JP2002037845A - Polyisocyanate polyaddition product, and dispersion agent and dispersion liquid by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyisocyanate polyaddition product which disperses well pigments or the like having a very fine average particle size, and to provide a dispersion agent and dispersion liquid by using the same. SOLUTION: A polyisocyanate compound containing an average of 3.5-8 isocyanate group is reacted with a polymer having univalent OH group, polymerdiol, monohydric alcohol in a specific composition. The polyisocyanate is obtained by reacting all residual isocyanate groups with a compound containing both active hydrogen and tertiary amino group in the molecule. The dispersion agent and dispersion liquid by using the same are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention resides in a novel polyisocyanate polyadduct and its use. Specifically, the present invention is capable of dispersing solid fine particles such as a pigment in an organic solvent or a synthetic resin compound. A novel polyisocyanate polyaddition compound useful as a dispersant, and a dispersion in which solids such as various pigments using the same are well dispersed.

[0002]

2. Description of the Related Art In order to uniformly disperse solid fine particles such as pigments in a liquid such as water or an organic solvent, or in a resin solution containing a high molecular compound such as a synthetic resin or the like, usually, agglomeration is required. It is necessary to disperse the particles obtained in a state into the primary particles with a strong shearing force and at the same time prevent the particles from reaggregating.

In order to achieve such an object, a dispersant is generally added. For example, JP-A-2-8212 discloses that a tertiary amine having an isocyanate group and an active hydrogen group, and a monofunctional or polyfunctional polyether having a hydroxyl group and a polyester are reacted in an equivalent amount or less. A polyisocyanate polyadduct and a dispersant using the same are described. In addition, Tokuhei 2-1
No. 9844 and Japanese Patent Publication No. 6-192 disclose a long-chain compound having a monofunctional hydroxyl group and a long-chain compound having a polyfunctional hydroxyl group, and a nitrogen-containing basic group having an active hydrogen atom as an isocyanate group. And polyisocyanate polyadducts obtained by an equivalent reaction, and a dispersant using the same.

[0004]

In recent years, in dispersions in which solid fine particles such as pigments are dispersed, the diameter of the solid fine particles to be dispersed has been remarkably reduced, and it has become difficult to achieve good dispersion. For example, pigments used in the production of pigment dispersions for optical applications, such as color resists used for producing color filters for liquid crystal screens, have an average particle size of 1 μm or less, and often 0.1
μm or less, making it difficult to produce a good dispersion.

On the other hand, it has been generally known that the selection of a dispersant has a different optimum composition depending on specific particles, solvents, and the like. Even when used as a dispersant for production, there is a problem that the viscosity is remarkably increased and the product cannot be used.

[0006]

Means for Solving the Problems As a result of intensive studies in view of such a situation, the present inventors focused on a polyisocyanate polyadduct used as a dispersant, and in the production method of this polyisocyanate polyadduct, By performing a reaction with a specific ratio of isocyanate groups in the step, and adding a specific production step, a polyisocyanate polyadduct of a specific composition can be obtained. The present inventors have found that pigments having a fine average particle size can be dispersed well and have completed the present invention.

Specifically, in the method for producing a polyisocyanate polyadduct, the isocyanate group in each of the following steps (A), (B) and (D) for producing a polyisocyanate polyadduct Characterized in that the reaction rate with the polyisocyanate is specific, and the step (C) is provided between the steps (B) and (D), thereby obtaining a polyisocyanate polyadduct having good dispersing performance. Is found.

That is, the gist of the present invention is that a polyisocyanate compound having an average of 3.5 to 8 isocyanate groups as a starting material and a polyisocyanate polyaddition obtained through the following steps (A) to (D): Exists in the compound. (A) a step of reacting a starting material polyisocyanate with an amount of a compound having one hydroxyl group that reacts with 15 to 40 equivalent% of all isocyanate groups. (B) the product of step (A) and 10 to 3 of the total isocyanate groups of the starting polyisocyanate in the product;
A step of reacting a compound having two hydroxyl groups with an amount which reacts with an isocyanate group which is 0 equivalent%. (C) the product of step (B) and from 5 to 60 of all isocyanate groups of the starting polyisocyanate in the product;
Carbon equivalent in an amount equivalent to 80% by weight or less of the total isocyanate groups of the starting material polyisocyanate in the amount equivalent to the total isocyanate groups reacted in the steps (A) and (B). A step of reacting with a substituted or unsubstituted alcohol represented by Formulas 1 to 10. (D) a step of reacting the product of step (C) with an active hydrogen and a compound containing a tertiary amino group in the same molecule in an amount that reacts with all the isocyanate groups in the product.

Still another aspect of the present invention resides in a dispersant containing the above-mentioned polyisocyanate polyadduct and a dispersion containing the polyisocyanate polyadduct and a particulate or fibrous solid.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

In the polyisocyanate compound having an average of 3.5 to 8 isocyanate groups in the present invention, the average number of the isocyanate groups of the polyisocyanate compound is preferably 4 to 6 on average. For example, a polyisocyanurate compound in which an isocyanurate ring is introduced (isocyanuration reaction) by trimerization of a polyisocyanate compound, an isocyanate group-terminated polyurethane polyisocyanate compound obtained by reacting a diisocyanate compound with a polyfunctional active hydrogen compound, Examples include a polyurea polyisocyanate compound, polymeric isocyanate, and diphenylmethane diisocyanate. Among them, a polyisocyanurate compound having an isocyanurate ring introduced by trimerization of the polyisocyanate compound is preferable.

