JP2003073992A - Isocyanate-including composition for aqueous binder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an isocyanate-including composition for a water-based binder that can increase the yield rate of an isocyanate component to organic and inorganic particles, when it is used as a binder for molded products made of the organic and inorganic particles, because the binder includes a specific amount of an anionic isocyanate and can achieve the existing level of performances in the strength and the dimensional stability with a minimal use of the binder. SOLUTION: This isocyanate-including composition includes (A) the anionic isocyanate in an amount of >=0.1 mass % based on the whole isocyanate- including composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to isocyanate-containing compositions for aqueous binders. More specifically, it relates to an isocyanate-containing composition for an aqueous binder containing a specific amount of anionic isocyanate.

[0002]

BACKGROUND OF THE INVENTION Conventionally, when a molded body is manufactured through a wet papermaking process, there are cases where an organic powder or granular material is used and where an inorganic powder or granular material is used. When organic powder is used, it is often the case that a lignocellulosic material is used. For example, wood fibers are molded into a plate shape with a density of 800 kg /
Those having m ³ or more are called hard boards and are useful as building materials. In addition, similarly, there is a pulp mold that is also formed from waste paper as a raw material for lignocellulosic materials. This is molded with a low specific gravity of 400 kg / m ³ or less,
It is useful as a cushioning material during packaging.

When inorganic powder is used, it has been proposed to manufacture a flame-retardant building material by molding it into a plate shape using mineral fibers such as rock wool and an inorganic filler such as calcium carbonate. . When a fibrous body is formed into a mat with a granular material or a binder by such a so-called wet method, moisture is sufficiently removed in order to reduce the load of the subsequent drying step (so-called “filtration”). However, this is sometimes referred to as "drainage".)
Filtration is performed by passing through a suction device. However, when suction is strongly applied, there is a problem that physically retained particles and binder fall out together with water.

In this case, since the filtered filtrate is usually recycled, it is possible that the particulate matter and the binder dropped into the filtrate by the suction can finally be retained in the fiber again. However, when an emulsion of isocyanates is used as a binder component, with polymeric MDI or the like that is mainly used as isocyanates, if filtration with suction is carried out, some of the isocyanates fall out in the filtrate, and NCO Since it reacts with water and becomes inactive, it cannot be recycled and there was a problem from the viewpoint of productivity.

Therefore, the yield of isocyanates into organic and inorganic powders (hereinafter sometimes referred to as "organic / inorganic powders") is improved, and the amount of isocyanates added is minimized. In addition, the emergence of an isocyanate component that can provide a board having excellent board strength and the like has been desired. Therefore, the inventors of the present application have conducted diligent research to solve the above problems, and as an isocyanate component, by using an isocyanate-containing composition containing a specific amount of anionic isocyanate, an organic-inorganic powder of the isocyanate component is obtained. It was found that the yields of 1) can be improved, and the effects similar to the conventional ones can be obtained with respect to the strength and dimensional stability of the board with the minimum addition amount, and the present invention has been completed.

[0006]

It is an object of the present invention to solve the problems associated with the prior art as described above, to improve the yield of the isocyanate component in the organic-inorganic powder and to minimize the amount of isocyanate added. However, it is an object of the present invention to provide an isocyanate-containing composition for an aqueous binder, which has effects equivalent to those of conventional ones with respect to board strength, dimensional stability, and the like.

[0007]

SUMMARY OF THE INVENTION An isocyanate-containing composition for an aqueous binder according to the present invention comprises an anionic isocyanate (A).
Is 0.1 mass% with respect to the isocyanate-containing composition.
It is characterized by being contained above. The isocyanate-containing composition for an aqueous binder according to the present invention contains an anionic isocyanate (A) and has a titer of 1 to 50 μeq of a poly (diallylmethylammonium chloride) solution by a streaming potential method in a pH range of 5 or more and 7 or less. / G.

The isocyanate-containing composition for the aqueous binder preferably comprises the anionic isocyanate (A), the unreacted isocyanate (B), and the nonionic compound (C) having a surface active action. The anionic isocyanate (A) is a polymeric MD.
It is preferably a modified form of I.

