JPH11292961A - Polyglycerol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject derivative having a wide range of miscibility to a resin for dispersing a pigment, having an excellent pigment dispersing property and useful as a dispersing agent for the pigment by making the free hydroxyl groups in a polyglycerol to a specific 3 kinds of states. SOLUTION: This polglycerol derivative is obtained by forming a state in which, among d × free hydroxy groups in a polyglycerol, k × hydroxy groups remain free, n × hydroxy groups bond with a fatty acid and/or a polyester and/or a polyamide through ester linkages, and m × hydroxy groups bond with phosphoric acid through ester linkages [provided that 1<=(n)<=0.5 (d)+2}, (m)=0-5, (k+m+n)=(d)+2]. As the fatty acid and/or polyester and/or polyamide, a polyester of formulae I and II [R<3> is a 2-20C alkylene; R<4> is H, a 1-20C alkyl or the like; R<5> is a 2-20C alkylene or the like; R<6> is a residue obtained by removing 2 hydroxyl groups from a polyalkylene glycol or the like; (a), (b) are each 2-100; sometimes having an ether bond in the above alkyl or alkylene chain] is preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of mixing a pigment with a resin and other raw materials in the production of colored paints, printing inks, copying toners, magnetic tapes, rubber magnets, molded products of color plastics, sealing agents and the like. In addition, the present invention relates to a pigment dispersing compound (pigment dispersant) that can be used for improving pigment dispersibility.

[0002]

2. Description of the Related Art Colored paints, printing inks, copying toners,
Magnetic tapes, rubber magnets, color plastic molded articles, sealing agents, and the like are pigment-containing resin compositions produced by mixing a pigment with resin and other raw materials.

[0003] However, the biggest problem in producing the pigment-containing resin composition in which the pigment is dispersed as described above is that the pigment particles are easily aggregated. This aggregation occurs at the time of dispersing the pigment, dissolving the pigment-containing resin composition, storing the pigment-containing resin composition, or molding color plastics or painting the pigment-containing resin composition.
As a result, the stability of the pigment-containing resin composition in which the pigment is dispersed is reduced, trouble during painting or molding, or gloss, coloring power, sharpness, and color of the finally obtained coating film or product are reduced. It is known that undesired phenomena such as separation, floating, and decrease in mechanical strength occur.

In order to solve the above problems, various pigment dispersants and dispersing agents have been proposed, and attempts have been made to improve pigment dispersion. For example, (a) a method using a nonionic, cationic or anionic surfactant as a dispersant or a dispersant, or a wetting agent such as an aliphatic polycarboxylic acid,
(B) a method of dispersing a pigment by using a bi-affinity substance in which a pigment-affinity substance and a medium-affinity substance are combined as described in British Patent Nos. 1108261, 1159252, and 1346298; A method of using a surfactant such as an alkylsilicone to reduce surface tension to prevent the occurrence of floating, and (d) a method of substituting a conventional pigment itself with a substituent instead of the pigment itself described in JP-A-51-18736. (E) mixing a pigment derivative (also a pigment) having the formula (1) and dispersing the pigment:
No. 82, JP-A-61-174939 and the like, wherein a compound obtained by reacting a polyalkyleneimine with a polyester compound is used as a dispersant;
8-38875, a method using a polyester containing, as an essential component, a unit formed by ring-opening of a lactone compound in a side chain, and using a polyallylamine as an adsorbing portion as a dispersant. , Etc. are known.

[0005]

However, the above (a) to (d)
With the dispersing aid or pigment dispersant used in the method (c), it is difficult to obtain a stable dispersion state of the pigment particles. Further, the pigment derivative having a substituent used in the method (d) has a pigment skeleton and is essentially colored, so that it cannot be used as a general-purpose dispersant for various pigments.

Further, the basic concept of the pigment dispersant related to the method (e) is described in Progress in Organic Ni coatings, Vol. 5 (1977) 237-24.
It is described on page 3 that, as the pigment dispersant, a compound which is solvated with a solvent and has both a side chain portion interacting with a resin involved in film formation and an adsorption portion adsorbed on a pigment is preferable. is there. However, in the method (e), the pigment dispersant obtained by the method described in JP-A-54-37082 specifically includes
Since the side chain portion of the dispersant is composed of a self-condensate of 12-hydroxystearic acid, it has a very low polarity and has a problem that the range of compatible resins is extremely narrow. Furthermore, since polyalkyleneimine having a highly branched structure is used as a component of the adsorbed portion to the pigment, the amino group of the adsorbed portion is susceptible to steric hindrance when adsorbed to the pigment, and is not suitable for dispersibility. That was enough. Also, in the pigment dispersant obtained by the method disclosed in JP-A-61-174939, the component of the portion adsorbed on the pigment is obtained by the method disclosed in the aforementioned JP-A-54-37082. Since a polyalkyleneimine is used in the same manner as the pigment dispersant to be obtained, the amino group in the adsorbed portion is susceptible to steric hindrance, and is insufficient in dispersibility. In addition, Japanese Patent Application Laid-Open No. 08-38 relating to recent developments
Even with the use of the dispersant disclosed in JP-A-875-875, the effect of dispersibility was insufficient.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have introduced an acidic phosphate group and a hydrophobic chain into the side chain of polyglycerin,
A novel compound, a polyglycerin derivative, having a wide range of compatibility with the resin in which the pigment is to be dispersed and having excellent pigment dispersing ability has been found, and the present invention has been completed based on such findings.

