JPS6059264B2 - Pigment composition containing phthalocyanine pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigment compositions containing phthalocyanine pigments.

Our GB 1263684 specification and claims states that: a metal phthalocyanine blue pigment in dry pigmented form is contacted with a polar aliphatic solvent which is at least partially miscible with water; In a pigment treatment process that consists of separating the solvent from the treated pigment, the metal phthalocyanine blue pigment has the following formula: (Formula ヰCuP
c represents a chlorinated or unchlorinated copper phthalocyanine residue, R represents a cyclic or acyclic alkyl group or aryl group having 1 to 20 carbon atoms, and R1 represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms; represents a cyclic or acyclic alkyl group or aryl group, these alkyl groups or aryl groups are unsubstituted or substituted with a hydroxyl group, an amino group, an alkylamino group or an amide group, and X and y are 1,2
or 3, but the sum of X and y is 2, 3 or 4
It is.

) A method for treating pigments consisting of adding a small proportion of copper phthalocyanine derivatives. The present inventors have discovered that by introducing dehydroabiethylamine, tertiary amines or quaternary ammonium salts into the copper phthalocyanine derivatives, the resulting compositions have improved fluidity, tinting strength and gloss of paints and inks. We have discovered an unexpected fact that is superior to what was previously known.

Accordingly, the present invention provides phthalocyanine pigments and pigments of the following formula 1: (wherein Pc represents a phthalocyanine residue and R is a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, an aryl group, an aralkyl group or a dehydroabidroxy group). represents an ethylamine residue, and R1 represents a hydrogen atom or a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, an aryl group or an aralkyl group, an alkyl group, a cycloalkyl group represented by R and R1, The aryl group or aralkyl group may optionally be substituted with one or more hydroxyl groups, X represents a number from 1 to 4, Y represents a number from 0 to 1 to 3, X and The sum of y represents 1 to 4.

) and, when y represents O to 3 in the above formula, a sufficient amount of dehydroabiethylamine represented by the following formula (■) to substantially neutralize the free sulfonic groups. , and when y represents 0, the following formula ■: or the following formula ■: (wherein R2, R3 and R each represent an alkyl group or an alkylene group, and R5 represents an alkyl, alkylene or aralkyl group) , 3, B(-' represents an anion species, the total number of carbon atoms in the cation part of the tertiary amine or quaternary ammonium salt is from 20 to 60, and the group R
At least one of 2, R3, R4 and R5 has a continuous backbone of at least 12 carbon atoms.

) and a sulfonated phthalocyanine derivative formed from a tertiary amine or a quaternary ammonium salt. Preferably two of said R groups have a backbone of at least 12 consecutive carbon atoms, and the total number of carbon atoms in the tertiary amine is preferably from 25 to 45.

Anion species B (-' preferably represents halide, acetate or hydroxide. Phthalocyanine dyes of formula 1 are metal-free or are zinc, copper, cobalt, nickel or other transition metal phthalocyanines. and can contain halogen atoms, especially chlorine atoms, in the phthalocyanine molecule.

The following formula (2): (wherein, CuPc represents a copper phthalocyanine residue, and x represents the above meaning.

) Copper phthalocyanine containing no halogen atom is preferred. Phthalocyanine dyes can be produced by commonly used methods, such as by contacting phthalocyanine with chlorosulfonic acid or fuming sulfuric acid for several hours under heat, then pouring into an aqueous sodium chloride solution, and recovering the breath cake by filtration. can.

Phthalocyanine pigments are metal-free or contain zinc,
It can be copper, nickel or other transition metal phthalocyanine and can contain up to 5% chlorine.

A preferred pigment is copper phthalocyanine, which may be in alpha or beta crystalline form or a mixture of both. The ratio of phthalocyanine pigment to sulfonated phthalocyanine dye represented by formula 1 is from 88:12 to 99:1 by weight, preferably from 92:8 to 96:4.

In the sulfonated phthalocyanine derivative formed by combining the compounds represented by formula 1 and ■, x may be 1 to 4 and y may be 0 to 3; .5 and y represents O to 3 are preferred.

