JP3413319B2 - Pigment dispersant and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pigment dispersant and a composition containing the same. More specifically, the present invention relates to a dispersant used for improving the dispersibility of a pigment when preparing a paint, a printing ink, and the like, and a composition containing the dispersant.

[0002]

2. Description of the Related Art Conventionally, when preparing paints, printing inks, etc., the dispersibility of the pigments contained therein is improved to improve the storage stability of the paints, shortening the dispersion time, preventing the phenomenon of color separation, and coating. Various dispersants are used for the purpose of improving the gloss of the film. For example, the dispersant used for this purpose is generally a compound of structure having a moiety that is adsorbed by the pigment and a moiety that is compatible with the vehicle for the paint or ink. The compound conventionally used for these purposes is a dispersible polymer having a polyester component and / or an acrylic component in the molecular chain.

Various functional groups have been used as the groups that are easily adsorbed by the pigment (hereinafter sometimes referred to as "adsorbed groups"), but many dispersants having an amino group in the molecular chain are used. Are known. For example, JP-A-53-1039
No. 88, a low molecular weight amino compound such as N, N-dimethylaminopropylamine is also disclosed in JP-A-61-1.
Japanese Patent No. 74939 describes a pigment dispersant using polyethyleneimine which is a high molecular weight amine compound. Among them, the low molecular weight amine compound has a low content of amino groups adsorbed on the pigment surface in its molecule, the adsorbability is insufficient, and when used as a pigment dispersant,
It did not exhibit a good pigment dispersion effect.

[0004]

On the other hand, a pigment dispersant containing polyethyleneimine as a group to be adsorbed as a high molecular weight amine compound is more suitable for various pigments than a dispersant using a low molecular weight amino compound. , Exhibits relatively good adsorptivity and dispersion effect. However, since polyethyleneimine generally has a highly branched structure and has a three-dimensionally complicated structure, when the pigment is adsorbed, the nitrogen atom of the imine is sufficiently present at the adsorbed site of the pigment. It was not able to act, and did not show sufficient adsorbed action to all pigments. Therefore, some pigments do not exhibit a sufficient pigment dispersion effect.

[0005]

In view of the present situation, the present inventor diligently studied for the purpose of providing a pigment dispersant and a composition containing the pigment dispersant, which have solved the problems and problems existing in the prior art. As a result, the polymer pigment dispersant obtained by reacting a polyester component having a specific structure in the molecular chain and a polyvinylamine component as an adsorbed group in the pigment dispersant is restricted by the type of pigment. However, they have found that they exhibit extremely good dispersion performance for a wide range of pigments, and completed the present invention.

That is, the first aspect of the present invention is that a carboxyl group-terminated polyester compound component (component A) essentially contains a unit formed in the molecular chain by ring-opening polymerization of a lactone compound represented by the following general formula (1). ) Is reacted with a polyvinylamine component (component B) whose amino group represented by the following general formula (2) is only a primary amine ,
Provided is a pigment dispersant comprising a reaction product having an amine value of 10 to 500 mgKOH / g .

[0007]

[Chemical 3] (R ¹ represents an optionally substituted aliphatic alkylene group having 1 to 10 carbon atoms.)

[0008]

[Chemical 4] (In the formula, k represents an integer of 2 to 2,500.)

The second aspect of the present invention is that the molecular weight of the component A is 10
Provided is the pigment dispersant according to the first aspect of the present invention, which is in the range of 0 to 5,000. A third aspect of the present invention provides the pigment dispersant according to the first aspect of the present invention, wherein the molecular weight of the component B is in the range of 100 to 100,000. A fourth aspect of the present invention provides a coating composition comprising the pigment dispersant according to the first aspect of the present invention as a dispersant. A fifth aspect of the present invention provides a printing ink composition comprising the pigment dispersant according to the first aspect of the present invention as a dispersant.

The present invention will be described in detail below. (Regarding Component A) Component A is a polyester compound component that essentially contains a unit produced by ring-opening polymerization of the lactone compound represented by the above general formula (1) and has a carboxyl group at the terminal. It is desirable that the carboxyl group exists only at one end of the polyester chain.