That is, the present invention provides a method for preparing polyglycerin d
Out of the free hydroxyl groups, k remain free, n are linked to fatty acids and / or polyesters and / or polyamides via ester linkages, and m are linked to phosphoric acid via ester linkages Polyglycerin derivative (where d, k, m and n are integers satisfying the following relational expressions: 1 ≦ n ≦ 0.
5 (d + 2), m = 0-5, and k + m + n = d +
2) a pigment dispersant containing the polyglycerin derivative as an active ingredient, a treated pigment obtained by treating a pigment with the pigment dispersant, a pigment-containing resin composition comprising the pigment dispersant, a resin and a pigment, and the pigment dispersant; The present invention relates to a paint or an ink composition comprising a pigment and a resin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the above-mentioned polyglycerin derivative of the present invention, that is, a pigment dispersible polyglycerin derivative, and a pigment dispersant, a treated pigment, a pigment-containing resin composition and the like containing the same as an active ingredient will be sequentially described. This will be described in detail.

The polyglycerin derivative of the present invention may be, for example, polyglycerin, a fatty acid and a polyester compound having a free carboxyl group, or a polyamide compound having a free carboxyl group.
After reacting with one or more compounds selected from the group of compounds (ester bond forming reaction) to obtain an intermediate of a polyglycerin derivative, phosphorus pentoxide or phosphorus oxychloride and necessary water are added thereto. The acid phosphate group (-
PO (OH) ₂ ) introduction reaction). More specifically, this polyglycerin derivative is, for example, a polyglycerin having a number average degree of polymerization of 2 to 20, a fatty acid having 6 to 30 carbon atoms, and a free radical represented by the following general formula (I) or (II). Having a carboxyl group of
Polyester can be used alone or in combination of two or more kinds, and further, phosphorus pentoxide or phosphorus oxychloride and necessary water can be used as raw materials. Here, the "necessary water" means, when phosphorus pentoxide is used for introducing the acidic phosphate group, an equimolar amount or less (0 to 1 times mol) of phosphorus pentoxide, and when phosphorus oxychloride is used. , 0 to 2 times the amount of phosphorus oxychloride. The same applies to the following.

[0011]

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In the formula, R ³ is a linear or branched alkylene group having 2 to 20 carbon atoms, R ⁴ is H or an alkyl or alkylene group having 1 to 20 carbon atoms,
⁵ represents a linear or branched alkylene group having 2 to 20 carbon atoms, -C ₆ H ₄ - or -CH = CH-, R ⁶ represents a linear or branched alkylene group having 2 to 20 carbon atoms Or a residue obtained by removing two hydroxyl groups from a polyalkylene glycol, and a and b are each independently 2
Represents an integer of from 100 to 100, and may have an ether bond in the chain.

The polyglycerin derivative of the present invention comprises
(I) a fatty acid, (ii) a polyester in which the repeating units in the above general formulas (I) and (II) are polymerized randomly or in blocks,
(Iii) a polyester of the general formula (I), (iv)
It can be produced by reacting the polyester of the general formula (II) or (v) a combination of two or more of these, and then reacting with phosphorus pentoxide or phosphorus oxychloride and necessary water.

As the polyglycerin used in the present invention, commercially available polyglycerin can be used. For example, "Polyglycerin #" manufactured by Sakamoto Pharmaceutical Co., Ltd.
310 "," polyglycerin # 500 "," polyglycerin # 750 "and the like. Polyglycerin may be synthesized in-house. In this case, glycerin may be synthesized in the presence of a catalyst such as sodium hydroxide, potassium hydroxide, sulfuric acid or the like.
It can be obtained by heating to ~ 250 ° C and performing dehydration condensation. The number average polymerization degree of the polyglycerin used in the present invention may be 2 to 20, but is more preferably 2 to 20.
Is preferred from the viewpoints of pigment dispersibility and coating film properties. The polyglycerin may contain a branched polyglycerin and a cyclic polyglycerin partially condensed at the β-position in addition to the linear polyglycerin condensed at the α-position. In the case of linear polyglycerin having a degree of polymerization of d, the number of free hydroxyl groups including both ends is d + 2, and in the case of cyclic polyglycerin, the number of free hydroxyl groups is d. Thus, the amount of branched and cyclic polyglycerin is as follows. Since the number is small, the number of free hydroxyl groups of the polyglycerin having the degree of polymerization d may be considered to be d + 2.

The fatty acid used for preparing the polyglycerin derivative of the present invention may be a branched or straight-chain saturated or unsaturated monocarboxylic acid. The fatty acid preferably has 6 to 30 carbon atoms, and more preferably has 6 to 20 carbon atoms from the viewpoint of reducing the viscosity. To be specific, caproic acid, enantiic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, myristic acid, behenic acid, palmitic acid, isostearic acid, stearic acid,
Examples include aliphatic monocarboxylic acids such as oleic acid, isononanoic acid, and arachiic acid.

The polyester used for preparing the polyglycerin derivative of the present invention includes the compounds represented by the above-mentioned general formula (I) or (II). Further, in addition to the above, the general formula (I) and the general formula (II)
It is also possible to use a polyester in which the repeating unit is randomly or blockwise polymerized.

The polyester of the general formula (I) can be prepared from a hydroxycarboxylic acid represented by the following general formula (III) or a lactone represented by the following general formula (IV) as a raw material.