It is preferable that the anionic isocyanate (A) is a polymeric MDI having an anionic functional group and the unreacted isocyanate (B) is a polymeric MDI. Moreover, when using the said polymeric MDI, it is preferable that the said isocyanate containing composition for aqueous binders is used for a board.

The titer is preferably 5 to 40 μeq / g. The isocyanate-containing composition for the aqueous binder is at least an aqueous slurry of organic-inorganic powder and granules, an emulsion dispersion of the isocyanate-containing composition for the aqueous binder, and a cationic flocculant are mixed to solidify the solid components. The obtained mixture can be filtered, and the solid component can be suitably used for a molded body obtained by heating and drying.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The isocyanate-containing composition for an aqueous binder according to the present invention contains a specific amount of anionic isocyanate (A). Further, the isocyanate-containing composition for an aqueous binder according to the present invention contains an anionic isocyanate (A) and has a titer of a polydiallylmethylammonium chloride solution measured by a streaming potential method in a pH range of 5 or more and 7 or less. , In a specific range.

Hereinafter, anionic isocyanate (A) contained in the isocyanate-containing composition for aqueous binder,
An isocyanate-containing composition for an aqueous binder, an unreacted isocyanate (B) as another component that may be contained in the composition, a nonionic compound (C) having a surface active action, and the like will be described. Anionic isocyanate (A) The isocyanate-containing composition for an aqueous binder according to the present invention is added as an aqueous binder used for adhering organic-inorganic powder and contains anionic isocyanate (A). The anionic isocyanate (A) is a compound (b) having an active hydrogen group that reacts with an isocyanate group and an anionic functional group (hereinafter the compound (b) may be referred to as an "anionic active hydrogen compound"), It is an isocyanate-modified product obtained by reacting with an isocyanate (a), and has an isocyanate group and an anionic functional group. Isocyanate (a) As the isocyanate (a) which is a raw material of the anionic isocyanate (A), a known isocyanate can be used. Preferably, a polyisocyanate having two or more molecular terminal isocyanate groups in the molecule is used.

Examples of such an isocyanate (a) include, for example, tolylene diisocyanate (TDI),
4,4'-diphenylmethane diisocyanate (MD
I), xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), 1,5-naphthalene diisocyanate (NDI), and liquid diphenylmethane diisocyanate liquefied by a conventionally known method described in JP-B-38-4576. Aromatic isocyanates such as liquid MDI), crude tolylene diisocyanate (crude TDI), polymethylene polyphenyl polyisocyanate (polymeric MDI or crude MDI); aliphatic isocyanates such as hexamethylene diisocyanate (HDI); isophorone diisocyanate (IPDI) ), Hydrogenated XDI (H6XDI), hydrogenated MDI (H12MDI), hydrogenated tetramethyl XDI, norbornane diisocyanate methyl (NBDI) and the like.

Further, an isocyanate group-terminated prepolymer using these isocyanates (hereinafter sometimes referred to as "urethane prepolymer"), carbodiimide modified product, uretonimine modified product, acylurea diisocyanate, isocyanurate modified product, trimethylolpropane adduct. Body, biuret modified product and allophanate modified product are also included.

Of these, aromatic isocyanates can be preferably used, and among the aromatic isocyanates, polymeric MDI and / or modified products thereof can be more preferably used.
It is particularly preferred to use I. When using the polymeric MDI, the average molecular weight of the polymeric MDI is 30.
Those in the range of 0 to 500 are preferable.

These isocyanate compounds may be used alone or in combination of two or more. Active hydrogen groups that react with isocyanate groups and anionic agents
Compound (b) having an active group (anionic active hydrogen compound
As the anionic active hydrogen compound (b), NCO
A compound having at least one active hydrogen group that reacts with a group and at least one anionic functional group that becomes an anion in water is included.

