JPS58225159A - Pigment dispersion - Google Patents

Abstract

PURPOSE:To obtain a pigment dispersion, prepared by using a bisphenol A type epoxy resin as a dispersion resin and a specific aromatic type compound or an organic dyestuff derivative as a dispersion assistant, and having improved compatibility with many resins and high dispersion stability. CONSTITUTION:A pigment dispersion consisting of a pigment, a dispersion resin, a dispersion assistant and if necessary an organic solvent. In the pigment disprsion, a bisphenol A type epoxy resin having preferably <=2,000 average molecular weight is used as the dispersion resin, and an aromatic type compound or an organic dyestuff derivative of the formula (Q is a residue of an aromatic polycyclic compound or organic dyestuff; A is direct bond, O, S, CO, etc.; R1 and R2 are H or 1-20C alkyl or aryl; R1 and R2 form a heterocyclic ring containing N, O or S; X and Y are halogen, CN, etc.; l and m are integers 0-2; n is an integer 1-6; p is 1 or 2) is used as the above-mentioned dispersion assistant. The ratio of the respective components based on 100pts.wt. pigment is preferably as follows: 5-100pts.wt. dispersion resin, 0.3-30pts.wt. dispersion assistant and 0-1,000pts.wt. organic solvent.

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 a pigment dispersion, 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.
It is also known that when producing paints, inks, etc. by diluting the dispersion with a resin face, solvent, etc., pigments tend to aggregate due to shock, resulting in undesirable phenomena such as a decrease in coloring effect and gloss. ing. Therefore, in such pigment dispersions, it is necessary to use a sufficient amount of dispersion resin relative to the pigment in order to prevent the undesirable phenomena described above.

It is also known that if the dispersion resin of the pigment dispersion has poor compatibility with the binder resin of the paint or ink, the coloring effect and gloss will decrease. Since this may have undesirable effects such as deterioration of physical properties and workability, 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 dispersing resin.

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 a wide variety of binder resins used in these products. Therefore, when manufacturing paints and inks,
Use a dispersion resin that is highly compatible with the same type of binder resin or at most two or three types of binder resin,
At present, a large number of coloring pigment dispersions are available. 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.
In a pigment dispersion consisting of a dispersion aid and, if necessary, an organic solvent, the dispersion resin is a bisphenol A type epoxy resin, and the dispersion aid is an aromatic compound or an organic dye derivative represented by the general formula below. The above pigment dispersion is characterized in that:

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

10-1-NR-1-S-1 -CO-1-8O2-1-CRR- -8O2NR-1 -CON R'- or a combination of these combination or the above bivalent combination Saturated with 1 to 20 carbon atoms bonded to a group or an unsaturated alkylene group ( In the formula, the alkylene group is (does not bond directly with the alkylene group of) Represents a phenylene group. RR is water Subatomic atoms or saturated carbon atoms of 1 to 20 or unsaturated alkyl group, ali represents a 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 a nitrogen, oxygen or sulfur atom with R1 and R2.

X, Y: mutually independent -R, -rogen atoms, -o
R", -N R'R", -8O2NRR -NR'-CO-R, -NO2, -CN.

-CF3 or -8O3M (M is Indicates 1 equivalent of mono- to trivalent cation ). R', R'' are hydrogen atoms child or saturated or carbon number 1 to 20 is an unsaturated alkyl group, aIJ-/L.

represents a group.

t, m = mutually independent integers 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. An object of the present invention is to provide a pigment dispersion with excellent leakability and versatility.

Pigments used in the present invention include soluble and insoluble azo pigments, condensed azo pigments, fuda'ar'11 pigments, quinacridone pigments, indolinone pigments, perylene, perinone pigments, dioxazine pigments, and vat dyes. pigments,
Organic pigments such as basic dye pigments and inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, Bengara, iron black, zinc white, navy blue, and ultramarine blue can be used.

The usage amount of the pigment exemplified above is 80% by weight of the pigment dispersion.
The following is preferable; if it exceeds 80% by weight, it may become difficult to handle due to increased viscosity.

When using a crushed inorganic pigment, a known coupling agent such as a silane coupling agent or a titanate coupling agent that has been effectively used for dispersing inorganic pigments can be added.

The bisphenol A type epoxy resin used as the dispersion resin in the present invention includes, for example, one manufactured by Shell Chemical Company under the trade name Epicoat, which is used in upper fabrics, and one manufactured by Dow Chemical Company under the trade name DER, which is used in upper cloths. Among them, those having an average molecular weight of 2000 or less, such as Epicoat 1004.1001.834.828, are preferably used.