More specifically, hydroxy acids, lactones,
Alternatively, it can be produced by adding a polymerization catalyst to a mixture of a hydroxy acid and a lactone and heating the mixture. The reaction temperature is 120
To 220 ° C, preferably 160 to 210 ° C. The reaction time is 0.5 to 72 hours. At this time, if the reaction is performed under a nitrogen stream, a polymer having a large degree of polymerization can be obtained. At this time, the use of a polymerization initiator facilitates the control of the reaction. When lactone is used as a raw material, a monocarboxylic acid as a polymerization initiator can be used in a ratio of 0 to 0.5 mol per 1 mol of lactone.

[0019]

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In the formula, R ³ represents a linear or branched alkylene group having 2 to 20 carbon atoms.

The above-mentioned hydroxy acids include ricinoleic acid, ricinolenic acid, 9- and 10-hydroxystearic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, lactic acid and the like. Also,
A mixture of two or more of these may be used. As a lactone,
ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, 4-methylcaprolactone, 2-methylcaprolactone and the like.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, Quaternary ammonium salts such as benzyltrimethylammonium iodide, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium iodine, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide , Benji In addition to quaternary phosphonium salts such as trimethylphosphonium iodo, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate, potassium benzoate, sodium benzoate, and the like Organic carboxylic acid salts, alkali alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride.

As the polymerization initiator, acetic acid, propionic acid, caprylic acid, nonanoic acid, capric acid, octylic acid,
Monocarboxylic acids such as aliphatic monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isononanoic acid and arachinic acid, and aromatic monocarboxylic acids such as benzoic acid and p-butylbenzoic acid.

The polyester of the general formula (II) can be prepared by reacting a diol represented by the following general formula (V) with a dibasic acid represented by the following general formula (VI).

More specifically, it can be produced by adding a polymerization catalyst to an equimolar mixture of the above diol and dibasic acid and heating. At this time, it is preferable to add the dibasic acid in a slight excess. The reaction temperature is from 120 to 220C, more preferably from 160 to 210C. The reaction time is 0.5
~ 72 hours. At this time, if the reaction is performed under a nitrogen stream, a polymer having a large degree of polymerization can be obtained. At this time, the use of a polymerization initiator facilitates the control of the reaction.

[0026]

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In the formula, R ⁵ is a linear or branched alkylene group having 2 to 20 carbon atoms, —C ₆ H ₄ − or —
CH = CH- and R ⁶ represents a linear or branched alkylene group having 2 to 20 carbon atoms or a residue obtained by removing two hydroxyl groups from polyalkylene glycol.

Examples of the above diol include alkylene glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol. And diols containing an ether bond such as triethylene glycol. As dibasic acids,
Examples include dibasic acids having an unsaturated bond such as maleic acid and fumaric acid, aromatic dibasic acids such as phthalic acid and terephthalic acid, and saturated dibasic acids such as adipic acid and sebacic acid.

As the polymerization catalyst and the polymerization initiator used for the reaction, the same ones as those used for producing the polyester represented by the general formula (I) can be used.

The polyester in which the repeating units of the above general formulas (I) and (II) are randomly polymerized includes hydroxy acid and / or lactone as well as the above-mentioned diol and an equimolar amount of a dibasic acid. It can be produced by adding a polymerization catalyst to a mixture of all four and heating the mixture. The reaction conditions can be the same as in the preparation of the polyester represented by the general formula (I).

Further, the above-mentioned general formula (I) and the above-mentioned general formula (I
The polyester in which the repeating unit (I) is polymerized in the form of a block can be obtained by preparing the polyesters of the general formulas (I) and (II) in advance and then dehydrating and condensing both.

The number average molecular weight of the polyester used in the present invention may be in the range of 100 to 20,000, but is preferably 100 to 10,000, more preferably 500 to 20,000, from the viewpoint of the pigment dispersing performance. 5,000 is most preferred. This is because, when the molecular weight is 20,000 or more, when the polyglycerin derivative of the present invention is used as a pigment dispersant, the length of the side chain of the dispersant is too long, which causes aggregation of the pigment particles, resulting in fluidity. This is to bring about a decrease in In order to obtain a polyester having a molecular weight in the above range, the molar ratio between the polymerization initiator and the starting materials, hydroxy acid, lactone, diol and dibasic acid is appropriately set, and the acid value of the reaction product in the course of the reaction. By observing the appropriate reaction time.

The reaction (ester bond formation reaction) between polyglycerin and a fatty acid and / or polyester introduced into its side chain will be described in detail. One mole of polyglycerin having d + 2 free hydroxyl groups is relative to the fatty acid and free carboxyl groups. Are mixed and reacted at a ratio of 1 mol or more in total, preferably 2 mol or more and 0.5 (d + 2) mol or less from the viewpoint of pigment dispersibility. This reaction proceeds almost quantitatively. As a result, n is the number of ester bonds by fatty acids and / or polyesters, and finally 1 ≦ n ≦ 0.5
(D + 2) polyglycerin derivative of the present invention can be obtained. At this time, different kinds of mixtures of different kinds of fatty acids or different kinds of polyesters may be reacted simultaneously using a mixture of different kinds of fatty acids or a mixture of different kinds of polyesters. A polymerization catalyst may be used for the reaction, and examples of the polymerization catalyst used include those described above in the production of polyester. Further, a solvent such as xylene or toluene may be used for the reaction.