Examples of the anionic functional group contained in the anionic active hydrogen compound (b) include a carboxyl group (-COOH) and a sulfonic acid group (-SO).
₃ H), a sulfuric acid ester group (—OSO ₃ H), a phosphoric acid ester group (—OPO ₃ H, —OPO ₂ H) and the like.
These anionic functional groups may be alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium, and ammonium salts such as NH ₄ ⁺ . Of these, compounds having a carboxyl group or a sulfonic acid group can be preferably used.

As the active hydrogen group which reacts with the NCO group,
Examples thereof include -OH group and -NH group. As such an anionic active hydrogen compound (b), a compound having a carboxyl group or a sulfonic acid group and an —OH group can be preferably used, and a compound having a carboxyl group and an —OH group is particularly preferable.

Specific examples of the preferable anionic active hydrogen compound (b) include glycolic acid, lactic acid, glyceric acid, dimethylolpropionic acid, dimethylolbutanoic acid, malic acid, tartaric acid and salicylic acid. Hydroxycarboxylic acids or derivatives thereof;
Examples thereof include hydroxysulfonic acids such as 2-hydroxyethanesulfonic acid and aminoethylsulfonic acid.

Further, using these compounds having an -OH group as an initiator, ethylene oxide, propylene oxide,
Polyether polyols obtained by reacting ε-caprolactam, alkylene oxides such as tetrahydrofuran, or ring-opening cyclic ethers can also be used as the anionic active hydrogen compound (b). Anionic Isocyanate (A) The anionic isocyanate (A) used in the present invention has an NCO group and an anionic functional group in one molecule, and specifically, the isocyanate (a) is used.
Derived from and the anionic active hydrogen compound (b)
And ingredients derived from.

As described above, the isocyanate (a) is preferably an aromatic isocyanate, more preferably polymeric MDI. The anionic active hydrogen compound (b) preferably has the carboxyl group or the sulfonic acid group, more preferably the carboxyl group. Therefore, the anionic isocyanate (A) is preferably a modified product of aromatic isocyanate, more preferably a modified product of polymeric MDI.

In the anionic isocyanate (A), the number of anionic functional groups in one molecule is not particularly limited, but it is usually sufficient that it has an average of one or more anionic functional groups, and preferably It is desirable to have an average of 1 to 5, more preferably an average of 1 to 3 anionic functional groups. In the anionic isocyanate (A), the number of NCO groups in one molecule is at least 1 NC.
It suffices to have an O group, preferably one or more, more preferably one or two.

The anionic isocyanate (A) is obtained by reacting the isocyanate (a) with the anionic active hydrogen compound (b). The method for synthesizing the anionic isocyanate (A) is not particularly limited, and the anionic isocyanate (A) may be obtained by directly anion-modifying the isocyanate or by adding anion-modified isocyanate in advance. For example, when the anionic isocyanate (A) directly anion-modifies the isocyanate, the isocyanate (a) is stoichiometrically excessive with respect to the anionic active hydrogen compound (b), and the isocyanate and the active hydrogen compound are collectively blended. Alternatively, it can be obtained by charging either one first and adding the other later and reacting at 60 to 120 ° C. for 1 to 15 hours. In order to accelerate the reaction, a known catalyst such as a tertiary amine may be added for the reaction to be produced.

The amount of the isocyanate (a) used with respect to the anionic active hydrogen compound (b) is specifically N.
CO / H (active hydrogen) (molar ratio), preferably 2.1
It is desirable to be 120 to 120, and more preferably 4.0 to 60. If the NCO / H is less than 2.1, the remaining anionic isocyanate (A) has a small amount of remaining NCO groups, and the compatibility with other isocyanates in the isocyanate-containing composition for an aqueous binder may decrease. If it exceeds 120, the content of the anionic group in the obtained anionic isocyanate (A) may decrease, which is not preferable.

Isocyanate-containing composition for aqueous binder
Material The isocyanate-containing composition for an aqueous binder according to the present invention only needs to contain the anionic isocyanate (A) in a specific amount, and the types of other components different from the anionic isocyanate (A) are not limited, but are preferable. As the other component, the isocyanate compound (a) is an isocyanate compound (B) which is not modified with the anionic active hydrogen compound (b) and / or the nonionic active hydrogen compound (hereinafter referred to as “unknown”). It is preferable that the reactive isocyanate (B) "). Such unreacted isocyanate (B) may contain the isocyanate (a) that has not been reacted in the production of the anionic isocyanate (A).

