JPH0339113B2 - - 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 It is known that when pigments are diluted with resin varnishes, solvents, etc. to produce paints, inks, etc., pigments tend to aggregate due to the shot, resulting in undesirable phenomena such as a decrease in coloring effect and gloss. .
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. As a dispersion resin, it may have undesirable effects such as a decrease in 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.

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 colored 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 resin. 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 comprising a pigment, a dispersion resin, a dispersion aid, and optionally an organic solvent, wherein the dispersion resin is a bisphenol A type epoxy resin, and the dispersion aid has the following general formula [ ] The above pigment dispersion is characterized in that it is an aromatic compound or an organic pigment derivative represented by the following.

General formula [] In the formula, Q: Residue of an aromatic polycyclic compound or 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, or a saturated or unsaturated alkylene group having 1 to 20 carbon atoms bonded to the above divalent bonding group (however, the alkylene group is represents a phenylene group (not directly bonded to an alkylene group). R′R″ is a hydrogen atom or a saturated or unsaturated alkyl group having 1 to 20 carbon atoms,
Represents an aryl group.

R ₁ , R ₂ : Hydrogen atoms, each independently having 1 or more carbon atoms
20 saturated or unsaturated alkyl groups, aryl groups, or R ₁ and R ₂ represent a heterocycle containing nitrogen, oxygen or sulfur atoms.

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'' are hydrogen atoms Alternatively, it represents 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 base pigments. Organic pigments such as color dye pigments and inorganic pigments such as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, begara, iron black, zinc white, navy 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 handle due to increased viscosity.

Further, when an inorganic pigment is used, a known coupling agent such as a silane coupling agent or a titanate coupling agent, which has conventionally been effectively used for dispersing inorganic pigments, can be added.

Examples of the bisphenol A type epoxy resin used as the dispersion resin in the present invention include those currently available on the market under the trade name Epicoat from Yer Chemical Co., and those under the trade name DER from The Dow Chemical Company. Especially when the average molecular weight
2000 or less, such as Epicote 1004, 1001,
834, 828, etc. are preferably used.

The amount of bisphenol A type epoxy resin used is
It can 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 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 will be impaired. Sometimes. 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 bisphenol A epoxy resin is used relative to the pigment, and pigments such as titanium dioxide are used. A relatively small amount of polyester oligomer is used for pigments that have low coloring power and hiding power and are often incorporated into paints and inks.

The pigment dispersion of the present invention has a bisphenol A type epoxy resin as an essential component as a dispersion resin, and other dispersion resin components include resins having good compatibility with the bisphenol A type epoxy resin, such as polyester oligomers, Alternatively, sucrose derivatives such as sucrose benzoate and sucrose acetate isobutyrate can also be used in combination.

The bisphenol A type epoxy resin 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 resin, polyvinyl chloride resin, polyvinyl acetate resin, polystyrene resin, polybutadiene resin, rosin ester gum, cellulose derivative, isocyanate prepolymer, etc., with a solid content weight ratio of 85/
15 (binder resin/bisphenol A type epoxy resin), no defects were found in the transparent coating film obtained by blending the composition.

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 an aromatic polycyclic compound represented by Q in the formula include naphthalene, anthracene, phenanthrene, pyrene, chrysene, indole, thiazole, benzimidazole, quinoline, acridone, anthraquinone, phenothiazine, quinazoline, and carbazole. Examples of 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, benzimidazolone, dianthraquinone, pyranthrone, and the like.

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 piperidinomethyl, dimethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, diethylaminopropyl, dibutylaminopropyl, piperidinoethyl, hypercorinoethyl, morpholinoethyl, and piperidinoethyl. nopropyl, pipecolinopropyl, diethylaminohexyl, diethylaminoethoxypropyl, diethylaminobutyl, dimethylaminoamyl, N,N-methyllaurylaminopropyl,
2-Ethylhexylaminoethyl, stearylaminoethyl, oleylaminoethyl, p-dimethylaminoethylsulfamoylphenyl, p-diethylaminoethylsulfamoylphenyl, p
-dimethylaminopropylsulfamoylphenyl, p-diethylaminoethylcarbamoylphenyl, and the like.