At this time, the reaction between polyglycerin and a fatty acid or / and a polyester having a free carboxyl group is an ester bond forming reaction via the former free hydroxyl group and the latter via a terminal free carboxyl group. Also,
When a polyester is used, transesterification occurs simultaneously depending on the type of the polyester used and the reaction conditions between these esters and the hydroxyl group of the side chain of polyglycerin.

Such an ester bond forming reaction according to the present invention is carried out at 90 to 240 ° C., preferably 100 to 220 ° C.
It is good to perform at ℃ When the temperature is higher than 250 ° C., the reaction product is colored. On the other hand, when the temperature is lower than 90 ° C., the reaction time becomes longer. When the reaction is carried out under a nitrogen stream, a less colored product is obtained.

In the present invention, the acidic phosphate group (-PO (O
H) ₂ ) In the introduction reaction, an intermediate of a polyglycerin derivative (a reaction product of an ester bond formation reaction between polyglycerin and the above fatty acid and / or polyester) is reacted with phosphorus pentoxide, and further, necessary water is reacted. And a method of reacting an intermediate of a polyglycerin derivative with phosphorus oxychloride and further reacting necessary water (phosphorous oxychloride reacts with an intermediate of a polyglycerin derivative to form -OP
Since it exists in the form of OCl ₂ , water is reacted to convert it to an acidic phosphate group —OPO (OH) ₂ ), and an intermediate of a polyglycerin derivative is reacted with phosphorus pentoxide previously reacted with predetermined water. A method of reacting an intermediate of a polyglycerin derivative with phosphorus oxychloride previously reacted with predetermined water, a method of introducing an acidic phosphoric acid group into a hydroxyl group, and a reaction temperature of 20. ~ 20
It is good to carry out at 0 ° C, preferably at 20 to 120 ° C. 200 ° C
If it is above, there are many reaction by-products and the product is colored, while if it is below 0 ° C., the reaction time will be long. When the reaction is carried out under a nitrogen stream, a less colored product is obtained. With respect to 1 mol of polyglycerin (intermediate of the derivative), m is the number of ester bonds by an acidic phosphate group, and phosphorus pentoxide is used in a proportion of m / 2 mol and phosphorus oxychloride is used in a proportion of mmol. Here, m is an integer of 0 to 5. This reaction also proceeds almost quantitatively.

The acid value (mgKOH / g) of the polyglycerin derivative of the present invention is preferably from 5 to 200 in terms of pigment dispersion. The molecular weight of the polyglycerin derivative of the present invention obtained by the above reaction is preferably from 2,000 to 100,000 when used as a pigment dispersant.

The polyglycerin derivative of the present invention has a fatty acid and / or a free carboxyl group after the polyglycerin is first reacted with phosphorus pentoxide or phosphorus oxychloride by reversing the order of the above-described reaction. It can also be obtained by reacting with polyester.

The polyglycerin derivative of the present invention has a property of dispersing a pigment well in a resin or an organic solvent, and thus can be used as a pigment dispersant. When the polyglycerin derivative of the present invention is used as a pigment dispersant, it may contain the organic solvent used during the production of the polyglycerin derivative, and another solvent may be newly added after distilling off the organic solvent used during the production. You can add it. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as n-hexane and n-heptane, ketones such as methyl ethyl ketone and acetone, and esters such as ethyl acetate and butyl acetate. Among them, aromatic hydrocarbons and aliphatic hydrocarbons are preferable.

By treating the pigment with the pigment dispersant of the present invention, a treated pigment can be obtained. Illustrative pigments to be treated with the pigment dispersants of the present invention are carbon black, acetylene black, pine smoke, graphite, ivory black, bone black, pine black,
Titanium dioxide, iron oxide black, manganese black, ilmenite black, yellow lead, cadmium yellow, zinc yellow, cyanamide lead, naples yellow, ultramarine yellow, male yellow, vermilion, cadmium red, antimony red, bengala, ultramarine red,
Ultramarine violet, cobalt violet,
Manganese violet, Prussian blue, cobalt blue, chromium oxide green, Guinea green, chrome green, green earth, patina,
Flower patina, iron oxide yellow, ocher, scena, amber, white carbon, synthetic silicate, amorphous silica, chalk,
Calcium carbonate, calcium sulfate, calcium hydroxide,
Powder, ground powder, talc, silica, glass powder, silica powder, diatomaceous earth, asbestos, wollastonite, calcium silicate, alumina, gypsum, powder with barn powder, barite powder, barium sulfate, barium carbonate, clay Inorganic pigments such as lead suboxide, and azo, diazo, condensed azo, thioindigo, indanthrone, quinacridone, anthraquinone, benzimidazolone, perylene, perinone, phthalocyanine, halogenated phthalocyanine Organic pigments such as organic pigments, anthrapyridine-based pigments, and dioxazine-based pigments.

The pigment dispersant of the present invention comprises,
In particular, it is compatible with inorganic pigments having a surface pH of from neutral to basic, and specifically, titanium dioxide, aluminum hydroxide and the like are good. The iron oxide may be used as a magnetic material such as a magnetic tape for purposes other than pigments,
Since the pigment dispersant of the present invention has a property of dispersing fine particle powder well in a resin or an organic solvent, such iron oxide is included in the pigment in a broad sense in the present invention.