The amount of bisphenol A type epoxy resin used is 10% of the pigment.
5 to 100 parts by weight relative to 0 parts by weight, preferably 5 to 5 parts by weight
It can be used in an amount of 0 parts by weight, more preferably 5 to 30 parts by weight. If the above-mentioned blending ratio is less than 5 parts by weight, the viscosity of the pigment dispersion may increase significantly and 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 bisphenol A epoxy resin in the paint or ink will increase, and the unique properties of the binder resin may be impaired. There is. It has great coloring power and hiding power, like carbon black.
For pigments that are mixed in a small amount in paints and inks, use a large amount of bisphenol A epoxy resin compared to the pigment, and use titanium dioxide, which has low coloring power and hiding power, and in a small amount to be mixed in paints and inks. For pigments with a large amount of polyester, a relatively small amount of polyester oligomer is used.

The pigment dispersion of the present invention uses bis 1' as the dispersion resin.
It contains phenol A type epoxy resin as an essential component, but bisphenol A is also used as another dispersion resin component.
A resin that is compatible with the type epoxy resin, such as polyester oligomer or sucrose benzoate,
Sucrose derivatives such as sucrose acetate isobutyrate can also be used in combination.

The bisphenol A epoxy resin used in the present invention has very good compatibility with binder resins used in paints and inks, such as amine resins, alkyd resins, polyester resins, acrylic resins, polyvinyl chloride resins, and polyvinyl chloride resins. Vinyl acetate resin, polystyrene resin, polybutadiene resin, rosin ester gum, cellulose derivatives,
Incyanate prepolymer etc. K, solid content weight ratio 85
/15 (binder resin/bisphenol A type epoxy resin), and no defects were found in the transparent coating film obtained by blending the binder resin/bisphenol A type epoxy resin.

In the present invention, the aromatic compounds and organic dye derivatives used as dispersion aids are represented by the general formula symbol, and the aromatic polynomial compound residues represented by Q in the formula include, for example, naphthalene, anthracene, phenanthrene, pyrene. , chrysene, indole, thiazole, benzimidazole, quinoline, acridone, anthraquinone, phenothiazine, quinazoline, carbazole, pensanthrone, perylene, and other aromatic poly-IJJ compound residues, and organic dye residues include Ab compounds, phthalocyanine, etc. , quinacridone, dioxazine, anthrapyrimidine,
Anthanthrone, indanthrone, frahanthrone, perinone, perylene, thioindigo, 4,4'-diamino-1,1-dianthraquinonyl, isoindolinone, quinophthalone, benzimidacylone, dianthraquinone,
A compound represented by the general formula 01 in which the residue such as pyranthrone is ff1-, filo' can be prepared by directly reacting an amine component with the substituted or unsubstituted aromatic polycyclic compound or organic dye derivative, or can be obtained by reacting an amine component with an aromatic polycyclic compound or an organic dye derivative having a functional group that easily reacts with the amine component.

Typical amine components introduced into the compound represented by the general formula are piperidinomethyl, dimethylamineethyl, diethylaminoethyl, dimethylaminepropyl, diethylaminepropyl, dibutylaminopropyl,
Piperidinoethyl, hypercorinoethyl, morpholinoethyl, piperidinoethyl, pipeco IJ/propyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminoethyl, dimethylaminoamyl, N1
N-methyl lauryl, aminopropyl, 2-ethylhexylaminoethyl, stearyl aminoethyl, oleylaminoethyl, p-dimethylaminoethylsulfamoylphenyl, p-diethylamineethylsulfamoylphenyl, p-dimethylaminepropyl These include 0rsulfamoylphenyl, p-diethylamineethylcarbamoylphenyl, and the like.

When the amine component described above is introduced into the side chain as shown in the general formula, it exhibits strong affinity with the anionic moiety of bisphenol A epoxy resin, reducing the viscosity of the pigment dispersion and improving its structure. It is thought that this contributes to improved fluidity, such as reduced viscosity, and dispersion stability, and the amount of dispersion resin used relative to the pigment can be reduced.

In addition, in the general formula, R and R represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an aryl group, or a petero ring containing a nitrogen or sulfur atom in R and R, but especially R, When R is an alkyl group having 1 to 4 carbon atoms, the pigment dispersion effect becomes extremely good. Furthermore, the amine compound used as a raw material can be easily produced, which is advantageous.