When the amine component described above is introduced into the side chain as represented by the general formula [], it exhibits strong affinity with the anionic moiety of the bisphenol A epoxy resin, reducing the viscosity of the pigment dispersion and reducing the viscosity of the pigment dispersion. It is thought that this contributes to improved fluidity, such as a reduction in structural viscosity, and to 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 heterocycle containing a nitrogen or sulfur atom with R' and R''. But especially
When R′ and R″ are alkyl groups having 1 to 4 carbon atoms,
The pigment dispersion effect becomes extremely good. Furthermore, the amino compound used as a raw material can be easily produced, which is advantageous.

Furthermore, aromatic compounds include -SO ₂ Cl, -COCl,
Since substituents such as -CH ₂ Cl can be introduced relatively easily, other terminals other than R ₁ and R ₂ of the amine component can be used with substituents such as -SO ₂ Cl, -COCl, -CH ₂ Cl, etc. It is substituted with an easily reactive amino group.

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 0.3 to 100 parts by weight of the pigment.
It is preferably 30 parts by weight; if it is less than 0.3 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.

The pigment dispersion of the present invention is preferably adjusted to a viscosity suitable for use using an organic solvent. The above-mentioned organic solvents include functional groups such as hydroxyl groups, which are generally used for crosslinking reactions in paints and inks,
Any solvent that does not contain amino groups, carboxyl groups, epoxy groups, methylol groups, etc. can be selected and used. Examples of the above-mentioned organic solvents include aromatic solvents such as xylene, toluene, and solvent naphtha, fatty solvents such as hexane, mineral spirits, 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 the components, including an organic solvent if necessary, and dispersing the pigment using a conventionally known dispersing machine such as a roll mill, colloid mill, sand mill, attritor, etc. can.

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 (-a).

Next, 100 parts of Phthalocyanine Blue, 25 parts of Epicote 828 (trademark manufactured by Ciel Chemical Co., Ltd.), 5 parts of the above dispersion aid (-a), and 120 parts of xylene were mixed uniformly, and further 1000 parts of 1/16 inch steel beads were mixed. was added and dispersed in a sheaker for 2 hours to obtain a dispersed paste.
Next, this dispersed paste was added with alkyd resin varnish for air-drying paints, amino alkyd resin varnish for baking paints, amino acrylic resin varnish for baking paints, and acrylic resin varnish for lacquers 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 we examined the whelks of these paints using a whelk cage (JISK-5400, 4, 5), we found that
The particle size was 10μ or less in all paints. or,
Each paint thinner has a food cup for air-dry alkyd resin paint, baked amino alkyd resin paint, and baked amino acrylic resin paint.
The viscosity was adjusted to 20 seconds (25℃) for No. 4 and 12 seconds (25℃) for the acrylic resin lacquer, and after spray painting on a tin plate, each paint was dried according to the specified schedule to prepare a coated plate. In both cases, clear, high-gloss, and good coating films were obtained. Furthermore, when the above viscosity-adjusted paint was poured into a test tube and left to stand,
All were stable for a long time.

Comparative Example 1 100 parts of phthalocyanine blue, 41.7 parts of alkyd resin varnish, phthalkyd 133-60 (trademark of Hitachi Chemical Co., Ltd., non-volatile content 60%), and 108.3 parts of xylene were mixed uniformly, and 1000 1/16 inch steel beads were added.
A dispersion process was carried out in the same manner as in Example 1 to obtain a comparative dispersion paste. Next, the resin varnish for paint used in Example 1 was blended and mixed with this comparative dispersion paste in the same manner as in Example 1. Comparative air-drying alkyd resin paint, comparative baking amino alkyd resin paint, and comparative baking An aminoacrylic resin paint and an acrylic resin lacquer for comparison were obtained and a paint test was conducted. 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.