Examples of the method of treating the pigment with the pigment dispersant of the present invention include a dry method using a Henschel mixer, a ball mill, an atomizer, a colloid mill, and a Banbury mixer, and a wet solvent for removing the solvent after treating in a solvent. Method can be used. If the solvent used in the wet solvent method is exemplified, toluene, aromatic hydrocarbons such as xylene, n-hexane, aliphatic hydrocarbons such as n-heptane, isopropanol, alcohols such as butanol, ethyl cellosolve, Examples thereof include ethers such as butyl cellosolve, ketones such as methyl ethyl ketone and acetone, esters such as ethyl acetate and butyl acetate, and water.

The pigment dispersant of the present invention can be used usually in an amount of 0.1 to 200% by weight in terms of a pigment dispersing compound (polyglycerin derivative) in treating the pigment.

A pigment-containing resin composition can be prepared by using the pigment dispersant of the present invention and further adding a pigment, a resin, and optionally a solvent. In this case, it goes without saying that the pigment dispersant and the pigment can be used in the form of a pigment (treated pigment) treated with the pigment dispersant of the present invention described above.

Specific examples of the pigment-containing resin composition include (colored) paints, printing inks, copying toners, rubber magnets used in copying machines, magnetic tapes, household goods and building materials. Examples include resin products using pigments such as colorant molded products and sealing agents used for construction and the like. The pigment-containing resin composition of the present invention is different from the conventional pigment-containing composition except that it contains the pigment dispersant of the present invention or is used after treating the pigment with the pigment dispersant of the present invention. , Their compositions and preparation methods are not different. It is well known that a pigment-containing resin composition comprises a resin, a pigment, a pigment dispersant, an organic solvent, and other appropriate additives.

The coloring paint is a main component for forming a coating such as a resin, and a sub-component for forming a coating which is added in a small amount to the main component.
Both elements are collectively referred to as coating elements (non-volatile components), and a solvent or diluent coating auxiliary element (the coating element and the coating auxiliary element are combined with a transparent paint (coloring agent)). ) Is added with a pigment and kneaded. Printing ink is produced by adding a pigment to a vehicle in which a resin is dissolved in a solvent. The copying toner is manufactured by kneading a resin and a magnetic material. A rubber magnet is manufactured by kneading a resin and a magnetic material. The magnetic tape is manufactured by applying a mixture composed of a magnetic material such as iron oxide, a solvent, a resin, and the like to a base resin tape. A color plastic molded product is manufactured by kneading a resin and a coloring pigment. The sealing agent is produced by kneading a resin and mainly an inorganic pigment.

In the present invention, an excellent pigment-containing resin composition can be prepared by adding the polyglycerin derivative of the present invention to these compositions or using a pigment treated thereby.

The resins to which the pigment dispersant of the present invention is applied include alkyd resins, polyester resins, acrylic resins, epoxy resins, polyurethane resins, silicone resins, fluorine resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, A wide range of resins such as, but not limited to, phenolic resins, vinyl chloride, polyethylene resins, and polypropylene resins.

The pigment dispersant of the present invention can be kneaded with a pigment, a resin, a solvent, and other additives to directly prepare a pigment-containing resin composition. (A kind of high-concentration pigment or pigment-containing resin composition of the present invention) (which is also included in the pigment-containing resin composition of the present invention), and then using the resin, a solvent, and the like, It can also be a containing resin composition.

The pigment dispersion base is the pigment dispersant of the present invention,
It may be composed of three components of a pigment (or a pigment (treated pigment) treated with the pigment dispersant of the present invention) and an organic solvent, and the three components may include a part of a dispersing resin (a resin for forming a film) or It is the same as the conventional pigment dispersion base that it may be composed of four components in which all components are added and further components in which additives such as an antifoaming agent and a surface conditioner are added. The pigment dispersion base of the present invention can be used as a paint by further adding a dispersing resin or other resin, or can be used as it is as a paint or printing ink.

Examples of the organic solvent in the pigment dispersion base or in the pigment-containing resin composition include toluene, xylene, high-boiling petroleum hydrocarbons, hydrocarbon solvents such as n-hexane, cyclohexane and n-heptane, methylene chloride, chloroform, dichloroethane. Such as halogenated hydrocarbon solvents, dioxane, tetrahydrofuran, butyl ether, butyl ethyl ether, ether solvents such as diglyme, methyl isobutyl ketone, cyclohexanone,
Ketone solvents such as isophorone, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ester solvents such as 2-methoxypropyl acetate, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, Ibutyl alcohol, t-butyl alcohol, amyl alcohol, n-hexyl alcohol, n-
Heptyl alcohol, 2-ethylhexyl alcohol,
Lauryl alcohol, stearyl alcohol, cyclopentanol, cyclohexal, benzyl alcohol,
alcohol solvents such as pt-butylbenzyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
In addition to the monoether solvents of alkylene glycols such as propylene glycol monobutyl ether, dimethylacetamide, amide solvents such as dimethylformamide, and the like, these are appropriately selected depending on the use of the pigment dispersion base or the pigment-containing resin composition, These can be used alone or in combination of two or more.

The above-mentioned pigment dispersion base and pigment-containing resin composition are prepared by using a roll mill, ball mill, sand ground mill, paint shaker, kneader, dissolver, ultrasonic disperser, etc. It can be manufactured by appropriately using and dispersing according to the use of each product.

In this case, the above treated pigment may be kneaded with a resin, or an integral blending method in which a pigment dispersant, a pigment and a resin are kneaded at the same time may be used.