As the polyisocyanate compound used in the production of the polyisocyanurate compound, any polyisocyanate compound may be used, and examples thereof include aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds. No.

Examples of the aliphatic diisocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, and lysine diisocyanate.

The alicyclic diisocyanate compounds include, for example, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate,
And hydrogenated diphenylmethane diisocyanate.

Examples of the aromatic diisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate,
4'-diphenylmethane diisocyanate, 2,4'-
Diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5- Diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, α,
α, α ′, α′-tetramethylxylylenediisocyanate, polyphenylenepolymethylene polyisocyanate, carbodiimide-modified 4,4′-diphenylmethane diisocyanate, uretonimine-modified and the like.

Among these polyisocyanate compounds, those having a cyclic structure, such as aromatic diisocyanate compounds and alicyclic diisocyanate compounds, are preferred. Particularly, isophorone diisocyanate, hydrogenated tolylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate and the like are preferred.

The polyisocyanurate compound may be produced by a conventionally known production method, for example, by reacting a diisocyanate compound in the presence of an isocyanuration catalyst. Conventionally known isocyanuration catalysts can be used, and specific examples thereof include 2,2.
4,6-tris (dimethylaminomethylphenol),
Tertiary amines such as triethylamine, N, N ′, N ″ -trisdimethylaminopropylhexahydrotriazine, tetraalkylalkylenediamine, diazabicyclooctane and lower alkyl substituted products thereof, tertiary amine and ethyl alcohol, Co-catalysts such as substituted carbamates, aldehydes, alkylene oxides, alkylene imines, ethylene carbonate, 2,3-butanedione, etc., tertiary alkyl phosphines, quaternaries such as tetramethyl ammonium, tetraethyl ammonium, tetrabutyl ammonium Alkyl ammonium hydroxide, trimethylhydroxypropylammonium, trimethylhydroxyethylammonium Quaternary ammonium salts such as kill ammonium hydroxide and the like.

Other specific examples of the isocyanuration catalyst include alkali metal salts of imides such as potassium phthalimide; quaternary onium hydroxy compounds of N, P, As, and Sb; onium hydroxy compounds of S or Se. Onium compounds, alkyl-substituted ethylene imines such as N-methylethylene imine, potassium acetate, sodium acetate, lead 2-ethylhexanoate, sodium benzoate,
Epoxy compounds, epoxy compounds, metal salts of carboxylic acids such as potassium naphthenate, magnesium naphthenate, oxides, hydroxides, carbonates of alkali metals and alkaline earth metals, metal salts of enolic compounds and phenols, etc. Tertiary amines, metal salts of aromatic secondary amines in combination with cocatalysts such as sodium salt of diphenylamine, various organic metals such as titanium tetrabutylate and tributylantimony oxide, aluminum chloride, Examples include Friedel-Crafts catalysts such as boron fluoride, chelate compounds of alkali metals such as sodium salicylaldehyde, and metal chelate compounds of β-diketones such as aluminum acetylacetone and lithium acetylacetone.

Among the above isocyanuration catalysts, N,
Tertiary amines such as N ′, N ″ trisdimethylaminopropylhexahydrotriazine and metal salts of carboxylic acids such as sodium acetate, cobalt acetate, potassium naphthenate and magnesium naphthenate are preferred.

The concentration of the isocyanurate catalyst varies depending on the catalyst used and the reaction temperature, but is usually selected from the range of 0.01 to 10% by weight based on the polyisocyanate compound.

In addition to the above catalysts, co-catalysts include aliphatic alcohols such as methanol, ethanol and butanol;
Polyhydric alcohols such as ethylene glycol, 1,3-butanediol, neopentyl glycol, and trimethylolpropane; polyethers such as polypropylene glycol; phenols, secondary amines and imidazoles; Normally, 0.
It is preferable to use them together in an amount of 0.05 to 10% by weight.

Alcohols such as aliphatic alcohols, polyhydric alcohols, and phenols as co-catalysts can be added simultaneously with the isocyanuration catalyst, or they are preliminarily reacted with diisocyanate compounds to form urethane bonds. Thereafter, it is also possible to carry out an isocyanuration reaction.

The reaction temperature for the isocyanuration is usually from 0 to
The temperature is in the range of 200 ° C, preferably 0 to 100 ° C. The isocyanuration reaction may be carried out using a suitable solvent. As the solvent used, inert solvents commonly used in polyurethane production, for example, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone,
Ethyl acetate, butyl acetate, ester solvents such as isobutyl acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate,
3-methyl-3-methoxybutyl acetate, ethyl-
Examples thereof include glycol ether ester solvents such as 3-ethoxypropionate, ether solvents such as tetrahydrofuran and dioxane, and aprotic polar solvents such as N-methylpyrrolidone. One or more of these may be used in any ratio. Can be used. The type of solvent used,
By selecting the amount and the resin concentration, the reaction solution can be adjusted to a viscosity according to the use conditions. The progress of the reaction
The reaction solution can be tracked by measuring the NCO content, infrared spectroscopy, refractive index, and the like.