Examples of the nonionic active hydrogen compound include alkyl group-terminated polyethylene glycol. Further, the isocyanate-containing composition for a water-based binder of the present invention may be used by adding another isocyanate compound before use. Specific examples of the unreacted isocyanate (B) include those described in the isocyanate (a). Among these, as the unreacted isocyanate (B), an aromatic isocyanate is preferably used. Among the aromatic isocyanates, polymeric MDI and / or its modified product can be more preferably used, and of these, it is particularly preferable to use polymeric MDI.

As the unreacted isocyanate (B), it is preferable to use the same isocyanate compound as the isocyanate (a) which induces the anionic isocyanate (A). By using compounds having the same isocyanate skeleton, the compatibility between isocyanates is improved, and when the powder and granules are adhered, even when water is sucked and filtered, the isocyanates are prevented from falling out into the filtrate. It is possible to improve the yield of the isocyanates in the cured product.

Further, the isocyanate-containing composition for aqueous binder contains a nonionic compound (C) having a surface-active action in order to enhance the dispersibility in water and the emulsifying property of the isocyanate-containing composition for aqueous binder. You may stay. As the nonionic compound (C) having a surface active action, a known nonionic surfactant or the isocyanate (a) is modified with a nonionic active hydrogen compound and is modified with an anionic active hydrogen compound. It may contain an unreacted isocyanate (hereinafter referred to as "nonionic isocyanate" in the present specification).

The isocyanate-containing composition for an aqueous binder according to the present invention is preferably used for boards, and particularly preferably used for adhering boards using mineral fibers. When used for boards, the isocyanates used are preferably polymeric MDI or its derivatives. Nonionic compound (C) having surface active action
Examples include ether type nonionic interfaces such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene polyoxypropylene block copolymer, and polyoxyethylene polyoxypropyl alkyl ether. Activator: Polyoxyethylene ether of glycerin ester, polyoxyethylene ether of sorbitan ester, ether ester type nonionic surfactant such as polyoxyethylene ether of sorbitol ester; polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, Sorbitan ester,
Ester-type nonionic surfactants such as propylene glycol ester and sucrose ester; nitrogen-containing nonionic surfactants such as fatty acid alkanolamides, polyoxyethylene fatty acid amides and polyoxyethylene alkylamines; and the isocyanate (a) Examples include self-emulsifying nonionic isocyanates obtained by reacting with a nonionic active hydrogen compound such as an alkyl group-terminated polyethylene glycol.

Of these, the nonionic compound (C) having a surface-active effect is preferably the above-mentioned nonionic isocyanate and has the same isocyanate skeleton as the isocyanate (a) which induces the anionic isocyanate (A). The nonionic isocyanate having is more preferable. By using a compound having the same isocyanate skeleton, the compatibility of the isocyanates is improved, and in the formation of a board using the isocyanate-containing composition for an aqueous binder of the present invention, even when suctioning and filtering water It is possible to prevent the isocyanate-containing composition for an aqueous binder from falling out of the filtrate, and to improve the yield of the isocyanate-containing composition for an aqueous binder in the cured product.

The content of the anionic isocyanate (A) in the isocyanate-containing composition for an aqueous binder varies depending on the number of anionic functional groups of the anionic isocyanate (A), and is 1 molecule in all the anionic isocyanate (A). The average number of anionic functional groups in the
Then, the content of the anionic isocyanate (A) is 0.1% by mass or more, preferably 0.5 to 15% by mass, and more preferably 2 to 6 with respect to the isocyanate-containing composition for the entire aqueous binder. It is desirable that the amount is% by mass.

When the anionic isocyanate (A) is contained in the isocyanate-containing composition for an aqueous binder in the above range with respect to the isocyanate-containing composition for an aqueous binder, water is filtered by suction in forming a molded article. Also in this case, the isocyanates can be prevented from falling out of the filtrate, and the yield of the isocyanates in the cured product can be improved.