The pigment-containing resin composition of the present invention can be put into distribution at a concentration that can be used as it is by appropriately adjusting the amount of the organic solvent in preparing the pigment-containing resin composition. Needless to say, it can be used by distributing it with a solvent and adjusting it to an appropriate concentration by a purchaser.

[0055]

The present invention will be specifically described below with reference to examples (including synthesis examples), use examples and comparative use examples. In the examples, “parts” and “%” are based on weight.

A: Synthesis of Polyester Having Carboxyl Group at Terminal (Examples 1 to 4): Example 1 (Synthesis of Polyester (1)) In a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet, and a reflux tube. Ricinoleic acid (Tokyo Kasei) 100.0
Parts and tetrabutyl titanate (manufactured by Junsei Chemical) 0.01
The mixture was heated to 160 ° C. over 4 hours under a nitrogen stream and heated at 160 ° C. for 2 hours.
Heating was performed until the amount became about mgKOH / g. Then
Cooled to room temperature.

Hereinafter, this reaction solution was used as polyester PE-1.
Called. The polyester contained in the polyester PE-1 has a number average molecular weight of 2190 and an acid value of 24.7 mgK.
OH / g.

Example 2 (Synthesis of Polyester (2)) In the same reaction flask as in Example 1, 100.0 parts of 12-hydroxystearic acid (manufactured by Junsei Chemical) and tetrabutyl titanate (manufactured by Junsei Chemical) were added. 01 parts was charged and heated to 160 ° C. over 4 hours under a nitrogen stream.
After heating at 0 ° C. for 2 hours, the acid value of the reaction solution was 25 mg KO.
Heating was performed until H / g was reached. Then, it was cooled to room temperature.

Hereinafter, this reaction solution was used as polyester PE-2.
Called. The polyester contained in the polyester PE-2 has a number average molecular weight of 2140 and an acid value of 25.3 mgK.
OH / g.

Example 3 (Synthesis of Polyester (3)) In the same reaction flask as in Example 1, 10.0 parts of 12-hydroxystearic acid (manufactured by Junsei Chemical), ε-
80.0 parts of caprolactone (manufactured by Junsei Chemical) and 0.01 part of tetrabutyl titanate (manufactured by Junsei Chemical) were charged, heated to 160 ° C. over 4 hours under a nitrogen stream, heated at 160 ° C. for 2 hours, and then subjected to ε. -Heating was performed until the remaining amount of caprolactone was 1% or less. Then, it was cooled to room temperature.

Hereinafter, this reaction solution was used as polyester PE-3.
Called. The polyester contained in the polyester PE-3 has a number average molecular weight of 2,920 and an acid value of 18.5 mgK.
OH / g.

Example 4 (Synthesis of Polyester (4)) In the same reaction flask as in Example 1, 90.0 parts of 12-hydroxystearic acid (manufactured by Junsei Chemical) and 8.9 of ethylene glycol (manufactured by Junsei Chemical) were used. , 21.1 parts of adipic acid (manufactured by Junsei Chemical) and 0.01 parts of tetrabutyl titanate (manufactured by Junsei Chemical) were charged, heated to 160 ° C over 4 hours under a nitrogen stream, and heated at 160 ° C for 2 hours. rear,
Heating was performed until the acid value of the reaction solution became about 24 mgKOH / g. Then, it was cooled to room temperature.

Hereinafter, this reaction solution was used as polyester PE-4.
Called. The polyester contained in the polyester PE-4 has a number average molecular weight of 2180 and an acid value of 24.8 mgK.
OH / g.

B: Synthesis of Intermediate of Polyglycerin Derivative (Examples 5 to 12): Example 5 (Synthesis of Intermediate of Polyglycerin Derivative (1)) A thermometer, a stirrer, a nitrogen inlet and a reflux tube were provided. In a reaction flask, 100 parts of polyester PE-1, 14 parts of diglycerin (manufactured by Tokyo Kasei) and 0.11 part of tetrabutyl titanate (manufactured by Junsei Chemical) were charged at a ratio of 0.11 part, and heated to 160 ° C. under a nitrogen stream. After heating for 4 hours and heating at 160 ° C. for 2 hours, heating was performed until the acid value of the reaction solution became about 1 mg KOH / g. Then, it was cooled to room temperature.

Hereinafter, this reaction solution is referred to as polyglycerin intermediate PG-1. The polyglycerin derivative intermediate contained in the polyglycerin intermediate PG-1 had a number average molecular weight of 2,482 and an acid value of 0.1 mgKOH / g.

Examples 6 to 10 (Synthesis of Intermediates of Polyglycerin Derivatives (2) to (6)) In the same manner as in Example 5, the target acid value (1 mg KOH / g) was obtained with the formulation shown in Table 1 below. (The acid value was confirmed by titration with KOH) to obtain polyglycerin intermediates PG-2 to PG-6. The same table also shows the number average molecular weight and acid value of each of the polyglycerin derivative intermediates in the obtained reaction solution.

Example 11 (Synthesis of Intermediate of Polyglycerin Derivative (7)) In the same reaction flask as in Example 5, 100.0 parts of stearic acid and polyglycerin (“Polyglycerin # 500” manufactured by Sakamoto Pharmaceutical Co., Ltd.) ) 176.0 parts and 0.28 part of tetrabutyl titanate (manufactured by Junsei Chemical Co., Ltd.) were charged, and the temperature was raised to 160 ° C. over 4 hours under a nitrogen gas stream.
After heating for an hour, heating was performed until the acid value of the reaction solution became about 1 mgKOH / g. Then, it was cooled to room temperature.

