composition shown in Table 2.

[Preparation Example 1: Preparation of polyol component (B-1)]
A polyol component (B-1) was prepared by mixing 80 parts by mass of the polyol (b13) and 20 parts by mass of the polyol (b15).

<Examples 1 to 4, Comparative Examples 1 to 6>
“A-1” to “A-4”, “A-6”, “A-8” to “A-12”, “A-13”, “A-14” as the isocyanate component, and “B” as the polyol component −1 ”was mixed in the combinations of Tables 3 and 4 so that isocyanate group / active hydrogen group = 1.00 (equivalent ratio) to obtain a polyurethane resin-forming composition. In addition, “A-5” and “A-7” were not mixed with “B-1” because they were poor in low-temperature storage stability and generated turbidity and solids.

<Viscosity measurement>
The viscosities of the above (A-1) to (A-14) at a liquid temperature of 25 ° C. were measured using a B-type rotational viscometer.

<Monomer MDI Content and (a1) Structure Content Measurement>
In the above (A-1) to (A-14), the monomer MDI content (PA%) and (a1) structure content (PA%) were determined by GPC measurement under the following conditions and methods.

〔Measurement condition〕
Measuring device: “HLC-8120 (trade name)” (manufactured by Tosoh Corporation)
Column: Columns filled with three kinds of TSKgel G3000HXL, TSKgel G2000HXL, and TSKgel G1000HXL (all trade names, manufactured by Tosoh Corporation) as packing materials were connected in series, and measured at a column temperature of 40 ° C.
Detector: RI (refractive index) meter Eluent: Tetrahydrofuran (THF) (Flow rate: 1 ml / min, 40 ° C.)
Calibration curve: A calibration curve was obtained using the following grade polystyrene (TSK standard POLYSTYRENE). F-2 (1.81 × 104) F-1 (1.02 × 104) A-5000 (5.97 × 103) A-2500 (2.63 × 103) A-500 (Mw = 6.82 ×) 102, 5.78 × 102, 4.74 ×× 102, 3.70 × 102, 2.66 × 102) Toluene (Mw = 92)
Sample: 0.05 g sample in 10 ml THF.

〔Measuring method〕
First, a calibration curve was obtained from a chart obtained by detecting the refractive index difference using polystyrene as a standard substance. Next, for each sample, from the chart obtained by detecting the difference in refractive index based on the same calibration curve, the PA% of the peak near the peak top molecular weight (number average molecular weight) 230 indicating the monomer MDI, and (a1) structure The PA% near the peak top molecular weight (number average molecular weight) 3800, 3360, 2600, 2000, 1260, 700 was determined.

<Low temperature storage stability>
The above (A-1) to (A-14) were left in a 0 ° C. environment for 3 months to confirm the appearance of the sample. A pale yellow transparent material was designated as “◯”, and a turbid or solid product was observed as “x”.

<Evaluation of hardness of cured product>
Each of the polyurethane resin-forming compositions having combinations shown in Tables 3 and 4 was degassed under reduced pressure (10 to 20 kPa for 3 minutes) and then poured into a stainless steel mold (100 mm × 100 mm × 8 mm). This was left to cure at 45 ° C. for 2 days and then demolded to obtain a cured product. About the obtained hardened | cured material, the Shore D hardness in 25 degreeC was measured. The results are shown in Tables 3 and 4. The hardness was measured according to JIS K 7312.

<Evaluation of initial mixing viscosity>
For the polyurethane resin-forming compositions having the combinations shown in Tables 3 and 4, the main agent and the curing agent were uniformly mixed so that the liquid temperature was 25 ° C. and the isocyanate group / active hydrogen group = 1.00 (equivalent ratio), respectively. The viscosity at the stage where the polyurethane resin-forming composition was obtained was measured. The results are shown in Tables 3 and 4.

<Evaluation of reactivity>
For the polyurethane resin-forming compositions having the combinations shown in Tables 3 and 4, the main agent and the curing agent are uniformly mixed so that the liquid temperature is 25 ° C. and the isocyanate group / active hydrogen group is 1.00 (equivalent ratio). And the curing agent = 100 g), and after increasing the viscosity using a rotational viscometer (B type, No. 4 rotor) in an atmosphere at 25 ° C., the mixing of the main agent and the curing agent was started. The time until the viscosity of the composition reached 50000 mPa · s was defined as the pot life, and the reactivity was evaluated. The results are shown in Tables 3 and 4. In consideration of moldability, the pot life was good if it was 2.5 minutes or more and less than 7 minutes.