The component A can be synthesized by various methods as described below. (a) Addition reaction for adding lactone compound to monocarboxylic acid compound, (b) Addition reaction for adding lactone compound to hydroxycarboxylic acid compound, (c) Three components of monocarboxylic acid compound, hydroxycarboxylic acid compound and lactone compound Condensation reaction of (d) dicarboxylic acid compound or diol component with a lactone compound, hydroxycarboxylic acid compound, monocarboxylic acid compound, or the like, (e) polyvalent carboxylic acid having a valence of 2 or more, or Examples thereof include a condensation reaction in which the acid anhydride compound, the polyhydric alcohol compound, the lactone compound, the hydroxycarboxylic acid compound, and the like are condensed.

Examples of the lactone compound represented by the above general formula (1) include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, γ-butyrolactone and 2-methylcaprolactone. , 4-methylcaprolactone and the like. These may be used alone or as a mixture of two or more kinds.

The monocarboxylic acid compound that can be used for the synthesis of the component A includes various aliphatic and aromatic carboxylic acids. Specific examples include acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, lauric acid, stearic acid, abietic acid, phenylacetic acid and methoxyacetic acid. These may be used alone or as a mixture of two or more kinds.

Hydroxycarboxylic acid compounds which can be used for the synthesis of the component A include aliphatic, aromatic and unsaturated hydroxycarboxylic acids. Specifically, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, P-hydroxyethyloxycarboxylic acid, 2-hydroxynaphthalene-3-
Carboxylic acid, 2-hydroxynaphthalene-6-carboxylic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, malic acid, tartaric acid, lactic acid, glycolic acid, glucon Acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2
-Oxidodecanoic acid, salicylic acid and the like. These may be used alone or as a mixture of two or more kinds.

Examples of the divalent or higher polycarboxylic acid or its acid anhydride compound include maleic acid, succinic acid, glutaric acid, fumaric acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, phthalic acid and isophthalic acid. , Terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, methyltetrahydrophthalic acid, or their anhydrides. These may be used alone or as a mixture of two or more kinds.

Examples of the polyhydric alcohol include aliphatic branched,
Examples include various alcohols having a linear structure, alicyclic and aromatic. Specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 3-methylpentanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol , 1,4-dibenzyl alcohol and the like.

In the addition reaction for adding the lactone compound to the monocarboxylic acid compound (a) for synthesizing the component A,
From the molar ratio of the initiator and the lactone compound, a carboxylic acid-modified polylactone compound having a higher molecular weight than the predicted molecular weight,
Alternatively, while the high molecular weight homopolymer of the lactone compound and the monocarboxylic acid may remain, the addition reaction of adding the lactone compound to the (b) hydroxycarboxylic acid compound is more preferable when the hydroxycarboxylic acid is a polymerization initiator. Which is advantageous because a polylactone compound having a molecular weight as designed can be easily obtained.

The synthesis reaction of the component A is preferably carried out by using a catalyst and a reaction solvent in order to increase the reaction rate and improve the heat exchange capacity, as in the usual esterification reaction, and the coloring of the product. In order to suppress the above, it is desirable to carry out the reaction under a stream of an inert gas such as nitrogen gas.

Examples of esterification catalysts that can be used include organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate and monobutyltin hydroxybutyl oxide, tin compounds such as stannous oxide and stannous chloride, tetrabutyl titanate, Examples thereof include tetraethyl titanate and tetrapropyl titanate. The amount of the catalyst used is preferably selected in the range of 0.1 to 3,000 ppm. When the amount of the catalyst used is 1 ppm or less, the ring-opening polymerization rate of lactones becomes extremely slow,
When it is 0 ppm or more, coloring of the component A becomes severe,
All of them are not preferable because they adversely affect the stability of the product.

The temperature for synthesizing the component A varies depending on the type of raw material, the molar ratio, the type and amount of catalyst, the type and amount of solvent, and the like, but is preferably selected in the range of 120 to 220 ° C.
When the reaction temperature is 120 ° C or lower, the reaction rate is extremely slow,
Above 210 ° C, side reactions other than addition reaction of lactones,
For example, decomposition of lactone polymer into lactone monomer,
Formation of a cyclic lactone dimer is likely to occur, a carboxyl group-terminated polylactone having a target molecular weight is difficult to synthesize, and the obtained polymer is easily colored, which is not preferable. Particularly preferred in the above temperature range is 160
It is in the range of to 210 ° C.