Hereinafter, this reaction solution is referred to as polyglycerin intermediate PG-7. The number average molecular weight and acid value of the polyglycerin derivative intermediate contained in the polyglycerin intermediate PG-7 are also shown in Table 1 below.

Example 12 (Synthesis of Intermediate of Polyglycerin Derivative (8)) In the same reaction flask as in Example 5, 100.0 parts of stearic acid and polyglycerin (“Polyglycerin # 500” manufactured by Sakamoto Pharmaceutical Co., Ltd.) 59.0 parts) and 0.16 part of tetrabutyl titanate (manufactured by Junsei Chemical) were charged, heated to 160 ° C. over 4 hours under a nitrogen stream, heated at 160 ° C. for 2 hours, and then acid value of the reaction solution. Was heated to about 1 mgKOH / g. Then, it was cooled to room temperature.

Hereinafter, this reaction solution is referred to as polyglycerin intermediate PG-8. Table 1 also shows the number average molecular weight and the acid value of the polyglycerin derivative contained in the polyglycerin intermediate PG-8.

[0071]

[Table 1]

[0072]

[Table 2]

C: Synthesis of polyglycerin derivative (Examples 13 to 22): Example 13 (Synthesis of polyglycerin derivative (1)) In a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet, and a reflux tube. , 100 parts of polyglycerin intermediate PG-1 and 160 parts of toluene (manufactured by Junsei Chemical Co., Ltd.) were added, and 5.7 parts of phosphorus pentoxide (manufactured by Junsei Chemical Co.) was added at 25 ° C. under a nitrogen stream, followed by stirring at 25 ° C. for 1 hour. Then, 0.7 parts of water was added, and the mixture was further stirred for 1 hour to obtain a reaction solution of a polyglycerin derivative.

Hereinafter, this reaction solution is referred to as a polyglycerin derivative PGP-1. This polyglycerin derivative PGP
Table 2 shows the number average molecular weight and the acid value of the polyglycerin derivative contained in -1.

Example 14 (Synthesis of polyglycerin derivative (2)) In the same reaction flask as in Example 13, 100 parts of polyester PG-2 and toluene (manufactured by Junsei Chemical)
173 parts, and adding 12.4 parts of phosphorus oxychloride (manufactured by Junsei Chemical Co., Ltd.) at 25 ° C. under a nitrogen stream, stirring at 25 ° C., further adding 2.9 parts of water and stirring for 1 hour, and stirring for 1 hour. A reaction solution was obtained.

Hereinafter, this reaction solution is referred to as a polyglycerin derivative PGP-2. This polyglycerin derivative PGP
Table 2 below shows the number average molecular weight and the acid value of the polyglycerin derivative contained in No.-2.

Examples 15 to 22 (Synthesis of Polyglycerin Derivatives (3) to (10)) In the same manner as in Example 13, the reaction was carried out until the target acid value was reached with the formulation shown in Table 2 below. Of reaction solutions PGP-3 to 10 were obtained. Table 2 also shows the number average molecular weight and acid value of each of the polyglycerin derivatives in the obtained reaction solution.

[0078]

[Table 3]

[0079]

[Table 4]

Example 23 (Preparation and Evaluation of Dispersion Resin Used for Evaluation) In a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet, a reflux tube, and a dropping funnel, 356.0 parts of xylene was charged, and 85 The temperature was raised to ° C. Then, 190.0 parts of methyl methacrylate and 160.
0 parts, 75.0 parts of 2-ethylhexyl methacrylate,
Styrene 60.0 parts, acrylic acid 5.0 parts, 2-hydroxyethyl methacrylate 110.0 parts, azobisisobutyronitrile 11.0 parts, dimethylacetamide 3
After continuously dropping 0.0 parts of the mixture over 2 hours,
The polymerization was carried out at 85 ° C. for 1 hour. Thereafter, a mixed solution in which 1.0 part of azobisisobutyronitrile was dissolved in 10.0 parts of dimethylacetamide was added thereto, and a further 8 parts were added.
The polymerization reaction was performed at 5 ° C. for 5 hours to complete the reaction (hereinafter, this reaction solution is referred to as acrylic resin ACJ).

Use Examples 1 to 19 The polyglycerin derivative PGP- obtained in Examples 13 to 22 was prepared according to the formulation of the pigment dispersion paste shown in Tables 3 to 5 below.
After mixing 1 to 10 and other raw materials, the pigment was uniformly dispersed with a paint shaker (manufactured by Red Devil Co.) to obtain a pigment dispersion paste. The obtained pigment dispersion paste is applied to a Brookfield viscometer “B-type viscometer” (Tokyo Keiki Co., Ltd.)
And the pigment-dispersed paste was stored at 50 ° C. for 5 days, and the viscosities at the initial stage and after 5 days were also measured with a “B-type viscometer”. (Viscosity after 5 days) / (initial viscosity) ) Is 2
The stability was indicated by determining the larger one as bad and the smaller than two as good in two steps.