The isocyanate components (A-1) to (A-4), (A-13) and (A-14) according to Production Examples 1 to 4, 13, and 14 shown in Tables 1 and 2 have a low viscosity. In addition, it has excellent low-temperature storage stability. In contrast, the isocyanate components (A-5) and (A-7) according to Production Example 5 and Production Example 7 have low viscosity but are inferior in low-temperature storage stability. In addition, the isocyanate components (A-9) to (A-12) according to Production Examples 9 to 12 are excellent in low-temperature storage stability but have a high viscosity.

As shown in Tables 3 and 4 above, the polyurethane resin-forming compositions according to Examples 1 to 6 all have a low initial mixing viscosity and a short pot life, so that the moldability is balanced. On the other hand, the polyurethane resin-forming compositions according to Comparative Example 1 and Comparative Example 2 have a low initial mixing viscosity, but take a long time to form a membrane module because of their long pot life. In addition, since the polyurethane resin-forming compositions according to Comparative Examples 3 to 6 all have high mixing viscosities, there is a concern that the filling property at the time of membrane module molding is inferior and poor filling occurs.

[Embodiment 2]
The following components were used in the examples and comparative examples.

IsoE1; Millionate NM (manufactured by Tosoh Corporation, isomer 55.0%)
IsoE2; Millionate MT (manufactured by Tosoh Corporation, isomer 1.0%)
Poly F1; 2-butanol (manufactured by Tokyo Chemical Industry)
Poly F2; 2-octyldodecanol (trade name Calcoal 200GD manufactured by Kao)
Poly F3; Tridecanol (manufactured by KH Neochem)
Amide G1; 3-aminophenylsulfonamide (manufactured by Tokyo Chemical Industry)
Amide G2; 2-aminobenzamide (manufactured by Tokyo Chemical Industry)
Methylene G3; acetylacetone (manufactured by Tokyo Chemical Industry)
Methylene G4; diethyl malonate (manufactured by Tokyo Chemical Industry)
Catalyst H1; 2-[{2- (dimethylamino) ethyl} methylamino] ethanol (trade name TOYOCAT RX5 manufactured by Tosoh Corporation)
Catalyst H2; 2- {2- (dimethylamino) ethoxy} ethanol (trade name TOYOCAT RX3 manufactured by Tosoh Corporation)
Catalyst H3; Trimethyloctylammonium formate Catalyst poison J; Benzoyl chloride (manufactured by Tokyo Chemical Industry)

Quantification of allophanate groups and isocyanurate groups was performed using ¹³ C-NMR.
(1) Measuring device: ECX400M (manufactured by JEOL Ltd.)
(2) Measurement temperature: 23 ° C
(3) Sample concentration: 0.1 g / 1 mL
(4) Solvent: Chloroform-d
(5) Coupling: None (6) Pulse waiting time: 2 seconds (7) Integration number: 8000 times (8) Evaluation method: From the area ratio of the carbonyl signal of each functional group shown below, the mole of each functional group The ratio was calculated.
・ Allophanate group: 151ppm, 156ppm
-Isocyanurate group: 149 ppm

In Examples and Comparative Examples, the predetermined amount means each composition amount shown in Table 5.

Example 7
A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H1 diluted to 1% with polyB1 was immediately added. About 20 minutes after addition of catalyst H1, the temperature of the liquid can be confirmed, and the reaction is followed while sampling the internal liquid and measuring the NCO content, and when the NCO content is predicted to be 22.8%, catalyst poison J Was added in a predetermined amount to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained. The properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.

Example 8
A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. When an increase in the liquid temperature was confirmed about 15 minutes after addition of the catalyst H1, a predetermined amount of amide G1 diluted to 1% with polyF1 was added. The reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to be 22.8%, a predetermined amount of catalyst poison J was added to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, so that the prepolymer (P-1) which was the object of the present invention was obtained. The properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.

Example 9
A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature stabilized at 110 ° C., a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H2 diluted to 1% with polyF1 was immediately added. About 80 minutes after addition of catalyst H2, the temperature of the liquid can be confirmed, and the reaction is followed while sampling the internal liquid and measuring the NCO content, and when the NCO content is predicted to be 22.8%, catalyst poison J Was added in a predetermined amount to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained. The properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.

Example 10
A predetermined amount of isoE1 was added to a 1-liter four-necked flask, and the temperature was adjusted to 70 ° C. while stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added while stirring, and then a predetermined amount of catalyst H3 diluted to 1% with poly F1 was immediately added. Next, a predetermined amount of amide G1 diluted to 1% with polyF1 was added, and then a predetermined amount of catalyst H2 diluted to 1% with polyF1 was immediately added, and the temperature was adjusted to 110 ° C. About 15 minutes after the addition of catalyst H3, the rise in the liquid temperature can be confirmed, and the reaction is followed while sampling the internal liquid and measuring the NCO content, and when the NCO content is predicted to be 22.8%, catalyst poison J Was added in a predetermined amount to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained. The properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.