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, Epicote
1001 (trademark manufactured by Ciel Chemical Co., Ltd.) 50% xylene solution
20 parts of the dispersion aid (-b) and 30 parts of xylene were uniformly mixed, 160 parts of 1.5 mm glass beads were added, and the mixture was subjected to sheaker dispersion for 1 hour to obtain a dispersed paste.
Next, polyester polyol resin varnish, acrylic polyol resin varnish,
Blend aminoacrylic resin varnish for baking paints so that the pigment content is 100% of the total binder resin, mix uniformly with a resolver to adjust the paint, and prepare polyester urethane resin paint base, acrylic urethane resin paint base, A baked amino acrylic resin paint was obtained. When these paint base ingredients and paints were examined for bulges using a bulge gauge (JIS K-5400, 4, 5), they were all 5 microns or less. 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 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, acrylic resin varnish,
Example 2 20 parts of Almatex 748-16 (trademark of Mitsui Toatsu Chemical Co., Ltd., non-volatile content 50%) and 30 parts of xylene were uniformly mixed, and 150 parts of 1.5 mm glass beads were added.
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 2 was blended and mixed with this dispersion paste for comparison 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 baking for comparison 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 xacridone 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 monosulfone of xacridone. I got a monster. This chlorosulfonated product was added to 300 parts of ice water to reslurry, then 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 a carbon soda aqueous solution, stirred for 1 hour, filtered, washed with water until the filtrate became neutral, and then dried to obtain the following quinacridone derivative (-c).

Next, 100 parts of Carbon Black, Epicote 828
(Trademark manufactured by Ciel Kagaku Co., Ltd.) 42.8 parts, 10 parts of the above quinacridone derivative (-c), and 180.5 parts of xylene were mixed uniformly, 1000 parts of 1/16 inch steel beads were added, and the mixture was dispersed for 2 hours to form a dispersed paste. I got it. Next, nitrified cotton varnish and lacquer acrylic resin varnish are added to this dispersion paste so that the pigment content is 10% of the total binder resin, and mixed uniformly with a dissolver to adjust the paint. An acrylic resin lacquer was obtained. 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 clear and had high gloss. In a sedimentation test of paints whose viscosity was adjusted to 12 seconds (25°C) using a food cup No. 4, they were all stable for a long time.

Comparative Example 3 100 parts of carbon black, 190.4 parts of nitrated cotton varnish (Daicel Corporation's nitrated cotton RS 1/2 seconds (isopropyl alcohol 25% wet) 30% ethyl acetate 30%, xylene 40% non-volatile content 22.5%), xylene 24.9 parts 1000 parts of 1/16-inch steel beads were added thereto, and dispersion treatment was carried out in the same manner as in Example 3 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 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 comprising a pigment, a dispersion resin, a dispersion aid and, if necessary, an organic solvent, wherein the dispersion resin is a bisphenol A type epoxy resin,
The above pigment dispersion, wherein the dispersion aid is an aromatic compound or an organic dye derivative represented by the following general formula []. General formula [] In the formula, Q: Residue of an aromatic polycyclic compound or 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, or a saturated or unsaturated alkylene group having 1 to 20 carbon atoms bonded to the above divalent bonding group (provided that the alkylene group is (not directly bonded to) represents a phenylene group. R′R″ represents a hydrogen atom or a saturated or unsaturated alkyl group or aryl group having 1 to 20 carbon atoms. R ₁ , R ₂ : Hydrogen atom, each independently having 1 to 20 carbon atoms
20 saturated or unsaturated alkyl groups, aryl groups, or R ₁ and R ₂ represent a heterocycle containing nitrogen, oxygen or ionic atoms. 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'' are hydrogen atoms Alternatively, it represents 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. 2. The pigment dispersion according to claim 1, comprising 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. 3. The pigment dispersion according to claim 1 or 2, wherein the bisphenol A type epoxy resin has an average molecular weight of 2000 or less.