The component A can be synthesized by charging the above raw materials into a reactor equipped with a dehydration tube and a condenser and reacting them in a stream of an inert gas such as nitrogen gas. When a solvent is used in the synthesis reaction system, it is preferable to use a dehydrated solvent such as toluene or xylene. After completion of the reaction, the solvent used in the synthetic reaction system may be removed by an operation such as distillation, or the B component and the A component, which will be described later, may be reacted and used as a part of the product.

The component A is a polyester compound which can be synthesized by the above-mentioned method, contains a polylactone unit produced by ring-opening polymerization of a lactone compound as an essential component, and has a terminal carboxyl group. The polyester component has a function of forming a three-dimensional repulsion layer around the pigment.

The component A preferably has an OH value of 0.5 to 200 and an acid value of 1 to 200. When the OH value or the acid value of the component A is less than 0.5, the viscosity of the polyester becomes extremely high, which is not preferable.
If it exceeds 00, the molecular weight of the polyester is too low, and after reaction of the component B, a side chain having a molecular weight that forms a sufficient steric repulsion layer cannot be obtained, which is not preferable.

The molecular weight of the polyester component in the dispersant of the present invention produced by the reaction with the component B described below is preferably in the range of 100 to 5,000. If the molecular weight of the polyester component in the dispersant is 100 or less, a sufficient three-dimensional repulsion layer cannot be formed around the pigment, and if the molecular weight is 5,000 or more, the molecular weight of the entire dispersant becomes too large. , The compatibility with paints and vehicles for ink is lowered, and further the pigment dispersibility is also lowered, which is not preferable. Here, the molecular weight of the polyester component means a value measured by an NMR method.

(About Component B) Component B is a polyvinylamine component represented by the above general formula (2). According to the experiment of the present inventor, the B component has a molecular weight of 100 to 1
It has been found that a range of 0,000 is preferred. When the molecular weight is 100 or less, the molecular weight of the entire pigment dispersant is too low, the number of adsorbed groups becomes too small, the effect of using the polyvinylamine compound is not obtained, and the molecular weight is 100,0.
When it is 00 or more, the molecular weight of the entire pigment dispersant becomes too large, which may lead to the association of the pigments with each other or decrease in dispersibility.

[0026]

DETAILED DESCRIPTION OF THE INVENTION

(Synthesis Method of Pigment Dispersant) Next, a synthesis method of the pigment dispersant according to the first aspect of the present invention will be described. The pigment dispersant of the present invention is obtained by reacting the A component and the B component. When the two are reacted, under mild reaction conditions, that is, at a low reaction temperature or a short reaction time, a salt is formed by the reaction between the carboxyl group in the molecular chain of component A and the amino group in the molecular chain of component B. To be done. Under severe reaction conditions, that is, at a high reaction temperature or a long reaction time, an amide bond is formed by the terminal carboxyl group of the component A and the amino group reaction of polyallylamine or the ester / amide exchange reaction. At this time, the A component lowers the molecular weight and is graft-bonded to the B component. The molecular weight of the grafted portion can be monitored by measuring the amine value. The pigment dispersant according to the present invention may contain a salt formed by the reaction of an amino group and a carboxyl group and an amide-bonded salt.

The molar ratio at the time of reacting both is preferably in the range of 1: 1 to 1:99 for the A component and the B component. When reacting both, A component and B component, the dehydration tube,
A method in which a reactor equipped with a condenser is charged and a dehydration polymerization is performed under a stream of an inert gas such as nitrogen gas and, if necessary, a catalyst, a dehydrating solvent such as toluene or xylene is used. The solvent used for the reaction can be removed by an operation such as distillation after completion of the reaction, or can be directly used as a part of the product.

The temperature at which both are reacted varies depending on the type of raw material, the molar ratio, the type and amount of catalyst, the type and amount of solvent, and the like, but is selected in the range of 90 to 210 ° C. When the reaction temperature is 90 ° C. or lower, the rate of the amidation reaction is extremely slow, and when the reaction temperature is 210 ° C. or higher, decomposition and coloring of the reaction product are likely to occur, which is not preferable. Particularly preferable temperature range is 100 to 170 ° C.

