JPH0322429B2 - - Google Patents

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, dispersion stability decreases, and dispersion body with resin varnish,
It is known that when pigments are diluted with a solvent or the like to produce paints, inks, etc., pigments tend to aggregate due to the shock, resulting in an undesirable phenomenon in which the coloring effect and gloss are reduced. 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 above-mentioned undesirable phenomena. 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 also a wide variety of binder resins used in these paints and inks. Therefore, in the production of paints and inks, there are currently many coloring pigment dispersions 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. Ta.
Under these circumstances, there has been a strong desire for 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 represented by the following general formula []. The above pigment dispersion is characterized in that it is an aromatic compound or an organic pigment derivative.

General formula [] In the formula, Q: a residue of an aromatic polycyclic compound or an organic dye residue; A: represents a direct bond or a divalent bonding group shown below.

-O-, -NR'-, -S-, -CO-, -
SO ₂ −, −CR′R″−, −SO ₂ NR′−, −
CONR′− or a combination thereof;
Alternatively, it represents a phenylene group, which is a saturated or unsaturated alkylene group having 1 to 20 carbon atoms (however, the alkylene group is not directly bonded to another alkylene group in the formula) bonded to the above divalent bonding group.
R′, R″ is a hydrogen atom or has 1 or more carbon atoms
Represents 20 saturated or unsaturated alkyl or aryl groups.

R ₁ , R ₂ : Hydrogen atom, each independent saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms, or R ₁ and R ₂ represent a heterocycle containing a nitrogen, oxygen or sulfur atom.

X, Y: mutually independent −R′, halogen atom, −OR′, −NR′R″, −COOR′, −
NHCOR′, −NHSOR′, −CONR′R″,
−SO ₂ NR′R″, NR′−CO−R″, −
NO ₂ , -CN, -CF ₃ or -SO ₃ M (M
represents 1 equivalent of a mono- to trivalent cation). R' and R'' represent a hydrogen atom or a saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms.

l, m: Represent 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. 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, and bases. Organic pigments such as color dye pigments and inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, red, iron black, zinc white, deep blue, and ultramarine blue can be used.

The amount of the pigment used in the above example is 80% of the pigment dispersion.
It is preferably less than 80% by weight, 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, and examples of polyols include ethylene glycol, propylene glycol, 1,3
- Diols such as butylene glycol, 2,3 butylene glycol, 1,4 butylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, and dicyclopentadiene diol, and triols such as glycerin, trimethylolethane, and trimethylolpropane. .

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. If the average molecular weight is less than 200, the pigment particles cannot be sufficiently stabilized in the pigment dispersion, and the average molecular weight
When it is larger than 2000, compatibility decreases and versatility is 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-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 is
If it exceeds 100 parts by weight, the polyester oligomer will occupy a large proportion of the paint or ink when using the pigment dispersion, and the unique properties of the binder resin may be impaired. In addition, for pigments such as carbon black, 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. 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,
Blended with polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polybutadiene resin, rosin ester gum, cellulose derivative, isocyanate prepolymer, etc. at a solid weight ratio of 85/15 (binder resin/polyester oligomer). No defects were found in the transparent coating film obtained.

In the present invention, the aromatic compound and organic dye derivative used as a dispersion aid have the general formula []
Examples of the residue of the aromatic polycyclic compound represented by Q in the formula include naphthalene, anthracene, phenanthrene, pyrene, chrysene, indole, thiazole, penzimidazole, quinoline, acridone, anthraquinone, phenothiazine, quinazoline, carbazole, Examples include residues of aromatic polycyclic compounds such as pensanthrone and perylene, and organic dye residues include azo compounds, phthalocyanine, quinacridone, dioxazine, anthrapyrimidine, anthanthrone, indanthrone, flavanthrone, perinone, and perylene. , thioindigo, 4,4′-diamino-1,1″-dianthraquinonyl, isoindolinone, quinophthalone,
Examples include residues such as benzimidazolone, dianthraquinone, and pyranthrone.

The compound represented by the general formula [] 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 having a functional group that easily reacts with the amine component. It can be obtained by reacting a group polycyclic compound or an organic dye derivative with an amine component.

Typical amine components introduced into the compound represented by the general formula [] are piperidinemethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, pipecolinoethyl, morpholinoethyl, and piperidinoethyl. Peridinopropyl, pipecolinopropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl, N,N-methyl-lauryl-aminopropyl, 2-ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, p-dimethyl Aminoethylsulfamoylphenyl, p
-diethylaminoethylsulfamoylphenyl, p-dimethylaminoprohylsulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl, and the like.

When the above-mentioned amine component is introduced into the side chain as represented by the general formula [], it shows strong affinity with anionic moieties such as carboxyl groups of polyester oligomers, and reduces the viscosity of the pigment dispersion. It is thought that this contributes to improved fluidity and dispersion stability, such as a decrease in structural viscosity, and the amount of dispersion resin used relative to the pigment can be reduced.