Next, using the above-mentioned pigment-dispersed paste, the raw materials were mixed in the same manner as in the coating compositions shown in Tables 3 to 5 to obtain a coating. This paint was diluted with thinner (xylene / 2-methoxypropyl acetate = 1/1 weight ratio) to form cup No. 4. Diluted to a viscosity of 25 seconds (25 ° C) with 4, spray coated on a 0.6mm thick zinc phosphate treated steel plate and baked at 140 ° C for 30 minutes. A test coated plate was obtained. According to JIS K5400 7.6, the obtained test coating plate was 20
The specular gloss (coating 20 degree gloss) is measured, and the coating is subjected to a moisture resistance test according to JIS K5400 9.2.
Judge in two stages, good and bad, and determine coating adhesion according to JIS
An adhesion test was carried out according to K5400 8.5.2.

Comparative Use Examples 1 to 7 According to the formulations shown in Tables 3 to 5, the glycerin derivative of the present invention was not used, or instead of the glycerin derivative of the present invention, Solsperse 3000 (COM-1) manufactured by Zeneca or Kusumoto Kasei was used. Dispalon DA-703-50 (C
OM-2) was used as a dispersant, and a dispersion paste and a coating material were prepared in the same manner as in the above-mentioned use example. In the same manner, test coating plates were prepared, and various coating performance tests were performed. The test results are shown in Tables 3 to 5.

[0084]

[Table 5]

[0085]

[Table 6]

[0086]

[Table 7]

[0087]

[Table 8]

[0088]

[Table 9]

[0089]

[Table 10]

[0090]

[Table 11]

[0091]

[Table 12]

As can be seen from Tables 3 to 5, use examples 1 to 19 using the polyglycerin derivative PGP-1 to 10 of the present invention were compared with comparative use examples 3 to 5 and 7 using no polyglycerin derivative. As a result, the dispersion paste was excellent in stability and film gloss, and did not adversely affect moisture resistance and adhesion. In addition, it was found that the composition had particularly excellent storage stability as compared with commonly used dispersants for inorganic pigments (Comparative Use Examples 1, 2 and 6).

From the above, it is understood that the polyglycerin derivative of the present invention is useful in the field of coloring materials.

[0094]

The polyglycerin derivative of the present invention has excellent compatibility with a wide range of resins and excellent dispersibility of (pigment) fine particle powders. Therefore, colored paints and printing inks produced using the same. For example, since the cohesiveness between pigment particles is refused, a coating film having excellent storage stability and excellent image clarity and smoothness is provided. For coloring of plastics, color unevenness is prevented, and for magnetic tape, the magnetic force density is improved.

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Claims (10)

[Claims] 1. In the d free hydroxyl groups of polyglycerin,
In a form in which k remains free, n is bonded to a fatty acid or / and a polyester or / and a polyamide via an ester bond, and m is bonded to a phosphoric acid via an ester bond. Characteristic polyglycerin derivatives. Here, d, k, m and n are integers satisfying the following relational expressions: 1 ≦ n ≦ 0.5 (d + 2), m =
0-5, and k + m + n = d + 2. 2. The polyglycerin derivative according to claim 1, wherein the fatty acid and / or the polyester and / or the polyamide are polyester. 3. The polyglycerin derivative according to claim 2, wherein the polyester is a polyester represented by the following general formula (I) or (II). Embedded image In the formula, R ³ is a linear or branched alkylene group having 2 to 20 carbon atoms, R ⁴ is H or an alkyl or alkylene group having 1 to 20 carbon atoms, and R ⁵ is 2 carbon atoms.
Linear or branched alkylene group of ~20, -C ₆ H ₄
— Or —CH ＝ CH—, wherein R ⁶ has 2 to 20 carbon atoms.
And a residue obtained by removing two hydroxyl groups from a linear or branched alkylene group or polyalkylene glycol, and a and b each independently represent an integer of 2 to 100, and also have an ether bond in the chain. Sometimes. 4. The polyglycerin derivative according to claim 1, wherein the fatty acid and / or polyester and / or polyamide is a fatty acid having 6 to 30 carbon atoms. 5. A polyglycerin, comprising 6 to 30 carbon atoms.
And / or the following general formula (I) or (II)
Is reacted with phosphorus pentoxide or phosphorus oxychloride and, if necessary, water to form -PO (O
H) The compound obtained by introducing _two groups.
5. The polyglycerin derivative according to any one of items 1 to 4. Embedded image In the formula, R ³ is a linear or branched alkylene group having 2 to 20 carbon atoms, R ⁴ is H or an alkyl or alkylene group having 1 to 20 carbon atoms, and R ⁵ is 2 carbon atoms.
Linear or branched alkylene group of ~20, -C ₆ H ₄
— Or —CH ＝ CH—, wherein R ⁶ has 2 to 20 carbon atoms.
And a residue obtained by removing two hydroxyl groups from a linear or branched alkylene group or polyalkylene glycol, and a and b each independently represent an integer of 2 to 100, and also have an ether bond in the chain. Sometimes. 6. The polyglycerol according to claim 1, wherein the polyglycerin has a number average molecular weight in the range of 80 to 1,800 (corresponding to the degree of polymerization d = 2 to 20). Glycerin derivatives. 7. A pigment dispersant comprising the polyglycerin derivative according to claim 1 as an active ingredient. 8. A treated pigment obtained by treating a pigment with the pigment dispersant according to claim 7. 9. A pigment-containing resin composition comprising the pigment dispersant, resin and pigment according to claim 7, or the treated pigment and resin according to claim 8. 10. A paint or ink composition comprising the pigment dispersant according to claim 7 or the treated pigment according to claim 8.