Examples of the catalyst that can be used when reacting the both include organic tin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate and monobutyltin hydroxybutyl oxide, and tin compounds such as stannous oxide and stannous chloride. , Titanium compounds such as tetrabutyl titanate, tetraethyl titanate and tetrapropyl titanate, organic acids such as p-toluenesulfonic acid and methanesulfonic acid, or inorganic acids such as sulfuric acid and phosphoric acid.

The amount of the catalyst used varies depending on the type of raw material, molar ratio, reaction temperature, type and amount of solvent, etc.
It is selected in the range of 1,000 ppm. Catalyst amount is 100
When it is 0 ppm or more, the reaction product is usually strongly colored, which adversely affects the stability of the product, which is not preferable. On the contrary, if the amount of catalyst is 0.1 ppm or less, the rate of amidation becomes extremely slow, which is not preferable. Especially preferred in the above range is 1 to 100 ppm. Further, when air is present in the reaction system, the reaction product tends to be colored, so it is desirable to carry out the reaction under a stream of an inert gas such as nitrogen gas.

The pigment dispersant according to the first aspect of the present invention thus obtained has an amine value of 1 according to the experiments of the present inventor.
0-500 mgKOH / g, more preferably 20-30
It is in the range of 0 mgKOH / g. When the amine value is 10 or less, the content of amino groups that have an adsorptive effect on the pigment is too small, and there is no sufficient pigment dispersing effect.
On the other hand, when the content is KOH / g or more, on the contrary, the polyester portion forming the three-dimensional repulsion layer is small and the dispersion stability of the pigment becomes insufficient.

In the pigment dispersant according to the first aspect of the present invention thus obtained, when one end of the polyester component is a carboxyl group and the other end is a hydroxyl group, in the baking step after coating, It reacts readily with the melamine resin or isocyanate, and this reaction causes the pigment dispersant to be incorporated firmly as part of the coating. Therefore, the pigment dispersant in the coating film does not cause bleeding or crystallization at all, and the pigment supplemented by this pigment dispersant hardly causes bleeding or reaggregation of the pigment.

(Method of Using Pigment Dispersant) The pigment dispersant according to the first aspect of the present invention is mixed with a pigment or a magnetic material and other additives and dispersed by a known method to obtain a coating composition and a printing ink. It can be used as a composition. That is, a coating composition and a printing ink composition can be obtained by dispersing a pigment, the present dispersant, a coating resin, and an appropriate solvent with a disperser and then blending them with a coating resin or an ink resin. The pigment dispersant according to the first aspect of the present invention has an adsorbable group that is easily adsorbed by a pigment or the like when used in these applications, and thus has sufficient adsorbability, and therefore has dispersibility of pigment, mill-base fluidity, pigment Storage stability of the dispersion,
Fulfills the function of improving.

Examples of pigments usable in combination with the pigment dispersant according to the first aspect of the present invention include inorganic pigments and organic pigments. The inorganic pigments include titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red iron oxide, yellow lead, carbon black, and the like, and the organic pigments include phthalocyanines, insoluble azo pigments, azo lake pigments, and condensed polycyclic pigments. Various pigments such as (slen-based, indigo-based, perylene-based, perinone-based, phthalone-based, dioxazine-based, quinacridone-based, isoindolinone-based, diketopyrrolopyrrole-based pigments) can be mentioned.

As the paint resin that can be used in combination with the present dispersant, general paint resins can be preferably used, but alkyd resin, oil-free alkyd resin, acrylic resin, urethane resin and the like are preferable. is there. Further, as other additives, a leveling agent, a defoaming agent, etc. can be used.

[0036]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples, examples and application examples, but the present invention is not limited to these description examples as long as the gist thereof is not exceeded. In the following description examples, “part” and “%” both mean “weight basis”.

In the following synthetic examples of the intermediate polyester compound (component A) and the description of the examples, O
The H value, the acid value, the amine value, the molecular weight of the dispersant, etc. are measured by the methods described below. (1) OH value: Based on JIS K-1557. (2) Acid value: According to JIS K-1557. (3) Amine value: determined by a titration method using hydrochloric acid. (4) Molecular weight of polyester chain in dispersant: JEOL JN
Using M-EX-270, proton NMR was measured by a NMR method at room temperature in a CDCl ₃ solvent. (5) Polyvinylamine molecular weight: GPC method and calculated molecular weight based on amine value were used together.