When the above-mentioned measurement reaches a predetermined isocyanate group content (or isocyanurate conversion rate), the reaction is stopped with a polymerization terminator suitable for the type of catalyst used, and the desired polyisocyanate compound is obtained. Can be obtained.

The reaction terminator used in this case is hydrochloric acid,
Phosphoric acid, inorganic acids such as phosphorous acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, dimethyl phosphate, diethyl phosphate, phosphate esters such as dibutyl phosphate,
Phosphorous esters such as monomethyl phosphite, monoethyl phosphite, monobutyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, methanesulfonic acid, p-toluenesulfonic acid, p-toluene Examples thereof include sulfonic acids such as methyl sulfonate and ethyl p-toluenesulfonate, and alkyl esters thereof, and perfluorinated sulfonic acids such as nonafluorobutanesulfonic acid. The addition amount of the reaction terminator is preferably in the range of an equivalent amount to twice the amount of the added catalyst.

The polyisocyanurate compound may contain a large amount of unreacted monomer depending on the isocyanuration rate, and when the unreacted monomer has an adverse effect, the unreacted monomer may be undesired by thin-film distillation or the like. The reaction monomer may be removed.

In the production of an isocyanate group-terminated polyurethane polyisocyanate compound obtained by reacting a diisocyanate compound with a polyfunctional active hydrogen compound, the diisocyanate compounds described above as diisocyanate compounds, and a modified buret thereof, uretonimine Modified products, carbodiimide modified products and the like can also be mentioned. These may be used alone or in combination of two or more at an arbitrary ratio.

Examples of the polyfunctional active hydrogen compound used in the production of the isocyanate group-terminated polyurethane polyisocyanate compound include polyfunctional hydroxy compounds. Specifically, glycerin, trimethylolpropane, trimethylolethane, 1,2,2 Polyhydric alcohols having three or more functional groups such as 6-hexanetriol, 2-hydroxyethyl-1,6-hexanediol, 1,2,4-butanetriol, erythritol, sorbitol, pentaerythritol, dipentaerythritol; ethylene glycol; Diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1 3-propane diol, 2,2
-Diethyl-1,3-propanediol, 2-methyl-
2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2, 4-pentanediol, 1,6-
Hexanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1, 8-octanediol, 1,9-nonanediol, 2-methyl-1,8-
Aliphatic glycols such as octanediol; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene. .

Description of Step (A) As the compound having one hydroxyl group to be reacted with the polyisocyanate compound in Step (A) of the present invention, any compound can be used. Examples thereof include polyether glycol, polyester glycol, and polycarbonate. It is preferable to use high molecular compounds in which one terminal hydroxyl group such as glycol and polyolefin glycol is alkoxylated with an alkyl group having 1 to 10 carbon atoms. Among them, polyethers represented by the following general formula (I) are preferred. R1O- (x) nH (I) (where, R1 represents a C1-C8 alkyl group, X represents an alkylene oxide group having 2-10 carbon atoms, and n represents 5
To 300. Examples of the polyethers represented by the general formula (I) include methoxylated polyethylene glycol at one end, ethoxylated polyethylene glycol at one end, polyethylene glycol at one end, butoxylated polyethylene glycol at one end, and methoxylated polypropylene at one end. Glycol, ethoxylated polypropylene glycol at one end,
One-terminal propoxylated polypropylene glycol, One-terminal butoxylated polypropylene glycol, One-terminal methoxylated polyoxytetramethylene glycol, One-terminal ethoxylated polyoxytetramethylene glycol, One-terminal propoxylated polyoxytetramethylene glycol, One-terminal butoxylated polyoxy Tetramethylene glycol and the like.

The number average molecular weight of the compound having one hydroxyl group in the step (A) is arbitrary, but is usually 500 or more.
It is preferably 700, and if the number average molecular weight is too small, the effect as a dispersant may be reduced when the polyisocyanate polyadduct is used as a dispersant. The upper limit of the number average molecular weight is also arbitrary, but is usually 5,000 or less, preferably 4,000 or less. If it is too large, the viscosity is remarkably increased during the production of the polyisocyanate polyadduct, or the effect when used as a dispersant. May decrease. For this reason, the number average molecular weight is preferably from 500 to 5,000, particularly preferably from 700 to 4,000.

The compound having one hydroxyl group is used in an amount which reacts with the polyisocyanate compound as a starting material and 15 to 40% by weight of the isocyanate group in the compound.
It is preferable to react 0 to 35 equivalent% with an amount which reacts. If the amount of the compound having one hydroxyl group is small, the effect when the polyisocyanate polyadduct is used as a dispersant may be reduced. Conversely, if the amount is too large, the viscosity is significantly increased during the production of the polyisocyanate polyadduct. Or the effect when used as a dispersant may be reduced.