This is an anionic isocyanate (A)
By containing an isocyanate-containing composition for an aqueous binder, the anionic functional group appearing on the particle surface of the isocyanate-containing composition for an aqueous binder obtained by emulsifying the isocyanate-containing composition for an aqueous binder, cationic aggregation It becomes easy to bond with the agent, and in combination with the interaction between the cationic flocculant and the organic-inorganic powder, the interaction of the isocyanate-containing composition for the aqueous binder with the organic-inorganic powder is mediated by the cationic flocculant. It is presumed that the yield of the isocyanate-containing composition for an aqueous binder in the cured product can be improved due to the increase.

In the above-mentioned isocyanate-containing composition for an aqueous binder according to the present invention, when water is added and emulsified and dispersed, the amount of surface charge of the emulsified and dispersed particles of the isocyanate-containing composition for an aqueous binder is within a certain range. is there.
Specifically, for an emulsion dispersion containing an isocyanate-containing composition for an aqueous binder, the titer of a poly (diallylmethylammonium chloride) solution by a streaming potential method in the range of pH 5 or more and 7 or less is 1 to 50 μeq, preferably 5-40 μeq, more preferably 10-30 μeq
It is desirable to be in the range of eq.

The titer indicates the surface charge amount of the isocyanate-containing composition for an aqueous binder, and the surface charge amount is the amount of the anionic isocyanate (A) contained in the isocyanate-containing composition for an aqueous binder. It is the charge amount of the anion in the isocyanate-containing composition for an aqueous binder, which is expressed by the anionic functional group.

The titration by the streaming potential method can be performed by a known method. Note that the titration by the streaming potential method is a method of measuring the surface charge amount of particles, in which a titration solution having counter ions is added to a sample solution having target particles having a charge, and the streaming potential is zero mV. The amount of charge of the target compound is measured from the consumption of the titrant required to reach the point.

In the present specification, the surface charge amount of the isocyanate-containing composition for an aqueous binder is measured by the streaming potential method by "PCD (Particle Charge)" of MuTEC.
Detector: particle surface charge amount measuring device) 03 ". As the standard solution, a poly (diallylmethylammonium chloride) solution was used, and the pH of the standard solution was set in the range of 5 to 7.

When the anionic isocyanate (A) is contained in the isocyanate-containing composition for an aqueous binder in an amount corresponding to the titration amount in the above range, when water is filtered by suction when forming a cured product. Also, it is possible to prevent the isocyanates from falling out in the filtrate,
The yield of isocyanates in the cured product can be improved. The reason is similar to the above.

If the titer is less than 1 μeq / g, it will be difficult to improve the yield of isocyanates. Further, when the titer is more than 50 μeq / g, the hydrophilicity of the isocyanate-containing composition for an aqueous binder becomes high, the water absorption rate of the obtained cured product becomes high, and the dimensional stability or strength of the cured product deteriorates. There is.

The isocyanate-containing composition for an aqueous binder is obtained by mixing, for example, the anionic isocyanate (A), the unreacted isocyanate (B) and the nonionic compound (C) having a surface active action. ,
For example, by stirring at a temperature of 50 to 150 ° C. for about 30 minutes to 5 hours, the anionic isocyanate (A), the unreacted isocyanate (B), and a nonionic compound (C) having a surface active action. It can be obtained as a composition in a solid or liquid state in which and are uniformly mixed.

Use The isocyanate-containing composition for an aqueous binder according to the present invention is preferably mixed with water and used as an emulsified dispersion. Such an emulsified dispersion, at least a water slurry of organic-inorganic powder, an emulsified dispersion of an isocyanate-containing composition, and a cationic flocculant are mixed to coagulate solid components, and then the resulting mixture is obtained. Can be suitably used as a binder for a molded product obtained by filtering and heating and drying the solid component.