[Synthesis Example 1: Synthesis of Intermediate 1] Dose 3 equipped with a condenser, a nitrogen gas introduction tube, a stirrer and a thermometer
In a liter reactor, caprolactone monomer 198
4.8 parts, 15.2 parts of glycolic acid and 0.1 part of tetrabutyl titanate were charged. While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas flow, and the caprolactone monomer remaining in the reaction system was reacted at this temperature until it became 1% or less by gas chromatography. It was The obtained intermediate polyester compound is O
H value is 6.0mgKOH / g, acid value is 6.2mgKOH
/ G. Hereinafter, this intermediate polyester compound is referred to as "intermediate 1".

[Synthesis Example 2: Synthesis of Intermediate 2] 1964 parts of caprolactone monomer, 36 parts of lactic acid and 0.1 part of tetrabutyl titanate were charged in the same reactor used in the synthesis of "Intermediate 1". It is. While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas stream, and the caprolactone monomer remaining in the reaction system was allowed to react at 1% or less at this temperature. The obtained intermediate polyester compound has an OH value of 11.2 mgKOH /
g, the acid value was 10.8 mgKOH / g. Hereinafter, this intermediate polyester compound is referred to as "intermediate 2".

[Synthesis Example 3: Synthesis of Intermediate 3] In the same reactor used in the synthesis of "Intermediate 1", 1961.3 parts of caprolactone monomer, 38.7 parts of caproic acid, and 0.1% of tetrabutyl titanate. Each section was prepared. While stirring the contents of the reactor, set the internal temperature to 1 under a nitrogen gas stream.
The temperature was raised to 70 ° C., and the reaction was continued until the caprolactone monomer remaining in the reaction system became 1% or less at this temperature, then the internal temperature was raised to 210 ° C., and the reaction was performed to obtain an intermediate polyester compound. The acid value of the product was 9.5 mgKOH / g. Hereinafter, this intermediate polyester compound is referred to as "intermediate 3".

Synthesis Example 4: Synthesis of Intermediate 4 In the same reactor used in the synthesis of "Intermediate 1", 926.3 parts of caprolactone monomer, 29 parts of caproic acid, 1044.7 of 12-hydroxystearic acid were added. And 0.1 part of tetrabutyl titanate were charged. While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas flow, and the reaction was continued at this temperature until the caprolactone monomer remaining in the reaction system was 1% or less. 210 ° C
The temperature was raised to, and the product was heated until the acid value of the product reached 7.2 mgKOH / g and reacted to obtain an intermediate polyester compound. Hereinafter, this intermediate polyester compound is referred to as "intermediate 4".

[Synthesis Example 5: Synthesis of Intermediate 5] In the same reactor used in the synthesis of "Intermediate 1", 976.8 parts of caprolactone monomer, 46.4 parts of caproic acid, and α-olefin monoepoxide AOE. X-24 (manufactured by Daicel Chemical Industries) 571.6 parts, adipic acid 405.2 parts,
0.1 part of tetrabutyl titanate was charged. While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas flow, and the reaction was continued at this temperature until the caprolactone monomer remaining in the reaction system was 1% or less. The temperature was raised to 210 ° C and the acid value of the product was 11.2.
It heated until it became mgKOH / g and it was made to react and the intermediate polyester compound was obtained. Hereinafter, this intermediate polyester compound is referred to as "intermediate 5".

[Synthesis Example 6: Synthesis of Intermediate 6] 1130.5 parts of caprolactone monomer, 23.2 parts of caproic acid and 4-caprolactone were placed in the same reactor used in the synthesis of "Intermediate 1".
846.3 parts of methylcaprolactone and 0.1 part of tetrabutyl titanate were charged. While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas flow, and the reaction was continued at this temperature until the caprolactone monomer remaining in the reaction system was 1% or less. 210 ° C
The temperature was raised to, and the product was heated until the acid value of the product reached 5.8 mgKOH / g and reacted to obtain an intermediate polyester compound. Hereinafter, this intermediate polyester compound is referred to as "intermediate 6".