Description of Step (B) As the compound having two hydroxyl groups in step (B) of the present invention, high molecular diols are preferable, and specifically, for example, polyether glycols, polyester glycols, polycarbonate glycols, Examples include polyolefin glycols and the like, and mixtures containing two or more of these. Among them, polyether glycols are preferable, and particularly those represented by the following general formula (II) are preferable. HO- (Y) mH (II) (where Y represents an alkylene oxide group having 2 to 10 carbon atoms, and m represents 5 to 300.) Polyether glycols represented by the general formula (II) Examples thereof include those obtained by homo- or copolymerization of an alkylene oxide, specifically, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyocta. Methylene glycol and mixtures of two or more thereof. Among them, polyethylene glycol, polypropylene glycol, polyoxytetraethylene glycol and the like are preferable.

The number average molecular weight of the compound having two hydroxyl groups in the step (B) is optional, but is usually 500 or more, preferably 700. If the number average molecular weight is too small, the polyisocyanate polyadduct may be used as a dispersant. When used as a dispersant, the effect as a dispersant may be reduced. The upper limit of the number average molecular weight is also arbitrary, but is usually 5,000 or less,
It is preferably at most 4,000, and if it is too large, the viscosity may be significantly increased during production of the polyisocyanate polyadduct, or the effect when used as a dispersant may be reduced. For this reason, the number average molecular weight is preferably from 500 to 5,000, particularly preferably from 700 to 4,000. Further, it is preferable that the number average molecular weight is not more than twice the number average molecular weight of the compound having one hydroxyl group in the above-mentioned step (A), because the dispersion performance of the polyisocyanate polyadduct finally improves. .

In the step (B), one of the isocyanate groups in the polyisocyanate compound as a starting material is used.
The compound having two hydroxyl groups is reacted with the product of step (A) in an amount to react with 0 to 30 equivalent%, preferably 10 to 25 equivalent%. If the amount of the compound having two hydroxyl groups is small, the effect when the polyisocyanate polyadduct is used as a dispersant may be reduced. Conversely, if the amount is too large, the viscosity is significantly increased during production of the polyisocyanate polyadduct. Or the effect when used as a dispersant may be reduced.

Description of Step (C) As the substituted or unsubstituted alcohol having 1 to 10 carbon atoms in step (C), any alcohol can be used. Specifically, for example, methanol, ethanol, propanol, isopropanol, butanol Pentanol, hexanol, heptanol, octanol, decanol and the like. Among them, those represented by the following general formula (III) are preferred, and methanol, ethanol, propanol and butanol are particularly preferred.

R2-OH (III) (where R2 represents an alkyl group having 1 to 6 carbon atoms) In the step (C), 5 to 60 equivalents of an isocyanate group in a polyisocyanate compound as a starting material. %
And reacts with isocyanate groups in an amount such that the sum of the isocyanate groups reacted in the above-mentioned steps (A) and (B) is 80 equivalent% or less of the total isocyanate groups of the polyisocyanate compound as a starting material. An amount of a substituted or unsubstituted alcohol having 1 to 10 carbon atoms is reacted. If this condition is satisfied, the reaction amount is arbitrary, but is preferably 10 to 50 equivalent% of the isocyanate group in the polyisocyanate compound as a starting material. If the amount is small, the viscosity may increase during the production of the polyisocyanate polyadduct, and the effect when the polyisocyanate polyadduct is used as a dispersant may decrease.
Conversely, if the amount is too large, the effect when the polyisocyanate polyadduct is used as a dispersant may be reduced.

What is important in the step C is to react the product of the step (B) with an alcohol, which is obtained if an amine such as n-butylamine is reacted instead of the alcohol. The viscosity of the dispersant solution using the polyisocyanate polyadduct increases significantly. The reason for this is not clear, but the hydrogen bonding force between the urea bonds generated by the reaction between the amine and the isocyanate group is stronger than the hydrogen bonding force between the urethane bonds generated by the reaction between the alcohols and the isocyanate group. Therefore, the viscosity may increase, and the strong hydrogen bonding force between the urea bonds may cause crystallization in some cases.

Description of Step (D) In the step (D), examples of the compound containing an active hydrogen and a tertiary amino group in the same molecule include those having an active hydrogen-containing group as the active hydrogen. For example, these groups include functional groups such as a hydroxyl group, an amino group, and a thiol group, and among them, an amino group, particularly a primary amino group, is preferable.

The tertiary amino group includes, for example, a dialkylamino group, a nitrogen-containing heterocyclic ring and the like, and particularly preferably a dimethylamino group, a diethylamino group, an imidazole group and the like. As the compound containing active hydrogen and a tertiary amino group in the same molecule, a compound represented by the following general formula (IV) is particularly preferable. H2N-R3-Z (IV) (where R3 represents an alkylene group having 2 to 6 carbon atoms, and Z represents a nitrogen-containing heterocyclic group or dialkylamino group having 1 to 10 carbon atoms.) Table represented by the general formula (IV) In the compounds to be prepared, examples of the dialkylaminoamine include N, N-dimethyl-1,3
-Propanediamine, N, N-diethyl-1,3propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N , N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N-dibutylethylenediamine, N, N-
Dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,
4-butanediamine, N, N-dibutyl-1,4-butanediamine and the like.

