JPS58145762A - Pigment dispersion - Google Patents

Abstract

PURPOSE:To provide a pigment dispersion showing stable pigment dispersion without lowering film performance, surface appearance, workabiity, etc., by incorporating a pigment, particular dispersion resin, particular dispersion auxiliary and, if necessary, org. solvent. CONSTITUTION:A pigment dispersion comprising a pigment, a dispersion resin consisting of a polyester oligomer, a dispersion auxiliary consisting of an arom. compd. or org. coloring matter derivative of formulaI(wherein Q is arom. polycyclic compd. residue, org. coloring matter residue ; A is a direct bounding, O, S, CO, SO2, a divalent group of formula II, III, IV or V, or 1-20C alkylene, phenylene connected with these groups; R' and R'' are H, 1-20C alkyl, aryl ; R1 and R2 are H, 1-20C alkyl, aryl, etc.; X and Y are R, halogen, OR', NO2, CN, CF3, or a group of formula VI, VII or VIII, etc.; l, m, and n are 0-20; n is 1-6 ; p is 1-2) and, if necessary, an org. solvent. It is excellent in compatibility with many resins used as a binder of coatings and inks and has the characteristics of high stability to dispersion even with a high content of the pigment.

Description

Detailed Description of the Invention The present invention provides a pigment dispersion for coloring that has excellent compatibility with many resins used as binders for paints and inks, and has good dispersion stability even when the pigment content is high. Regarding. Conventionally, a paste-like pigment dispersion in which a pigment is dispersed in a dispersion resin and a solvent has been widely used for coloring solvent solution type paints and inks. However, in such pigment dispersions, if the amount of resin used relative to the pigment is reduced in order to improve the coloring effect, the viscosity of the dispersion increases and becomes difficult to handle, and the dispersion stability decreases. When producing paints, inks, etc. by diluting the broken dispersion with resin phenylene, solvents, etc., pigments tend to aggregate due to shock, resulting in an undesirable phenomenon in which the coloring effect and gloss deteriorate. known to occur. Therefore, in such a pigment dispersion, it is necessary to use a sufficient amount of dispersion resin relative to the pigment in order to prevent the undesirable phenomenon described above. It is also known that if the dispersion resin of the pigment component 3- dispersion has poor compatibility with the binder resin of the paint or ink, the coloring effect and gloss will decrease. It is necessary to select a resin that is the same type or sufficiently compatible with the binder resin of the paint or ink as the dispersion resin, as this may have undesirable effects such as deterioration of the physical properties and workability of the film. .

On the other hand, in order to meet the various demands of society, many varieties of paints and inks with various characteristics are required, and there are also a wide variety of binder resins used in these paints and inks. Therefore, in the production of paints and inks, a large number of coloring pigment dispersions are currently prepared using dispersion resins that are highly compatible with the same type of binder resin or at most two or three types of binder resins.

Under such circumstances, there has been a strong desire for the emergence of a general-purpose pigment dispersion that can be used for coloring a wide variety of paints and inks.

That is, the present invention provides a pigment dispersion consisting of a pigment, a dispersion resin, a dispersion aid, and, if necessary, an organic solvent, in which the dispersion resin is a polyester oligomer, and the dispersion aid is an aromatic compound represented by the following general formula. The above pigment dispersion is characterized in that it is a group compound or an organic pigment derivative.

General type seal In the formula, Q: residue of aromatic polycyclic compound or organic dye residue A: Direct binding or as shown below. represents a divalent bonding group.

-o-1-NR'-1-S-1 -CO-1-8O2-1-CR:R''--8O2NRnie, -coNm-t or a combination thereof, or the above divalent bonding group A bonded saturated or unsaturated alkylene group having 1 to 20 carbon atoms (however, the alkylene group is not directly bonded to other alkylene groups in the formula) Represents a phenylene group. R', R:'' is a hydrogen atom Or saturated with 1 to 20 carbon atoms! or represents an unsaturated alkyl or ayl group.

RIXR2: represents a hydrogen atom, an independent saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an aryl group, or a heterocycle containing nitrogen, oxygen-1, or sulfur atom in R1 and R2.