[Synthesis Example 7: Synthesis of Intermediate 7] In the same reactor used in the synthesis of "Intermediate 1", 1845.3 parts of caprolactone monomer, 154.7 parts of caproic acid, and 0.1% of tetrabutyl titanate were added. Each section was prepared.
While stirring the contents of the reactor, the internal temperature was raised to 170 ° C. under a nitrogen gas stream, and the caprolactone monomer remaining in the reaction system was reacted at this temperature until it became 1% or less,
The internal temperature was raised to 210 ° C and the acid value of the product was 37.4 mg.
The mixture was heated to KOH / g and reacted to obtain an intermediate polyester compound. Hereinafter, this intermediate polyester compound is referred to as "intermediate 7".

Example 1: Synthesis of Dispersant 1 In the same reactor used in the synthesis of "Intermediate 1", 1,000 parts of "Intermediate 1" was charged first, and then polyvinylamine (molecular weight 10, 000) was prepared in 140 parts. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 77 mgKOH / g. The average molecular weight of the polyester component containing polycaprolactone as a main component was about 1,000, which was measured by NMR for the product. Hereinafter, this dispersant is referred to as "dispersant 1".

Example 2: Synthesis of Dispersant 2 In the same reactor used in the synthesis of "Intermediate 1", 1,000 parts of "Intermediate 2" was charged, and then polyvinylamine (molecular weight 10, 000) was charged in 95 parts. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 40 mgKOH / g. The average molecular weight of the polyester component of the product measured by NMR was about 1,000. Hereinafter, this dispersant is referred to as "dispersant 2".
Called.

Example 3: Synthesis of Dispersant 3 The same reactor used in the synthesis of "Intermediate 1" was charged with 1,000 parts of "Intermediate 2" and then polyvinylamine (molecular weight 10, 000) was charged in 90 parts. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 38 mgKOH / g. The average molecular weight of the polyester component of the product measured by NMR was about 1,000. Hereinafter, this dispersant is referred to as "dispersant 3".
Called.

Example 4: Synthesis of Dispersant 4 In the same reactor used in the synthesis of "Intermediate 1", 1,000 parts of "Intermediate 3" were first charged, and then polyvinylamine (molecular weight 10, 000) was charged in 90 parts. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 4 hours. The amine value of the product was 38 mgKOH / g. The average molecular weight of the polyester component of the product measured by NMR was about 1,000. Hereinafter, this dispersant is referred to as "dispersant 4".
Called.

Example 5 Synthesis of Dispersant 5 In the same reactor used in the synthesis of "Intermediate 1", 1,000 parts of "Intermediate 4" was charged first, and then polyvinylamine (molecular weight 10, 000) was prepared in 93 parts. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 41 mgKOH / g. The average molecular weight of the polyester component of the product measured by NMR was about 1,000. Hereinafter, this dispersant is referred to as "dispersant 5".
Called.

Example 6 The same reactor used in the synthesis of "Intermediate 1" was charged with 1,000 parts of "Intermediate 4" and then 70 parts of polyvinylamine (molecular weight 10,000). . While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 40 mgKOH / g. Regarding the polyester component of the product, NM
The average molecular weight measured by the R method was about 1500. Hereinafter this product is referred to as "dispersant 6".

Example 7 The same reactor used in the synthesis of "Intermediate 1" was charged with 1,000 parts of "Intermediate 4" and then 118 parts of polyvinylamine (molecular weight 10,000). . While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 3 hours. The amine value of the product is 81 mgKOH / g
Met. Also, regarding the polyester component of the product, N
The average molecular weight measured by the MR method was about 1,000. Hereinafter this product is referred to as "dispersant 7".

Example 8 The same reactor used in the synthesis of "Intermediate 1" was charged with 1,000 parts of "Intermediate 5" and then 115 parts of polyvinylamine (molecular weight 10,000). . While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 4 hours. The amine value of the product is 79 mgKOH / g
Met. Also, regarding the polyester component of the product, N
The average molecular weight measured by the MR method was about 1500.
Hereinafter this product is referred to as "dispersant 8".