In the compound represented by formula (IV), the nitrogen-containing heterocycle having 1 to 10 carbon atoms includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring,
5-membered nitrogen-containing heterocyclic ring such as benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring And a nitrogen-containing 6-membered heterocyclic ring. Among them, an imidazole ring or a triazole ring is preferable.

Examples of the amino compounds having a nitrogen-containing heterocycle include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1,2,2. 4-triazole, 3-amino-5-phenyl-1H-1,3,4-triazole, 5
-Amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

Of the compounds represented by formula (IV), 1- (3-aminopropyl) imidazole and N, N-dimethylaminopropanediamine are particularly preferred.

The specific production recipe in the method for producing a polyisocyanate polyadduct of the present invention may be performed according to a known method for producing a polyisocyanate polyadduct. Solvents used in the method for producing a polyisocyanate polyadduct are usually acetone, methyl ethyl ketone, methyl isobutyl ketone, silopentanone, cyclohexanone, ketones such as isophorone, ethyl acetate,
Esters such as butyl acetate and cellosolve acetate, hydrocarbons such as benzene, toluene, xylene and hexane, ethers such as tetrahydrofuran, diethyl ether, ethylene glycol diethyl ether and diethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, propylene Glycol monomethyl ether acetate, ether acetates such as diethylene glycol monomethyl ether acetate, dimethylformamide, N-methylpyrrolidone, aprotic polar solvents such as dimethyl sulfoxide and the like, and these may be used alone or in combination of two or more at an arbitrary ratio May be. In these solvents, the boiling point is 100-200.
C, preferably in the range of 120 to 170C.

In the reaction with the isocyanate group in each step, a catalyst or the like may be used if necessary. For example, examples of the catalyst include tertiary amine catalysts such as triethylamine and dimethylaniline, and metal catalysts such as tin and zinc.

Although the number average molecular weight of the polyisocyanate polyadduct of the present invention is arbitrary, the number average molecular weight in terms of polystyrene is 2,000 to 40,000, among which 4,000 to 4,000.
It is preferably 20,000. If the number average molecular weight is low, the effect when used as a dispersant may be reduced,
On the other hand, if it is too large, the viscosity may increase during the production of the polyisocyanate polyadduct, and the effect when used as a dispersant may decrease.

When the polyisocyanate polyadduct of the present invention is used as a dispersant, the above-mentioned reaction product of the polyisocyanate polyadduct can be used as it is as a dispersant, or it can be used as a dispersant. You may use what added the additive. In this dispersion, the concentration of the polyisocyanate polyadduct (solid content), which is a solid content, is arbitrary, but is usually 10 to 60 wt%, preferably 15 to 50 wt%. In addition, the viscosity of the dispersion may be appropriately adjusted depending on the situation where the dispersion is used.
00 mPa · sec is practically suitable.

In the dispersion using the polyisocyanate polyadduct of the present invention as a dispersant and containing a particulate or fibrous solid, the concentration of these solids is optional.
Usually, it is 2 to 50% by weight, preferably 5 to 30% by weight. The viscosity of the dispersion may be appropriately adjusted depending on the situation in which it is used, for example, by adding propylene glycol monomethoxy acetate or the like.

The solid used in the dispersion generally has a particle size of 5 to 0.001 μm, preferably 0.5 to 0.01 μm.
And the shape is arbitrary such as granular, fibrous, or plate-like. Specifically, pigment fine particles such as anthraquinone pigments, perylene pigments, azo pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; abrasive particles such as alumina, silica, titania, and chromium oxide; , Graphite, titanium black and the like.

Dispersions produced by using the polyisocyanate polyadduct of the present invention as a dispersant, such as pigment inks, enable a high degree of dispersion of pigment particles and lower the viscosity of inks, and are used as paints and printing inks. Excellent in smoothness, gloss, and chromaticity. In addition, it is possible to disperse ultrafine pigments for optical applications, which are usually difficult to disperse, and it is possible to significantly improve the performance of color filters for various displays and the like.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention.

The content and molecular weight of free isocyanate in the following Examples and Comparative Examples were measured by the methods described below. The evaluation of the dispersant solution containing the polyisocyanate polyadduct obtained in each of Examples and Comparative Examples was performed in Evaluation Tests 1 to 3 described later, and the results are summarized in Table 1. [Method for measuring free isocyanate content] 1 / 2N-di-n
-Analyte (prepolymer) is collected in a stoppered Erlenmeyer flask containing 20 ml of a butylamine / toluene solution,
Back titration was performed with a 1 / 2N-HCl aqueous solution. [Measurement Method of Viscosity] The viscosity of the dispersant solution was measured using a rotational viscometer (DV-III + manufactured by Brookfield) at a rotation speed of 20 rpm and a standard rotor at 25 ° C. [Molecular Weight Measurement Method] The molecular weight of the obtained polyisocyanate polyadduct was measured by preparing a LiBr / NMP solution,
PC device HLC8120 (manufactured by Tosoh Corporation), column sup
The number average molecular weight in terms of standard polystyrene was determined as the molecular weight at 80 ° C. using erHM-L.