Example 11
A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F2 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF2 was added. When an increase in the liquid temperature was confirmed approximately 15 minutes after addition of the catalyst H1, a predetermined amount of amide G2 diluted to 1% with polyF2 was added. The reaction was followed while sampling the internal solution and measuring the NCO content, and when the NCO content was predicted to be 13.8%, a predetermined amount of catalyst poison J was added to stop the reaction. The synthesized prepolymer was a pale yellow transparent liquid at 25 ° C., and the amount of isocyanurate groups was small, so that the prepolymer (P-2) which was the object of the present invention was obtained. The properties and the molar ratio of each functional group are shown in Table 5, and the transition of the NCO content during the reaction is shown in FIG. The reaction was stable and control of the reaction was easy.

Example 12
A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F3 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of methylene E3 diluted to 1% with polyF3 was added, and then a predetermined amount of catalyst H1 diluted to 1% with polyF3 was immediately added. About 20 minutes after the addition of catalyst H1, the temperature of the liquid can be confirmed, and the reaction is followed while sampling the internal liquid and measuring the NCO content, and when the NCO content is predicted to be 16.1%, catalyst poison J Was added in a predetermined amount to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, so that the prepolymer (P-3) which was the object of the present invention was obtained. Table 5 shows the properties and the molar ratio of each functional group, and FIG. 2 shows the transition of the NCO content during the reaction. The reaction was stable and control of the reaction was easy.

Example 13
A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F3 was added while stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of methylene G4 diluted to 1% with polyF3 was added, and then a predetermined amount of catalyst D1 diluted to 1% with polyF3 was immediately added. About 20 minutes after the addition of catalyst H1, the temperature of the liquid can be confirmed, and the reaction is followed while sampling the internal liquid and measuring the NCO content, and when the NCO content is predicted to be 16.1%, catalyst poison J Was added in a predetermined amount to stop the reaction. The synthesized prepolymer was a light yellow transparent liquid at room temperature, and the amount of isocyanurate groups was small, and the prepolymer which was the object of the present invention was obtained. Table 5 shows the properties and the molar ratio of each functional group, and FIG. 2 shows the transition of the NCO content during the reaction. The reaction was stable and control of the reaction was easy.

Comparative Example 7
A predetermined amount of isoE2 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. About 15 minutes after addition of the catalyst H1, the rise in the liquid temperature was confirmed, and the reaction was followed. However, the reaction temperature could not be controlled due to rapid exotherm, and the prepolymer which is the object of the present invention was not obtained because of gelation. It was. Therefore, it could not be used as a prepolymer that solves the first problem.

Comparative Example 8
A predetermined amount of isoE1 was added to a 1 liter four-necked flask, and the temperature was adjusted to 50 ° C. with stirring under a nitrogen stream. Next, a predetermined amount of poly F1 was added with stirring, and the temperature was raised to 110 ° C. after the exothermic reaction of the urethanization reaction had subsided. When the internal temperature was stabilized at 110 ° C., a predetermined amount of catalyst H1 diluted to 1% with polyF1 was added. About 10 minutes after addition of catalyst H1, the rise in the liquid temperature could be confirmed, and the reaction was followed. However, the reaction temperature could not be controlled due to rapid exotherm, so when the internal temperature reached 124 ° C, catalyst poison J was removed. The reaction was stopped by adding a predetermined amount. The synthesized prepolymer was a pale yellow transparent liquid at room temperature, but the amount of isocyanurate groups was large and the prepolymer which was the object of the present invention was not obtained. From the viewpoint that the reaction cannot be controlled, it has been difficult to use it as a prepolymer that solves the first problem.

Examples 14 to 16
As in Examples 1 to 4, “P-1”, “P-2”, “P-3” as the isocyanate component, “B-1” as the polyol component, and the isocyanate group / activity in the combinations shown in Table 6 A polyurethane resin-forming composition was obtained by mixing so that hydrogen group = 1.00 (equivalent ratio). According to this example, by applying the allophanate group-containing polyisocyanate composition capable of easily controlling the reaction according to Embodiment 2 to the polyurethane resin-forming composition of Embodiment 1, the mixed viscosity and the pot life are satisfied. Can be said.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

Japanese Patent Application No. 2015-252102 filed on December 24, 2015, Japanese Patent Application No. 2016-58205 filed on Mar. 23, 2016, Japanese Patent Application filed on Sep. 23, 2016 The entire contents of the specification, claims, drawings and abstract of application 2016-185222 are hereby incorporated herein by reference as the disclosure of the specification of the present invention.