Furthermore, aromatic compounds include -8O2C7゜-COCt
, -CH2C1, etc. can be introduced relatively easily, so the other terminals other than R+ and R2 of the amine component are -8
It is substituted with an amine group that easily reacts with substituents such as 02Cl, -C0C-1, and -CH2C1.

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 0.3 to 30 parts by weight per 100 parts by weight of the pigment, and if it is less than 0.3 parts by weight, the effect as a dispersion aid is insufficient. Moreover, even if more than 30 parts by weight is used, the effect of the amount used cannot be obtained.

The pigment dispersion of the present invention is preferably adjusted to a viscosity suitable for use using an organic solvent. The above organic solvent may be selected from among solvents that do not contain functional groups that are generally used for 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 organic solvents include aromatic solvents such as xylene, toluene, and solvent naphtha; aliphatic solvents such as hexane, mineral spirit, and ethylcyclohexane; and ethyl acetate and n-acetic acid.
Butyl, esters such as seronrubu acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone,
This can be done with ketone solvents such as isophorone.

The pigment dispersion of the present invention can be prepared by premixing all components, including an organic solvent if necessary, using a conventionally known dispersing machine such as a roll mill or a colloid mill.

"Parts" and "%" in which the pigment is dispersed using a sand mill, attritor, etc. are "parts by weight" and "% by weight," respectively.
”.

Example 1 Equimolar amounts of β-oxynaphthoic acid in benzene. □Ao =
7 degrees □ Koyu, 1 ka. □ゎ□ 11 After the chloride was synthesized and the reaction was completed, the following amine (II) was added and the mixture was further heated and stirred under reflux for 1 hour to obtain the following dispersant (+-a).

Next, 100 parts of Phthalocyanine Blue (Epicor) 8
28 (Trademark manufactured by Shell Kagaku ■) 25 parts, the above dispersion aid (1
-a) 5 parts and 120 parts of xylene are uniformly mixed, and 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, alkyd resin varnish for air-drying paints, bumino alkyd resin face for baking paints, aminoacrylic resin varnish for baking paints, and acrylic resin face for lacquers were added to this dispersed paste so that the pigment content was 20% of the total binder resin. They were blended and mixed uniformly using a Decilper 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. When these paints were examined for blobs using a blob cage (JISK-5400, 4, 5), the blobs were 10 μm 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 A4 for 20 seconds (2
5°C), 12 seconds (2°C) for acrylic resin lacquers
After adjusting the viscosity to 5°C) and spray painting on a tinplate plate, each paint was dried to a prescribed degree to prepare a coated plate, and a clear, high-gloss, good coating film was obtained in all cases. 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, 41.7 parts of Phthalkyd 133-60 (Hitachi Chemical Trademark, non-volatile content 60%), and 108.3 parts of Xyref were mixed uniformly, and 1/16 inch steel beads were added. 10
00 copies and perform the dispersion process in the same manner as in Example 1,
A comparative dispersion paste was obtained. Next, the paint resin phene 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 lacquer were obtained and a paint test was conducted. 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.

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, Epicote 1001
(Trademark manufactured by Shell Chemical Co., Ltd.) 20 parts of 50% xylene solution,
10 parts of dispersion aid (1-b) and 30 parts of xylene were uniformly mixed, 160 parts of 1.5r'rf+1 glass powder was added, and the mixture was dispersed in a shaker for 1 hour to obtain a dispersed paste. Next, add polyester polyol resin phenol, acrylic polyol resin varnish, and amine acrylic resin varnish for baking paints to this dispersion paste so that all the pigment content (one part of the inner resin) is added to the dispersion paste.
The mixtures were mixed uniformly using a DeSilver to prepare paints to obtain a polyester urethane resin paint base, an Ac 1-Nor urethane resin paint base, and a baked amino Ac 1-Nor urethane resin paint. (JIS K-5400, 4, 5)
When the whelks were examined, they were all less than 5μ. Next, in the polyester urethane resin paint base material and acrylic urethane resin base material described in ``2'', a curing agent is added.
1j After adding the specified incyanate curing agent and mixing thoroughly, and for the baked aminoacrylic resin paint mentioned above, add paint thinner and adjust the viscosity to 20 seconds (25°C) using a Ford cup A4. , spray painted on the 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.
．． 150 parts of 5 mm glass beads were added and the dispersion treatment was carried out in the same manner as in Example 2 to obtain a comparative dispersion paste. Next, the paint resin phene used in Example 2 was blended and mixed with this comparative dispersion paste in the same manner as in Example 2 to obtain a comparative polyester urethane resin paint base, a comparative acrylic urethane resin paint base, and a comparative acrylic urethane resin paint base. 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, for all comparative paints, 1
Bubble of 00 μm or more was observed, and the surfaces of all the obtained coating films were rough and had low gloss.