Example 1 A trimer of tolylene diisocyanate (Mitec G, manufactured by Mitsubishi Chemical Corporation) under a nitrogen atmosphere
P770A, resin solid content 49 wt%, butyl acetate solution,
The average isocyanate group per molecule is 4.1 (isocyanate group content is 7.8% by weight), 440 g, dibutyltin dioctoate as catalyst, 1.1 g, and sufficiently dehydrated PGMEA (propylene glycol) as solvent 912 g of monomethyl ether acetate)
The mixture was heated and dissolved at 0 ° C. for 30 minutes.

Then, under stirring, polyethylene glycol (Uniox M-2000, manufactured by NOF Corporation) 400 having a methoxy group at one end and a number average molecular weight of 2,000.
g, and the isocyanate group content is 1.5% of the theoretical remaining amount.
The reaction was carried out at 70 ° C. for 2 hours until the amount became wt% (step (A)).

Then, polypropylene glycol having a number average molecular weight of 1,000 (manufactured by Sanyo Chemical Co., Ltd., Sannics PP)
(-1000), and the reaction was carried out at 80 ° C. for 2 hours until the isocyanate group content reached 1.0 wt% of the theoretical remaining amount (step (B)).

Next, n-propanol (PrOH) 9.
5 g was added, and the isocyanate group content was 0.1% of the theoretical remaining amount.
The reaction was carried out at 40 ° C. for 1.5 hours until the content became 6 wt% (step (C)).

Finally, aminopropylimidazole (AP
I) 32.5 g was added and reacted at 40 ° C. for 1 hour,
All remaining isocyanate groups were reacted (step (D)).

From the above steps, a solution containing a polyisocyanate polyadduct having a solid content of 40 wt% (dispersant solution)
I got The viscosity of the dispersant solution was 1,730 mPa · sec, and the polystyrene reduced number average molecular weight of the polyisocyanate polyadduct was 7,800.

Example 2 The amount of PGMEA used in the reaction was 1085 g, the amount of polyethylene glycol was 520 g,
The amount of PrOH was changed to 8.3 g, the isocyanate group was reacted up to the theoretical reaction amount, and in step (D), A
The reaction was carried out in the same manner as in Example 1 except that the PI amount was changed to 27.5 g, to obtain a dispersant solution having a solid content of 40 wt%. The viscosity of this dispersant solution is 2000 mPa · sec.
Met.

Example 3 The amount of PGMEA used in the reaction was 1143 g, the amount of polyethylene glycol was 560 g,
The amount of PrOH was changed to 5.9 g, and isocyanate groups were respectively reacted to the theoretical reaction amount.
The reaction was carried out in the same manner as in Example 1 except that the amount of PI was changed to 30 g, to obtain a dispersant solution having a solid concentration of 40 wt%. The viscosity of this solution was 2880 mPa · sec.

Example 4 Except that the amount of PGMEA used in the reaction was 1255 g and the amount of polyethylene glycol was 640 g, the isocyanate group was reacted up to the theoretical reaction amount, and the amount of API was changed to 25 g in step (D). The reaction was carried out in the same manner as in Example 3, and the solid content concentration was 40
A wt% dispersant solution was obtained. The viscosity of this dispersant solution is 4
080 mPa · sec.

Example 5 The amount of PGMEA used in the reaction was 537 g, and polyethylene glycol was used as a polyethylene glycol (A) having a molecular weight of 750 and a methoxy group at one end.
The reaction was carried out in the same manner as in Example 1 except that the isocyanate group was reacted until the theoretical reaction amount was changed to 150 g, and a dispersant solution having a solid concentration of 40 wt% was obtained. The viscosity of this dispersant solution is 840 mPa · se
c.

Example 6 The amount of PGMEA used in the reaction was 903 g, and the amount of PrOH was 9.7 g. The isocyanate group was reacted to the theoretical reaction amount, and dimethylaminopropylamine was used in place of the API in step (D). The reaction was carried out in the same manner as in Example 1 except that 26.5 g of (DMPA) was used to obtain a dispersant solution having a solid content of 40 wt%. The viscosity of this dispersant solution is 1320 mPa · se
c.

Example 7 Mitec GP750A manufactured by Mitsubishi Chemical Corporation as a trimer of tolylene diisocyanate
(Resin solid content 50 wt%, butyl acetate solution, average isocyanate group per molecule is 5.8 (isocyanate group content is 7.8% by weight)) 630 g, 3600 g of PGMEA to be added, PrOH The NCO group was reacted up to the theoretical reaction amount as 9.7 g, and the API amount was 75.2.
The reaction was carried out in the same manner as in Example 1 except that the amount was changed to g, to obtain a dispersant solution having a solid content concentration of 20 wt%. The viscosity of this dispersant solution was 612 mPa · sec.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that the amount of PGMEA used in the reaction was changed to 928 g, the amount of API was changed to 52.5 g, and the step (C) was not performed. After the addition of the API in the step (D), the reaction solution gelled and showed no fluidity, and no dispersant solution was obtained. Comparative Example 1 is out of the scope of the present invention in that PrOH is not used (the step (C) is not performed).