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 heterocycle containing a nitrogen or sulfur atom. But especially
When R', R'' is an alkyl group having 1 to 4 carbon atoms,
The pigment dispersion effect becomes extremely good. It is also advantageous because the amino compound used as a raw material can be easily produced.

Furthermore, aromatic compounds include -SO ₂ Cl, -COCl,
Since substituents such as -CH ₂ Cl are relatively easily introduced, other terminals other than R ₁ and R ₂ of the amine component react with substituents such as -SO ₂ Cl and -COCl-CH ₂ Cl. Preference is given to those which are easily substituted with amino groups.

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 [] to the pigment is 0.5 to 100 parts by weight of the pigment.
It is preferably 30 parts by weight; if it is less than 0.5 parts by weight, no effect as a dispersion aid will be obtained, and if it is used in an amount greater than 30 parts by weight, the effect of the amount used will not be obtained.

In the present invention, it is preferable to use an organic solvent in order to adjust the viscosity of the pigment dispersion to a viscosity suitable for use. The above-mentioned organic solvent is selected from among solvents that do not contain 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. be able to.
Examples of the above-mentioned organic solvents include aromatic solvents such as xylene, toluene, and solvent naphtha, hexane,
Examples include mineral spirits, aliphatic solvents such as ethylcyclohexane, ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and isophorone.

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

Examples and comparative examples will be given and explained below. Note that "parts" and "%" in the examples are "parts by weight" and "% by weight", respectively.

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

Next, 100 parts of phthalocyanine blue, polyester oligomer, 25 parts of TOESTAR L-010 (trademark manufactured by Toyo Ink Manufacturing Co., Ltd., nonvolatile content 100%), 5 parts of the above dispersion aid (-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 sheaker for 2 hours to obtain a dispersed paste. Next, alkyd resin varnish for air-drying paints, amino alkyd resin varnish for baking paints, aminoacrylic resin varnish for baking paints, and acrylic resin varnish 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 resolver 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 bubbling cage (JISK-5400, 4, 5), the blobs were 10μ or less in all paints. In addition, with each paint thinner, for air-dry alkyd resin paint, baked amino alkyd resin paint, and baked amino acrylic resin paint, use food cup No. 4 for 20 seconds (at 25°C), and for acrylic resin lacquer for 12 seconds (at 25°C). ), the viscosity was adjusted to 100%, and the coating was spray-coated onto a tin plate, and then the respective paints were dried as required to prepare coated plates. In all cases, clear, high-gloss, and good coatings were 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, 41.7 parts of phthalkyd 133-60 [trademark of Hitachi Chemical Co., Ltd., nonvolatile content 60%], and 108.3 parts of xylene were mixed uniformly in a mayonnaise bottle, and then 1/16
Example 1: Adding 1000 parts of inch steel beads
Dispersion treatment was performed in the same manner as above to obtain a comparative dispersion paste. Next, the resin varnish for paint used in Example 1 was added to this comparative dispersion paste.
A comparative air-dry alkyd resin paint, a comparative baked amino alkyd resin paint, a comparative baked amino acrylic resin paint, and a comparative acrylic resin lacquer were obtained by blending and mixing in the same manner as above, and a paint test was conducted. As a result, both comparative paints
Bubbles of 100μ or more were observed, and the surfaces of all the resulting coating films were rough 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, and then Example 1
The following dispersion aid (-b) was obtained by reacting with the amine () used in .

Next, 100 parts of titanium white, polyester oligomer, Elberon 5803 [trademark of Bayer AG,
Non-volatile content 100%] 10 parts, dispersion aid (-b) 10 parts,
40 parts of xylene was mixed uniformly, 160 parts of 1.5 mm glass beads were added, and the mixture was dispersed in a sheaker for 1 hour to obtain a dispersed paste. Next, polyester polyol resin varnish, acrylic polyol resin varnish, and aminoacrylic resin varnish for baking paints are blended into this dispersed paste so that the pigment content is 100% of the total binder resin, and the mixture is uniformly mixed with a dissolver to form a paint. were adjusted to obtain a polyester urethane resin paint base, an acrylic urethane resin paint base, and a baked amino acrylic resin paint. These paint base ingredients and paints are tested using a tube gauge [JIS K-5400, 4, 5].
When I examined the whelk, the size of the welt was less than 5μ. Next, to the above polyester urethane resin paint base and acrylic urethane resin paint base, add a specified isocyanate hardener as a hardener and mix thoroughly. were added, the viscosity was adjusted to 20 seconds (25°C) using a food cup No. 4, and spray painting was performed on a tin plate. When each paint was dried in a prescribed manner and a coated plate was prepared, a clear, high-gloss, and good coating film was obtained in each case.