X, Y: Mutually independent − to 1 logen atoms, −〇k
, -NR'politics', -COOR:, -NHCOR', -NH8OR:, -c ON R: R'', -8O2
N.R.R.

NR'-CO-politics', =N02, -CN.

-CF3 Sword or One 803M (M is Indicates 1 equivalent of mono- to trivalent cation ). R' and R' are hydrogen atoms A carbon atom or a saturated atom having 1 to 20 carbon atoms. is an unsaturated alkyl group, aryl represents a group.

4m: Represents a mutually independent integer of 0 to 2.

n: represents an integer from 1 to 6.

p: represents an integer of 1 to 2.

The purpose of the present invention is to easily and stably disperse pigments without deteriorating the properties of many types of paints and inks with different binder resins, such as coating performance, coating surface condition, workability, etc. The purpose of the present invention is to provide a pigment dispersion with excellent versatility.

In the present invention, pigments include soluble and insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene/perinone pigments, dioxazine pigments, vat dye pigments, Organic pigments such as basic dye pigments and carbon black,
Inorganic pigments such as titanium oxide, yellow lead, cadmium yellow, cadmium red, Bengara, iron black, zinc white, navy blue, and ultramarine blue can be used.

The amount of the above-mentioned pigment used is preferably 80% by weight or less of the pigment dispersion, and if it exceeds 80% by weight, it may become difficult to apply and handle due to increased viscosity.

In the present invention, the polyester oligomer used as the dispersion resin is obtained by transesterifying a condensation product of a polybasic acid and a polyol, or a condensation product of a polybasic acid and a monohydric alcohol such as methanol or ethanol, with a polyol. Examples of the polybasic acids mentioned above include aromatic dibasic acids such as phthalic acid, isophthalic acid, and terephthalic acid, and aliphatic acids such as glutaric acid, succinic acid, adipic acid, azelaic acid, and sebacic acid. Dibasic acids include aliphatic unsaturated dibasic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid. Examples of cleaved polyols include ethylene glycol, glopylene glycol, and 1,3-phthylene glycol. Diols such as recall, 2, 3 phthylene gelicol, 1.4 phthylene gelicol, neohentyl glycol, diethylene glycol, dipropylene glycol, synchropentalene diol, triols such as glycerin, trimethylolethane, trimethylolpropane, etc. Can be mentioned.

The average molecular weight of the polyester oligomer used in the present invention is preferably in the range of 200 to 2,000, more preferably in the range of 400 to 1,000. Average molecular weight is 20
If it is less than 0, the pigment particles cannot be sufficiently stabilized in the pigment dispersion, and if the average molecular weight is greater than 2,000, the compatibility will decrease and versatility will be impaired.

The polyester oligomer may be used in an amount of 5 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 30 parts by weight, based on 100 parts by weight of the pigment. If the above blending ratio is less than 5 parts by weight, the viscosity of the pigment dispersion may increase significantly and it may become difficult to handle, or a large amount of the organic solvent described below will be required, resulting in a small content of pigment, making it impractical. On the other hand, if the above blending ratio exceeds 100 parts by weight, when using a pigment dispersion, the proportion of the polyester oligomer in the paint or ink will become too large, and the unique properties of the binder resin may be impaired. . In addition, for pigments such as carbon blanks, which have high coloring power and hiding power and are only incorporated in small amounts in paints and inks, a large amount of polyester oligomer is used relative to the pigment, and pigments such as titanium dioxide, which have high coloring power and hiding power, are used in a small amount. A relatively small amount of polyester oligomer is used for pigments that have low strength and are incorporated in large amounts in paints and inks.

The polyester oligomer used in the present invention has very good compatibility with binder resins used in paints and inks, such as amino resins, alkyd resins, polyester resins, acrylic resins, polyvinyl chloride resins, and polyvinyl acetate resins. In a transparent coating film obtained by blending polystyrene resin, polybutadiene resin, rosin ester gum, cellulose derivative, isocyanate prepolymer, etc. so that the solid content weight ratio is 85/15 (binder resin/polyester oligomer), I can't find any flaws.