Comparative Example 2 A reaction was carried out in the same manner as in Example 5 except that the amount of PGMEA used in the reaction was changed to 553 g, the amount of API was changed to 52.5 g, and the step (C) was not performed. After adding the API in step (D), the reaction solution gelled and did not show fluidity, and no dispersant solution was obtained. Comparative Example 2 is out of the scope of the present invention in that PrOH was not used (the step (C) was not performed).

Comparative Example 3 The amount of PGMEA used in the reaction was 1543 g, the amount of polyethylene glycol was 840 g,
The reaction was carried out in the same manner as in Example 1 except that the amount of PrOH was changed to 2.4 g and the isocyanate group was reacted up to the stoichiometric amount, and the amount of the API used in the step (D) was changed to 20 g. After adding the API in step (D), the reaction solution gelled and did not show fluidity, and no dispersant solution was obtained. Comparative Example 3 is out of the scope of the present invention in that the reaction rate of the isocyanate group after completion of the step (C) is 81%, which is out of the range of "80 equivalent% or less" which is the scope of the present invention.

Comparative Example 4 The amount of PGMEA used in the reaction was 635 g, the amount of polyethylene glycol was 200 g,
The reaction was carried out in the same manner as in Example 1 except that the amount of PrOH was changed to 7.2 g and the isocyanate group was reacted up to the theoretical reaction amount, and the amount of the API used in step (D) was changed to 50 g. A dispersant solution having a concentration of 40 wt% was obtained. The viscosity of this dispersant solution was 3330 mPa · sec. In Comparative Example 4, the reaction rate of the isocyanate group after the completion of the step (A) was low, which was within the range of the present invention from "15 to 40".
It is outside the scope of the present invention in that it is out of "equivalent%".

Comparative Example 5 The amount of PGMEA used for the reaction was 1180 g, the amount of polyethylene glycol was 600 g,
The reaction was carried out in the same manner as in Example 1 except that the amount of PrOH was changed to 18 g and the isocyanate group was reacted up to the theoretical reaction amount, and the amount of the API used in step (D) was changed to 2.5 g. A dispersant solution having a concentration of 40 wt% was obtained. The viscosity of this solution was 1400 mPa · sec. In Comparative Example 5, the conversion of the isocyanate group after the completion of the step (C) was 98 equivalent%, which is within the scope of the present invention "80".
It is out of the scope of the present invention in that it is out of "equivalent%".

[Comparative Example 6] In the step (C), Pr-O
The reaction was carried out in the same manner as in Example 1 except that 11.7 g of n-butylamine was used instead of H, and the solid content was 40 g.
A wt% dispersant solution was obtained. The viscosity of this solution is 3530
mPa · sec. Comparative Example 6 was outside the scope of the present invention because an alkylamine was used without using a substituted or unsubstituted alcohol having 1 to 10 carbon atoms.

Comparative Example 7 The amount of Pr-OH used in the reaction was 1.3 g, and the amount of API in step (D) was 92.0 g.
The reaction was carried out in the same manner as in Example 7 except that the amount was changed to 5 g. After adding the API in step (D), the reaction solution gelled and did not show fluidity, and no dispersant solution was obtained. Comparative Example 7 was prepared using Pr- used in step (C).
This is outside the scope of the present invention in that the isocyanate group reaction equivalent in the step (C) is out of the range of “5 to 60 equivalent%”, which is within the scope of the present invention, because the OH content is small.

[Evaluation Test 1] 10 parts of Pigment Green PG36 as a pigment and Solsperse S as a dispersing aid
12000 (manufactured by Zeneca Corp.), and 4 parts by weight of the dispersant solution obtained in Examples 1, 2, 4 and Comparative Examples 4 to 7 in terms of solid content with respect to the pigment. And PGMEA as a solvent was added so that the total amount was 60 parts to obtain a mixture. The mixture was placed in a metal cylindrical container together with 120 g of 0.5 mmφ zirconia beads, and dispersed in a paint shaker for 8 hours to prepare a pigment ink. The viscosity of the obtained ink was measured. Table 1 shows the results. Similarly, commercially available dispersants BYK161, BYK170, BY
The same dispersion was performed using K182 (both manufactured by Big Chemie Co., Ltd.). Table 1 shows the results.

[Evaluation Test 2] Pigment Yellow PY150 (10 parts) was used as a pigment, and the dispersant solution obtained in Examples 1, 3 to 6 and Comparative Examples 4 and 5 was 5 parts by weight based on the solid content of the pigment. And PGMEA as a solvent was added so that the total amount was 60 parts to obtain a mixture. The mixture was placed in a metal cylindrical container together with 120 g of 0.5 mmφ zirconia beads, and dispersed in a paint shaker for 4 hours to prepare a pigment ink. The viscosity of the obtained ink was measured. Table 1 shows the results. In the same manner, the same dispersion was carried out using the aforementioned commercially available dispersants BYK161, BYK170 and BYK182. Table 1 shows the results.