Specifically, an emulsion dispersion containing the isocyanate-containing composition for an aqueous binder according to the present invention, wood fiber, used paper, pulp, bagasse, straw, rice straw,
Lignocellulosic powders such as kenaf and Kolyan stem,
Mineral fibers such as rock wool, slag wool, mineral wool, nickel wool, glass fiber, and, if necessary, calcium carbonate, silica sand, microsilica, slag,
Aqueous slurry containing organic-inorganic powder such as inorganic filler such as aluminum hydroxide, other binder resin such as phenol resin, polyaluminum chloride-based compound such as polyaluminum chloride, cation-based aggregation such as polyacrylamide Agent and other papermaking additives such as sizing agent, coagulant, defoaming agent and the like are supplied to a stirrer in a predetermined amount to coagulate solid components to form a slurry. The solid component is composed of an isocyanate-containing composition for an aqueous binder, an organic-inorganic powder such as lignocellulosic fibers and / or mineral fibers and / or inorganic fillers, a cationic coagulant, and other resins.

Then, the slurry-like mixture mixed in the stirrer is supplied to a paper making machine to make a paper, and then filtered (dehydrated) to obtain a plate-like wet mat made of solid components. When forming such a wet mat,
In order to reduce the drying load in the subsequent drying step, it is necessary to perform the filtration sufficiently, and usually the filtration is performed using a suction device.

Since the wet mat uses the isocyanate-containing composition for an aqueous binder according to the present invention containing a specific amount or a specific titration amount of anionic isocyanate (A) as the isocyanate, as described above,
The yield of the isocyanate component in the wet mat can be increased, and the isocyanate component flowing out into the filtrate can be significantly reduced. For example, in the present invention, the content of the isocyanate-containing composition for an aqueous binder that has flowed out into the filtrate after filtration is preferably 30% by mass or less, and more preferably the total amount of the isocyanate-containing composition for an aqueous binder before filtration. Can be in the range of 1 to 20 mass%.

The wet mat thus obtained can be formed into a desired molded product through steps such as heating, compression and drying. Further, since the obtained molded body uses the isocyanate-containing composition for the aqueous binder containing a specific amount of anionic isocyanate (A), the molded body can have a water absorption rate excellent in practicality. Therefore, the molded product produced by the method of the present invention is excellent in strength and dimensional stability. For example, the water absorption of the board thus obtained (water absorption after soaking in water at 20 ° C. for 24 hours) can be preferably 55% or less, more preferably 50% or less.

If necessary, such a molded body is cut into a desired size or molded into a desired shape, subjected to surface processing, actual processing, painting, etc., and used for various purposes as a final product such as a building material. You can

[0047]

The isocyanate-containing composition for an aqueous binder according to the present invention contains a specific amount of anionic isocyanate. Therefore, when the composition is used as a binder for a molded article made of organic / inorganic powder or the like, isocyanate It is possible to improve the yield of the components to the organic-inorganic powder and to obtain the same effect as the conventional one with respect to the strength and dimensional stability of the molded product with the minimum addition amount.

[0048]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In addition, "part" in an Example means a "mass part."

[0049]

Example 1 960 parts of Polymeric MDI (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Cosmonate M-50) in a 1-liter separable flask and methoxy-terminated polyethylene glycol (produced by NOF CORPORATION, trade name) : 30 parts of Uniox M550 and lactic acid (Wako Pure Chemical Industries, Ltd.)
(Manufactured by Mitsui Chemical Co., Ltd.), and the mixture was stirred for 2 hours while keeping the internal temperature at 80 ° C under a nitrogen stream. The resulting reaction product (hereinafter referred to as "A-1")
Has a viscosity of 290 mPa · s / 25 ° C. and an NCO content of 29.5%.

The reaction product (A-1) was added to distilled water to a concentration of 1%, and the mixture was stirred at 1200 rpm for 1 minute using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.),
An emulsion was obtained. The pH was 6.7. This emulsion was used as a streaming potential colloid titrator MODEL manufactured by MuTEC.
The surface charge was measured using PCD-03. The titer of 1 / 400N poly (diallylmethylammonium chloride) solution at this time was 10.2 μeq / g. This indicates that the charge on the surface of the emulsified particles is an anion.