In the present invention, aromatic compounds and organic dye derivatives used as dispersion aids are represented by the general formula
Examples of residues of aromatic polycyclic compounds represented by are aromatic compounds such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, indole, thiazole, benzimidazole, quinoline, acridone, anthraquinone, phenothiazine, quinazoline, carbazole, pensanthrone, and perylene. Examples of organic dye residues include azo compounds, phthalocyanine, quinacridone, dioxazine, anthrapyrimidine, anthanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo, 4.4' -diamino-1
, 1''-dianthraquinonyl, isoindolinone, quinophthalone, benzimidacylone, dianthraquinone, pyranthrone and the like.

The compound represented by the general formula symbol can be prepared by directly reacting an amine component with the substituted or unsubstituted aromatic polycyclic compound or organic dye derivative, or by reacting an aromatic compound with a functional group that easily reacts with the amine component. It can be obtained by reacting a polycyclic compound or an organic dye derivative with an amine component.

Typical amine components introduced into the compound represented by the general formula are piperidinomethyl, dimethylamineethyl, diethylaminoethyl, dimethylaminepropyl, diethylaminepropyl, dibutylaminopropyl,
Piperidinoethyl, piperidiethyl, morpholinoethyl, piperidinopropyl, pibecolinogropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl, N, N-
Methyl-lauryl-aminoflovir, 2-ethylhexylaminoethyl, stearyl aminoethyl, oleylamino 12-ethyl, P′-′methylaminoethylsulfamoylphenyl, p′:”ethylamineethylsulfamoylphenyl, p-dimethyl These include amine prohylsulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl, and the like.

When the above-mentioned amine component is introduced into the side chain as shown in General Nita, it exhibits strong affinity with anionic moieties such as carboxyl groups of polyester oligomers, reducing the viscosity of the pigment dispersion and reducing the viscosity of the pigment dispersion. decrease in structural viscosity, etc.
It is thought that this contributes to improved fluidity and dispersion stability, and the amount of dispersion resin used relative to the pigment can be reduced.

In addition, in the general formula symbol, m and R'' have 1 to 20 carbon atoms.
a saturated or unsaturated alkyl group, or an aryl group, or R' and m' represent a heterocycle containing a nitrogen or sulfur atom, especially m and R'' are an alkyl group having 1 to 4 carbon atoms. When this happens, the pigment dispersion effect is extremely good. This is advantageous because it is possible to easily produce a shredded amine compound as a raw material.

Furthermore, aromatic compounds include -8O2C7゜-COCz
, -CH2Cl, etc. can be introduced relatively easily, so the terminals other than R1 and R2 of the amine component are -8
Those substituted with amine groups that easily react with substituents such as 02Ct and -COCt-CH2Cl are advantageous.

That is, diamine is preferable as the amine component introduced into the compound represented by the general formula.

The amount of the dispersion aid represented by the above general formula for the pigment is preferably 0.5 to 30 parts by weight per 100 parts by weight of the pigment, and if it is less than 0.5 part by weight, it will not be effective as a dispersion aid. Moreover, even if more than 30 parts by weight is used, the effect of using it cannot be obtained.

In the present invention, it is preferable to use an organic solvent in combination to adjust the viscosity of the pigment dispersion to an appropriate viscosity. The above-mentioned organic solvent may be selected from among solvents containing functional groups that are generally used in crosslinking reactions in paints and inks, such as hydroxyl groups, amine groups, carboxyl groups, epoxy groups, and methylol groups. Can be used. Examples of the above-mentioned organic solvents include aromatic solvents such as xylene, toluene, and solvent naphtha; aliphatic solvents such as hexane, mineral spirit, and ethylcyclohexane; ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate; acetone and methyl ethyl ketone. , methyl isobutyl ketone, isophorone, and other ketone solvents.

The pigment dispersion of the present invention can be produced by premixing all components including an organic solvent and dispersing the pigment using a conventionally known dispersing machine such as a roll mill, colloid mill, hole mill, sand mill, attritor, etc.

Examples and comparative examples will be given and explained below. In addition, "part" in the example
and "%" are "1 part by weight" and "percent by weight", respectively.