Example 9 The same reactor used in the synthesis of "Intermediate 1" was charged with 1,000 parts of "Intermediate 6" and then 90 parts of polyvinylamine (molecular weight 10,000). . While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 5 hours. The amine value of the product was 40 mgKOH / g. Regarding the polyester component of the product, NM
The average molecular weight measured by the R method was about 1,100.
Hereinafter this product is referred to as "dispersant 9".

Example 10 The same reactor used in the synthesis of "Intermediate 1" was initially charged with 1,000 parts of "Intermediate 6", and then polyvinylamine (molecular weight 10,000).
I prepared 100 copies. While stirring the contents of the reactor, the internal temperature was raised to 100 ° C. under a nitrogen gas stream, and the reaction was carried out at this temperature for 4 hours. The amine value of the product is 79 mgKOH /
It was g. The average molecular weight of the polyester component of the product measured by the NMR method was about 1,150. Hereinafter, this product is referred to as "dispersant 10".

[Examples 11 to 20 and Comparative Example 1 Preparation Example of Pigment Composition by Pigment Dispersant]
A paint resin (polyester and acrylic resin), a pigment, a solvent, and the like were blended, glass beads were further added, and the mixture was dispersed for 2 hours with a disperser (manufactured by Red Devil Co.) to disperse the pigment with a pigment dispersant. A pigment composition was obtained. The resulting pigment composition was evaluated for millbase fluidity by the method described below. The evaluation results are shown in the table.
1, shown in Table-2 and Table-3.

(1) Millbase fluidity A The composition was visually observed immediately after the pigment composition was prepared, and those having good fluidity were designated as "good" and those not dispersed were designated as "not dispersed". (2) Mill-base fluidity B A pigment composition was prepared and then left at room temperature for 24 hours, and the composition was visually observed in the same manner as above. The display is the same as above.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

From Table-1 to Table-3, the following is clear. 1. The dispersion composition of the pigment prepared by using the pigment dispersant according to the first aspect of the present invention has excellent mill-base fluidity and storage stability of the dispersion composition (Examples 11 to 11). 20). 2. On the other hand, the pigment dispersion compositions prepared without using the pigment dispersant according to the first aspect of the present invention have poor dispersibility (see Comparative Examples 1 to 5).

[0061]

INDUSTRIAL APPLICABILITY The present invention has the following special advantageous effects and its industrial utility value is extremely large. 1. The pigment dispersant according to the first aspect of the present invention has a group to be adsorbed that exhibits an adsorbing ability for a large number of various pigments, and thus has a function of improving the dispersibility of a large number of various pigments. 2. The dispersion composition of the pigment dispersed by the pigment dispersant according to the first aspect of the present invention exhibits excellent mill-base fluidity. 3. The pigment dispersion composition dispersed by the pigment dispersant according to the first aspect of the present invention exhibits excellent storage stability.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI C09D 17/00 C09D 17/00 (56) References JP-A-7-207012 (JP, A) JP-A-2-296878 (JP , A) JP 7-149855 (JP, A) JP 62-201927 (JP, A) JP 61-163977 (JP, A) JP 9-157374 (JP, A) JP 8-38875 (JP, A) JP 48-79178 (JP, A) JP 5-271593 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09B 67/20 C08G 63/91 C09C 3/10 C09D 7/12 C09D 11/02 C09D 17/00 B01F 17/06 B01F 17/52

Claims (5)

(57) [Claims] 1. A carboxyl group-terminated polyester compound component (component A) essentially containing a unit produced by ring-opening polymerization of a lactone compound represented by the following general formula (1) in the molecular chain, Ami represented by formula (2)
Polyvinylamine component (B containing only primary amines)
Component), which has an amine value of 10 to 500
A pigment dispersant comprising a reaction product of mgKOH / g . [Chemical 1] (R ¹ represents an optionally substituted aliphatic alkylene group having 1 to 10 carbon atoms.) (In the formula, k represents an integer of 2 to 2,500.) 2. The molecular weight of the component A is 100 to 5,000.
The pigment dispersant according to claim 1, which is within the range. 3. The B component has a molecular weight of 100 to 100,0.
The pigment dispersant according to claim 1, which is in the range of 00. 4. A coating composition comprising the pigment dispersant according to claim 1 as a dispersant. 5. A printing ink composition comprising the pigment dispersant according to claim 1 as a dispersant.