Unbleached kraft pulp (manufactured by Nippon Paper Industries Co., Ltd.)
2% slurry was subjected to beater treatment (beating) according to the Canadian Standard Freeness (freeness) measuring method described in JIS P8121 until the value reached 350 ml. The reaction product (A-1) was added dropwise to the slurry so that the dry pulp content was 5%, and the mixture was emulsified by stirring. Next, polyaluminum chloride (produced by Sumitomo Chemical Co., Ltd.) was added in an amount of 1% per dry pulp in terms of Al ₂ O ₃ . The pH of the slurry at this time is 6.4.
Met. This slurry was put into a paper making apparatus so that the weight of the slurry would be 50 g / m ^2, and a filtration operation was performed using a 60 mesh net.

The strained paper was dried, and nitrogen in the paper was analyzed by the Kjeldahl nitrogen analysis method to measure the yield of the polymeric MDI. The result was 91.0%. In addition,
The yield was calculated by the following formula.

[0053]

[Equation 1]

[0054]

[Comparative Example 1] 970 parts of Polymeric MDI (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Cosmonate M-200) and a methoxy-terminated polyethylene glycol (manufactured by NOF Corporation, trade name) in a 1-liter separable flask. : UNIOX M550) (30 parts) was added, and the mixture was stirred and mixed for 2 hours while keeping the internal temperature at 80 ° C. under a nitrogen stream. The obtained reaction product (hereinafter referred to as "B-1") has a viscosity of 230 mPa · s /.
At 25 ° C, the NCO content was 30.2%.

The reaction product (B-1) was added to distilled water so as to have a concentration of 1%, and the mixture was stirred at 1200 rpm for 1 minute using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.),
An emulsion was obtained. The pH was 6.7. This emulsion was used as a streaming potential colloid titrator MODEL manufactured by MuTEC.
The surface charge was measured using PCD-03. The titer of the 1 / 400N poly (diallylmethylammonium chloride) solution at this time was 3.5 μeq / g. This indicates that the charges on the surface of the emulsified particles are cations.

Using this reaction product (B-1), Example 1
Paper was made in the same manner as in. The strained paper is dried, nitrogen in the paper is analyzed by the Kjeldahl nitrogen analysis method, and the yield of the polymeric MDI is the same as in Example 1 (however, in the above formula, (B-1) instead of (A-1)). Was used.)
Was measured. The result was 62.4%.

Claims (8)

[Claims] 1. An isocyanate-containing composition for an aqueous binder, characterized in that the anionic isocyanate (A) is contained in an amount of 0.1% by mass or more based on the isocyanate-containing composition. 2. A titer of a poly (diallylmethylammonium chloride) solution containing anionic isocyanate (A) and having a pH of 5 or more and 7 or less by a streaming potential method is 1 to 50 μeq / g. Isocyanate-containing composition for aqueous binder. 3. The isocyanate-containing composition for an aqueous binder comprises the anionic isocyanate (A),
The isocyanate-containing composition for a water-based binder according to claim 1 or 2, comprising an unreacted isocyanate (B) and a nonionic compound (C) having a surface active action. 4. The anionic isocyanate (A)
Is a modified form of polymeric MDI, and the isocyanate-containing composition for aqueous binders according to any one of claims 1 to 3, wherein 5. The anionic isocyanate (A) is a polymeric MDI having an anionic functional group,
The unreacted isocyanate (B) is a polymeric MDI
The isocyanate-containing composition for an aqueous binder according to any one of claims 1 to 4, wherein 6. The isocyanate-containing composition for an aqueous binder according to claim 4 or 5, wherein the isocyanate-containing composition for an aqueous binder is used for a board. 7. The isocyanate-containing composition for an aqueous binder according to claim 2, wherein the titer is 5 to 40 μeq / g. 8. An isocyanate-containing composition for an aqueous binder is a solid component obtained by mixing at least an aqueous slurry of organic-inorganic powder and granules, an emulsion dispersion of the isocyanate-containing composition for an aqueous binder, and a cationic flocculant. The composition according to any one of claims 1 to 7, which is a composition used for a molded body obtained by filtering the obtained mixture after heating, and heating and drying the solid component. Isocyanate-containing composition for binder.