Example 1 A chloride was synthesized by heating and stirring β-ochinaphthoic acid with an equimolar amount of 15-thionyl chloride in benzene under reflux for 1 hour. After the reaction was completed, the following amine (n) was added and further refluxed. The mixture was heated and stirred for 1 hour to obtain the following dispersion aid (2).

Next, 100 parts of phthalocyanine blue, polyester oligomer, TOESTAR-L-010 (trademark manufactured by Toyo Ink Manufacturing Co., Ltd., non-volatile content 100%): 125 parts, 5 parts of the above-mentioned dispersion aid (1-a), and 120 parts of xylene were uniformly added. The mixture was mixed, 1000 parts of 1/16 inch steel beads were further added, and the mixture was dispersed in a shaker for 2 hours to obtain a dispersed paste. Next, add an alkyd resin face for air-drying paint, an amino alkyd resin face for baking paint, an aminoacrylic resin varnish for baking paint, and an acrylic resin face for lacquer to this dispersed paste so that the pigment content is 20% of the total binder resin. were mixed uniformly using a DeSilver to prepare paints to obtain an air-dry alkyd resin paint, a baked amino alkyd resin paint, a baked amino acrylic resin paint, and an acrylic resin lacquer. Apply these paints to the tube cage (J
When the blobs were examined using ISK-5400, 4, and 5), they were 10 microns or less in all paints. Also, with each paint thinner, for air-dry alkyd resin paint, baked amino alkyd resin paint, and baked amino acrylic resin paint, use Ford Cup & 4 for 20 seconds (25°C),
For the acrylic resin lacquer, the viscosity was adjusted to 12 seconds (25°C), and after spray painting on a tin plate, each paint was dried according to the specified schedule to prepare a coated plate. A coating film was obtained. Furthermore, when the viscosity-adjusted paints were poured into test tubes and left to stand, all were stable for a long time.

Comparative Example 1 100 parts of Phthalocyanine Blue, alkyd resin varnish, Phthalkyd 133'-60 [Hitachi Chemical Trademark,
417 parts of non-volatile content 60%] and 108.3 parts of xylene were uniformly mixed in a mayo-zubin, 1000 parts of 1/16 inch steel beads were added, and a dispersion treatment was carried out in the same manner as in Example 1. A dispersed paste was obtained. Next, the paint resin varnish used in Example 1 was blended and mixed with this comparative dispersion paste in the same manner as in Example 1 to obtain a comparative air-drying alkyd resin paint, a comparative baking amino alkyd resin paint, and a comparative baking amino alkyd resin paint. A baked amino acrylic resin paint and a comparative acrylic resin paint were obtained and a paint test was conducted. As a result, all comparative paints had a
Bubbles of 0μ or more were observed, and all of the obtained coatings had rough surfaces and low gloss.Also, in the sedimentation test, all comparative paints sedimented early.

Example 2 Anthraquinone-2-carboxylic acid was chlorinated to form a carboxylic acid chloride, which was then reacted with the amine (II) used in Example 1 to obtain the following dispersion aid (1-b).

Next, 100 parts of titanium white, polyester oligomer, Elberon 58o3 [trademark of Bayer AG, nonvolatile content 100'%:] 110 parts, 10 parts of dispersing agent (1-b), and 40 parts of xylene were uniformly mixed, 160 parts of glass peas were added and dispersed for 1 hour to obtain a dispersed paste. Next, polyester polyol resin varnish, acrylic polyol resin varnish,
Blend aminoacrylic resin varnishes for baking paints so that the non-pigment content is 100% of the total binder resin, mix uniformly with DeSilver to adjust the paint, and prepare polyester urethane resin paint base, acrylic urethane resin paint base, A baked amino acrylic resin paint was obtained. These paint main ingredients and -J9 top paint were tested using a tube gauge [JIS K-5400, 4, 5
] When the whelks were examined with a hawk, they were all less than 5μ. Next, to the polyester urethane resin paint main ingredient and the acrylic urethane resin paint main ingredient, a specified incyanate curing agent is added as a curing agent and mixed thoroughly. The viscosity was adjusted to 20 seconds (25° C.) using a Ford Cup Tsuta 4, and spray paint was applied to a tin plate. When each paint was dried as specified and coated plates were prepared, clear, high-gloss, and good paint films were obtained in all cases.