1. 1. Transition of reaction time and NCO content in Example 7. 2. Transition of reaction time and NCO content in Example 8 3. Transition of reaction time and NCO content in Example 9 4. Transition of reaction time and NCO content in Example 10 5. Transition of reaction time and NCO content in Example 11 6. Transition of reaction time and NCO content in Comparative Example 8 7. Transition of reaction time and NCO content in Example 12 Transition of reaction time and NCO content in Example 13

Claims (16)

1. A polyurethane resin-forming composition containing an isocyanate component (A) and a polyol component (B), and an isocyanate group-containing compound (a1) represented by the following general formula (1) in the isocyanate component (A) An allophanate group-containing polyurethane resin-forming composition to be contained.
   

   

   (Wherein R ₁ represents a residue other than the active hydrogen group of the active hydrogen group-containing compound (b1), X represents an oxygen or sulfur atom, and R represents an unreacted isocyanate group of the isocyanate group-containing compound (a2). M represents an integer of 1 or 2. When m is 1, n represents an integer of 1 to 30, and when m is 2, n represents an integer of 1 to 15. )
2. 2. The allophanate group-containing polyurethane resin-forming composition according to claim 1, wherein the isocyanate component (A) is liquid at normal temperature.
3. The content of the isocyanate group-containing compound (a1) represented by the general formula (1) in the isocyanate component (A) is 20 to 90 peak area% in gel permeation chromatography measurement. 3. The allophanate group-containing polyurethane resin-forming composition according to 1 or 2.
4. The isocyanate group-containing compound (a1) is an allophanate group-containing polyisocyanate composition that is a reaction product of diphenylmethane diisocyanate and an alcohol, and the molar ratio of allophanate groups to isocyanurate groups is 80:20 to 100: 0. , A carboxylic acid amide, a sulfonic acid amide, and at least one selected from the group consisting of active methylene compounds represented by the formula (2) and a tertiary amine catalyst as an allophanatization reaction aid and no metal catalyst 4. The allophanate group-containing polyurethane resin-forming composition according to claim 1, which is an allophanate group-containing polyisocyanate composition.
   

   

   (Wherein R ₂ 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 ₃ and R ₄ 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)
5. The allophanate group-containing polyurethane resin-forming composition according to any one of claims 1 to 4, wherein the isocyanate group-containing compound (a2) is an aromatic isocyanate having two or more isocyanate groups.
6. The allophanate group-containing polyurethane resin-forming composition according to any one of claims 1 to 5, wherein the isocyanate group-containing compound (a2) is diphenylmethane diisocyanate.
7. 7. The allophanate group-containing polyurethane resin-forming composition according to claim 1, wherein the active hydrogen group-containing compound (b1) is a monool or diol having 1 to 70 carbon atoms.
8. Use of the allophanate group-containing polyurethane resin-forming composition according to any one of claims 1 to 7 as a sealing material for a membrane module.
9. A method for producing an allophanate group-containing polyurethane resin, comprising reacting the isocyanate component (A) according to any one of claims 1 to 7 with a polyol component (B).
10. A sealing material comprising a cured product of the allophanate group-containing polyurethane resin-forming composition according to claim 1.
11. A membrane module sealed with the sealing material according to claim 10.
12. An allophanate group-containing polyisocyanate composition that is a reaction product of diphenylmethane diisocyanate and alcohol, wherein the molar ratio of allophanate group to isocyanurate group is 80:20 to 100: 0, and carboxylic acid amide, sulfonic acid amide, And an allophanate group comprising at least one selected from the group consisting of active methylene compounds represented by the general formula (2) and a tertiary amine catalyst as an allophanatization reaction auxiliary agent and containing no metal catalyst. Containing polyisocyanate composition.
    

    

    (Wherein R ₂ 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 ₃ and R ₄ 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)
13. (E) diphenylmethane diisocyanate and (F) at least one alcohol component in the presence of (G) at least one selected from the group consisting of carboxylic acid amides and sulfonic acid amides and active methylene compounds represented by formula (2) (H) A method for producing an allophanate group-containing polyisocyanate composition characterized in that the catalyst is allophanatized with a tertiary amine as a catalyst (J) and the reaction is stopped by a catalyst poison.
    

    

    (Wherein R ₂ 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 ₃ and R ₄ 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)
14. The method for producing an allophanate group-containing polyisocyanate composition according to claim 13, wherein (F) a tertiary amine and a quaternary ammonium salt are used in combination as a catalyst to form an allophanate.
15. (F) The manufacturing method of the allophanate group containing polyisocyanate composition of Claim 13 or 14 characterized by not containing a metal catalyst as a catalyst.
16. 16. The method for producing an allophanate group-containing polyisocyanate composition according to claim 13, wherein the molar ratio of the allophanate group to the isocyanurate group is 80:20 to 100: 0.

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