Comparative example 2 100 parts of titanium white, acrylic resin varnish,
20 parts of Almatex 748-16 [trademark of Mitsui Toatsu Chemical Co., Ltd., non-volatile content 50%] and 30 parts of xylene were mixed uniformly, 150 parts of 1.5mmφ glass beads were added, and the mixture was dispersed in the same manner as in Example 2. A comparative dispersion paste was obtained. Next, the 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 comparative polyester urethane resin paint base, a comparative acrylic urethane resin paint base, and a comparative baking were prepared. An aminoacrylic resin paint was obtained, and a paint test was conducted in the same manner as in Example 2. As a result, both comparative paints
Bubbles of 100μ or more were observed, and the surfaces of all the resulting coating films were rough and low gloss.

Example 3 Add 10 parts of unsubstituted quinacridone to 100 parts of chlorosulfonic acid at 10 to 20°C, stir at 40 to 50°C for 3 hours, pour into 1000 parts of ice water, filter, and wash with water to obtain quinacridone monosulfone. The compound was obtained. This chlorosulfonated product was reslurried with 300 parts of ice water, 20 parts of N,N-diethylaminopropylamine was added, stirred at below 10°C for 4 hours, filtered,
Washed with water. Next, 0.5% of 300 copies of this water cake
The mixture was added to an aqueous sodium carbonate solution, stirred for 1 hour, filtered, washed with water until neutral, and dried to obtain the following quinacridone derivative (-c).

Next, 100 parts of carbon black, polyester oligomer CKS-760 [trademark of Nippon Gosei Kagaku Kogyo Co., Ltd.,
Non-volatile content 90%] 47.6 parts, 10 parts of the above-mentioned quinacridone derivative (-c), and 175.7 parts of xylene were uniformly mixed, 1000 parts of 1/16 inch styrene beads were added, and the mixture was subjected to Sheaker dispersion for 2 hours to obtain a dispersed paste.
Next, nitrified cotton varnish and acrylic resin varnish for lacquer were added to this dispersion paste so that the pigment content was 10% of the total binder resin.
A paint was prepared by uniformly mixing with a resolver to obtain a nitrified cotton lacquer and an acrylic resin lacquer. 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 coating films obtained were all clear and had high gloss. 12 seconds (25
In the sedimentation test of the paints whose viscosity was adjusted to 30°F (°C), they were all stable for a long time.

Comparative Example 3 100 parts of carbon black, nitrated cotton varnish [Daicel Corporation nitrated cotton RS 1/2 seconds (IPA 25% wet) 30% ethyl acetate 30%, xylene 40% non-volatile content 22.5%]
Mix 190.4 parts and 24.9 parts of xylene uniformly, and make 1/16
A comparative dispersion paste was obtained by adding 1000 parts of inch steel beads and carrying out the dispersion treatment in the same manner as in Example 3. 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 nitrified cotton lacquer and a comparative acrylic resin lacquer. I did a paint test. As a result, bulges of 100 μm or more were observed in all comparative paints, and the resulting paint films all had rough surfaces and low gloss. Also, in the sedimentation test, all comparative paints sedimented early.

Claims (1)

[Scope of Claims] 1. A pigment dispersion consisting of a pigment, a dispersion resin, a dispersion aid, and, if necessary, an organic solvent, wherein the dispersion resin is a polyester oligomer, and the dispersion aid is represented by 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 formula [] In the formula, Q: a residue of an aromatic polycyclic compound or an organic dye residue; A: represents a direct bond or a divalent bonding group shown below. -O-, -NR'-, -S-, -CO-, -
SO ₂ −, −CR′R″−, −SO ₂ NR′−, −
CONR- or a combination thereof;
Alternatively, it represents a phenylene group, which is a 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) bonded to the above divalent bonding group.
R′, R″ is a hydrogen atom or has 1 or more carbon atoms
20 saturated or unsaturated alkyl groups,
Represents an aryl group. R ₁ , R ₂ : Hydrogen atom, each independent saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms, or R ₁ and R ₂ represent a heterocycle containing a nitrogen, oxygen or sulfur atom. X, Y: mutually independent −R′, halogen atom, −OR′, −NR′R″, −COOR′, −
NHCOR′, −NHSOR′, −CONR′R″,
−SO ₂ NR′R″, NR′−CO−R″, −
NO ₂ , -CN, -CF ₃ or -SO ₃ M (M
represents 1 equivalent of a mono- to trivalent cation). R′, R″ represent a hydrogen atom or a saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms. l, m: represent mutually independent integers of 0 to 2. n: 1 to 6 p: represents an integer of 1 to 2. 2. A patent claim consisting of 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 item 1.3 The polyester oligomer has an average molecular weight of 200 to 200.
2000. The pigment dispersion according to claim 1 or 2, which is in the range of