Comparative Example 2 100 parts of titanium white, 20 parts of acrylic resin varnish, Almatex 748-16 [Mitsui Toatsu Chemical trademark, non-volatile content 50%], and 30 parts of xylene were uniformly mixed.
160 parts of 1.5 mmφmm glass beads were prepared and subjected to dispersion treatment in the same manner as in Example 2 to obtain a comparative dispersion paste. Next, the 20-paint resin varnish used in Example 2 was blended and mixed with this comparative dispersion paste in the same manner as in Example 2, and a polyester urethane resin paint base for comparison, an acrylic urethane resin paint base for comparison, and a comparative acrylic urethane resin paint base were mixed. A baked amino acrylic resin paint was obtained, and a paint test was conducted in the same manner as in Example 2.

As a result, bulges of 100 microns or more were observed in all of the comparative paints, and the surfaces of the resulting paint films were all rough and had low gloss.

Example 3 1 part of unsubstituted quinacridone was added to 100 parts of chlorosulfonic acid at 10 to 20°C, stirred for 3 hours at 40 to 50°C, 1000 parts of ice water was added, filtered, and washed with water to obtain quinacridone monomer. A sulfonated product was obtained. This chlorosulfonated product was re-slurized with 30 parts of ice water, and 20 parts (
7) Add N,N-diethylaminopropylamine to 1
The mixture was stirred at 0° C. or lower for 4 hours, filtered, and washed with water. Next, this water cake was added to 300 parts of 0.5% sodium carbonate aqueous solution, stirred for 1 hour, filtered, washed with water using a neutral soap, and dried to obtain the following quinacridone derivative (+-1).

Next, 100 parts of carbon black, 476 parts of polyester oligomer CKS-760 [Nippon Gosei Kagaku Kogyo ■ trademark, nonvolatile content 90%], and the above quinacridone derivative (1 (!)
') 10 parts, Ki and Ren 175.7 parts were mixed uniformly, 1
1,000 parts of /16 inch steel beads were added and dispersed in a shaker for 2 hours to obtain a dispersed paste. Next, a nitrified cotton varnish and an acrylic resin varnish for lacquer are added to this dispersion paste so that the amount of non-pigment content is 10% of the total binder resin, and the mixture is uniformly mixed in a desilver to prepare a paint. Cotton lacquer and acrylic resin lacquer were obtained. When a paint test was conducted on these paints in the same manner as in Example 1, the blobs of all paints were 10 μm.
The resulting coatings were clear and high-gloss.
23=. In the sedimentation test of paints whose viscosity was adjusted to 12 seconds (25°C) using Ford Cup Rot 4, all were stable for a long time.

Comparative Example 3 100 parts of carbon black, nitrified cotton varnish [Daicel@
Nitrified cotton R8 1/2 seconds (IPA 25 humid) 30% ethyl acetate 30 parts, xylene 40% non-volatile content 22.5%': 1
190.4 parts of xylene and 24.9 parts of xylene were uniformly mixed,
A comparative dispersion paste was obtained by adding 1000 parts of /16 inch steel beads and carrying out the dispersion treatment in the same manner as in Example 3. Next, the resin varnish for paint used in Example 3 was blended and mixed with this comparative dispersion paste in the same manner as in Example 3 to obtain a comparative nitrified cotton varnish and a comparative acrylic resin varnish. A paint test was conducted in the same manner as in 3.

As a result, bulges of 100 microns or more were observed in all of the comparative paints, and the surfaces of the resulting paint films were all rough and had low gloss. Also, in the sedimentation test, all comparative paints sedimented early.

Patent applicant: Toyo Ink Mfg. Co., Ltd. Procedural amendment (voluntary) 9th day of 1980 To the Commissioner of the Patent Office 1 Indication of case 1981 Patent Application No. 28196 2 Title of invention Pigment dispersion 3 , Relationship with the person making the amendment Column 5 of ``Detailed explanation of the invention in the patent applicant's specification'' Contents of the amendment As shown in the attached sheet (1) Akira: Book 4R1, page 4, line 10, ``Amount used ” is corrected to “Usage amount”.