[Evaluation Test 3] Pigment Yellow PY138 (10 parts) was used as a pigment, and the dispersant solutions obtained in Examples 1, 4, 6, and 7 and Comparative Examples 5 and 6 were added to the pigment at a solid content of 5 parts. PGMEA as a solvent was added so as to be 60 parts by weight to obtain a mixture. The mixture was placed in a metal cylindrical container together with 120 g of 0.5 mmφ zirconia beads, and dispersed in a paint shaker for 1 hour to prepare a pigment ink. The viscosity of the obtained ink was measured. Table 1 shows the results.

[0074]

[Table 1]

As is clear from Table 1, the pigment dispersion (ink) using the polyisocyanate polyadduct of the present invention has a very low viscosity as compared with the comparative example, and maintains a good dispersion state. You can see that.

[0076]

EFFECT OF THE INVENTION The polyurethane dispersant of the present invention can increase the degree of dispersion and reduce the viscosity of the ink in the production of pigment inks, especially for fine pigments. The ink dispersed using the dispersant exhibits particularly excellent performance not only in ordinary coating and printing applications but also in optical applications such as color filters.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yuji Soejima 1000-cho, Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Pref. EE056 EQ016 EU026 EU236 FA016 FA046 FD016 FD096 GH01 4J034 AA04 AA06 BA06 BA07 CA02 CA03 CA04 CA05 CA13 CB01 CB03 CB04 CB05 CB07 CC03 CC08 CC12 CC23 CC26 CC29 CC30 CC33 CC34 CC35 CC37 CC39 CC44 CC45 CC52 DB01 CC01 DF02 DG02 DG03 DG04 DG06 DG08 DG09 DG14 GA05 GA23 GA33 GA44 HA02 HA06 HA07 HB06 HB08 HB09 HB11 HB12 HC03 HC09 HC12 HC13 HC17 HC22 HC25 HC26 HC35 HC44 HC45 HC46 HC52 HC61 HC63 HC64 HC67 HC70 HC02 HC02 KB08 JA14 KC13 KC16 KC17 KC18 KC23 KC27 KC35 KD01 KD02 KD03 KD04 KD05 KD07 KD08 KD12 KD15 KD17 KD21 KD22 KD25 KE02 RA17

Claims (7)

[Claims] 1. A polyisocyanate polyaddition compound obtained from a polyisocyanate compound having an average of 3.5 to 8 isocyanate groups as a starting material and obtained through the following steps (A) to (D). (A) A step of reacting a starting material polyisocyanate compound with a compound having one hydroxyl group in an amount that reacts with 15 to 40% by weight of all isocyanate groups. (B) the product of step (A) and 10 to 3 of the total isocyanate groups of the starting polyisocyanate in the product;
A step of reacting a compound having two hydroxyl groups with an amount that reacts with an isocyanate group that is 0 equivalent%. (C) the product of step (B) and from 5 to 60 of all isocyanate groups of the starting polyisocyanate in the product;
Carbon equivalent in an amount equivalent to 80% by weight or less of the total isocyanate groups of the starting material polyisocyanate in the amount equivalent to the total isocyanate groups reacted in the steps (A) and (B). A step of reacting with a substituted or unsubstituted alcohol represented by Formulas 1 to 10. (D) a step of reacting the product of step (C) with an active hydrogen and a compound containing a tertiary amino group in the same molecule in an amount that reacts with all the isocyanate groups in the product. 2. The polyisocyanate polyadduct according to claim 1, wherein the compound having one hydroxyl group is a compound represented by the following general formula (I) and having a molecular weight of 500 to 5,000. R1O- (x) nH (I) (where, R1 represents a C1-C8 alkyl group, X represents an alkylene oxide group having 2-10 carbon atoms, and n represents 5
To 300. ) 3. The polyisocyanate polyadduct according to claim 1, wherein the compound having two hydroxyl groups is a polyether polyol having a molecular weight of 500 to 5000 and represented by the following general formula (II). HO- (Y) m-H (II) (where Y is an alkylene oxide group having 2 to 10 carbon atoms, and m represents 5 to 300) 4. The method according to claim 1, wherein the substituted or unsubstituted alcohol having 1 to 10 carbon atoms in the step (C) is represented by the following general formula (III). Isocyanate polyadduct R2-OH (III) (where R2 represents an alkyl group having 1 to 6 carbon atoms) 5. The compound according to claim 1, wherein the compound containing active hydrogen and a tertiary amino group in the same molecule is a compound represented by the following general formula (IV). The polyisocyanate polyaddition compound according to the above. H2N-R3-Z (IV) (where R3 represents an alkylene group having 2 to 6 carbon atoms, and Z represents a nitrogen-containing heterocyclic group having 1 to 10 carbon atoms or a dialkylamino group.) 6. A dispersant comprising the polyisocyanate polyadduct according to claim 1. 7. A dispersion comprising at least the polyisocyanate polyadduct according to claim 1 and a granular or fibrous solid.