Example 3 10 parts of mf-converted quinacridone was added to 100 parts of chlorosulfonic acid at 10-20°C, stirred at 40-50°C for 3 hours, poured into 1000 parts of ice water, filtered and washed with water to obtain quinacridone monosulfone. I got a monster. This chlorosulfonated product was added to 300 parts of ice water and reslurized, and then 20 parts of N1N-diethylaminoprobylamine was added for 10 minutes.
The mixture was stirred for 4 hours at a temperature below 0.degree. C., filtered, and washed with water. Next, this water cake was added to 300 parts of 0.5 carbon powder aqueous solution, stirred for 1 hour, filtered, washed with water until the filtrate became neutral, and dried to obtain the following quinacridone derivative (1-c). .

(1-1) Next, 100 parts of carbon black, Ebiko) 828 (
42.8 parts of Shell Chemical Co., Ltd. trademark), 10 parts of the above quinacridone derivative (+-C), and 1805 parts of xylene were uniformly mixed, 100 parts of 1/16 inch steel beads were added, and the mixture was dispersed using a shaker for 2 hours. Got the paste. Next, add nitrified cotton varnish and acrylic resin varnish for lacquer to this dispersed paste so that the pigment valve is 10% of the total binder resin.
%, and mixed uniformly in a DeSilver to prepare a paint to obtain a nitrocotton lacquer and an acrylic resin lacquer. A paint test was conducted on these paints in the same manner as in Example 1, and all of the paints had blobs of 10 μm or less, and the resulting paint films were all clear and had high gloss. Ford Cag & 4 for 12 seconds (25℃
Even in sedimentation tests of paints whose viscosity was adjusted to

Comparative Example 3 100 parts of carbon black, nitrated cotton varnish (Daicel Co., Ltd. nitrated cotton R8I/, 2 seconds (isopropyl alcohol 25%)
Mix 190.4 parts of 30% ethyl thiacetate, 40% ethyl thiacetate, 225% non-volatile content) and 24.9 parts of xylene, add 1000 parts of 1/16 inch steel beads, and use the same method as in Example 3. A dispersion treatment was performed to obtain a comparative dispersion paste. Next, the paint resin varnish 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 nitrocotton lacquer and a comparative acrylic resin lacquer. I did a paint test. 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 Manufacturing Co., Ltd. (1

Claims (3)

[Claims] (1) In a pigment dispersion consisting of a pigment, a dispersion resin, a dispersion aid, and, if necessary, an organic solvent, the dispersion resin is a bisphenol A type epoxy resin, and the dispersion aid is represented by the general Nita below. The above pigment dispersion is characterized in that it is an aromatic compound or an organic pigment derivative. In the general formula: Q: Residue of an aromatic polycyclic compound or organic dye residue A: Represents a direct bond or a divalent bonding group shown below. 10-1-NR'-1-s-1-C0-1-8O2-1
cttt-1-δ (J2NK-1-CONR- or a combination thereof, or a saturated or unsaturated alkylene group having 1 to 20 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. RR represents a hydrogen atom or a saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms. R1, R2: hydrogen atom, Each independently represents a saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms, or R1 and R2 represent a petro ring containing nitrogen, oxygen or an ionic atom. X, Y: mutually independent distarved halogen atoms; -0R1-N m m', -cooR', -rutcoR'. -N HS OR', -CONRR. -S O2NR'R', -NR'-CO-R',' -N O2, -CN. - Represents CF3 or -8O3M (M represents 1 equivalent of a mono- to trivalent cation). R' and R' represent a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or an aryl group. 1, rrB represents a mutually independent integer of 0 to 2. n: represents an integer of 1 to 6. p: represents an integer of 1 to 2. (2) 100 parts by weight of pigment, 5 to 100 parts by weight of dispersion resin
Part by weight side: 0.3 to 30 parts by weight and organic solvent 0 to 100
The pigment dispersion according to claim 1, comprising 0 parts by weight of X. (3) Claim 1 in which the bisphenol A epoxy resin has an average molecular weight of 2000 or less.
The pigment dispersion according to item 1 or 2.