(2) Page 7, line 5 of the specification "Alkyl" is corrected as "alkyl group".

(3) Page 7, line 11 of the specification Correct "hetero ring" to "1 hetero ring".

(4) Insert the following sentence in the 5th to 6th lines of page 9 of the specification, "Due to thickening, it may become difficult to handle."

"In addition, when inorganic pigments are used, coupling agents such as silane coupling agents and titanate coupling agents that have been effectively used in the dispersion of conventionally known inorganic pigments can be added." (5) Specification Insert the following sentence between Group 1 unsaturated dibasic acid J and "etc." on page 9, line 18 of the book.

Examples include "triol" and 1, "and polycyclopentadiene-based polycarboxylic acids such as cyclopentadiene cyclocarboxylic acid" (6), page 10, line 6 of the specification. ” Insert the sentence i--F between.

“And polycyclopentadiene polyols” (7
) Page 11 of the specification, line 5, 1 is ``inherent''.

(8) On page 12, line 9 of the specification, "penzimidazole" is corrected to "benzimidazole."

(9) Page 15, line 12 of the specification Correct rO, 5J to IO, 3J.

(10) Page 15, line 13 of the specification Correct "0.5 part by weight" to "0.3 part by weight".

(11) Page 17, line 6 of the specification Correct r (2) J to r (1-a) J.

(12) From the bottom of page 20 of the specification, line 9, line 1, ``Bayer'' is corrected to ``DuPont.''

(13) "1r4.7.6 copies" in line 6 from the bottom of page 23 of the specification is corrected to "r47.6 copies."

2 - Procedural amendment (method) July 1980 Mr. Commissioner of the Japan Patent Office■, Indication of the case Patent Application No. 28196 of 1981 2, Title of the invention Pigment dispersion 3, Person making the amendment Relationship between patent applicant

Claims (1)

[Claims] 1. A pigment dispersion consisting of a pigment, a dispersion resin, a dispersion aid, and an organic solvent if necessary, wherein the dispersion resin is a polyester oligomer, and the dispersion aid has the following general formula. The above-mentioned pigment dispersion is characterized in that it is an aromatic compound or an organic pigment derivative shown below. General Nita Formula Q: Residue of aromatic polycyclic compound or organic dye residue A: Directly bonded or represents a divalent bonding group shown below. 10-1-N R'-1-S-1-CO-1~502-
1-cm is -, -8O2NR2, -413- -C0NR-, or a combination thereof, or a saturated or unsaturated alkylene group with 1 to 2 carbon atoms bonded to the above divalent bonding group. (However, the alkylene group does not directly bond to other alkylene groups in the formula.) Represents a phenylene group. R-R'' represents a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 20 carbon atoms or an aryl group. R1, R2: hydrogen atom, each independently a saturated or unsaturated alkyl group having 1 to 20 carbon atoms 7) Furkyl group, aryl group modifiers R1 and R2 represent a heterocycle containing nitrogen, oxygen or sulfur atoms. X, Y: mutually independent 1R', halogen atom, -OR', -N R' R ”,-COOR'
, -N HCOR', 2- -N HS OR', -CON R'R'', -3O2N
R'R'', NR'-Co-R'', -NO2, -CN. -CF3 or -8O3M (M represents 1 equivalent of a mono- to trivalent cation). R' and R'' represent a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or an aryl group. z, rn: represent mutually independent integers of 0 to 2. n: 1 Represents an integer from 1 to 6. p: represents an integer from 1 to 2. 2 100 parts by weight of pigment, 5 to 100 parts by weight of dispersion resin, 0.3 to 30 parts by weight of dispersion aid, and 0 to 1000 parts by weight of organic solvent.
The pigment dispersion according to claim 1, comprising parts by weight. 3 Polyester oligomer has an average molecular weight of 200 to 20
The pigment dispersion according to claim 1 or 2, which has a pigment dispersion in the range of 0.00.