In the sulfonated phthalocyanine derivative formed by combining the compound represented by formula 1 with the compound represented by formula (1) or (2), x may be 1 to 4 and y may be 0, but x may be 1 to 2. Preference is given to compounds of formula 1 which represent .5.

Compounds of formula II may be based on specific alkyl or alkylene amines, but are more conveniently obtained from mixtures of hydrocarbon residues of naturally occurring oils and fats, such as tallow, corn oil, fish oil or whale oil. Good. Such suitable tertiary amines include dimethyl tallow, dimethyl hydrogenated tallow, dimethyl soybean oil, dimethyl octadecyl, dimethyl eicosanyl, dimethyl docosanyl, monomethyl di(dodecyl), monomethyl (hydrogenated tallow), monomethyl di eicosanyl. , monomethyl didocosanil,
Mention may be made of tridodecyl and triotadecylamine or mixtures thereof. The substituents R and R1 of the sulfonated phthalocyanine dye represented by formula 1 have 1 carbon atom.
to 22 cyclic or acyclic alkyl, aryl or aralkyl groups, each represents, for example, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl, hexadecyl, octadecyl, eicosyl, phenyl, benzyl. and dodecylphenyl or 2-hydroxyethyl groups. The sulfonated phthalocyanine derivative formed by combining the compounds represented by formulas 1 and 2 is, for example, a copper phthalocyanine containing X sulfone groups and Y sulfonyl chloride or sulfonamide groups, which is substantially free of free sulfone groups. It can be prepared by reaction with a sufficient amount of dehydroabiethylamine to neutralize and react with the sulfonyl chloride groups, if present.

The sulfonated phthalocyanine derivative formed by combining the compounds represented by formulas 1 and 2 is, for example, a phthalocyanine compound containing It can be prepared by reacting with one or more species of amines.

When the amine of formula (1) is capable of forming a solution in an aqueous mineral or organic acid solution, the sulfonated phthalocyanine-amine derivative can be prepared in an aqueous solution.

Alternatively, it can be prepared in a suitable solvent and the product removed, for example, by precipitation with water or optionally by addition of water and removal of the solvent by distillation. Such solvent preparation methods are particularly useful for amines that do not readily form solutions in aqueous acids. Suitable solvents include, for example, acetone, methyl ethyl ketone, ethanol and methanol, with isopropanol being particularly preferred. Further, the sulfonated phthalocyanine-amine derivative can be produced in an aqueous solution using a water-soluble compound represented by formula (1). Sulfonated phthalocyanine derivatives can be added to pigments at various stages of their manufacture, processing, or use.

This is an aqueous slurry of pigment or British Patent No. 11408.
It can be added during treatment of pigments with solvents, such as the solvent treatment described and claimed in No. 36. In these two cases, the sulfonated derivative can be prepared in advance and then added as a powder, press cake, slurry or "solution," or it can be prepared in situ within the aforementioned limits on solubility and amine type. Alternatively, a pre-prepared sulfonated derivative can be added during kneading of the pigment in the application system, for example in a bead mill, or simply mixed with the pigment powder before use. This is a feature of the composition of the present invention.Addition methods include (a) adding the phthalocyanine dye and amine separately to the aqueous pigment slurry to form a sulfonated derivative in situ; (C) in situ derivatization during solvent treatment of pigments according to the procedure described in GB 1 140 836; A method in which a previously prepared derivative is added is preferred.

The pigment compositions of the present invention can be used to color a variety of media.

They can be used in decorative paints, gravure printing inks, nitrocellulose, alkydo-M/F (melamine/formaldehyde) resins and acrylic-M/F resin systems, but especially in media containing a high proportion of hydrocarbons in the solvent. Are suitable. Another feature of the pigment composition of the present invention is the high pigment content and excellent tinting power when kneaded in a hydrocarbon solvent in the absence of a resin and later added to ink and coating media. The ability to provide fluid dispersions of

With respect to this aspect of the invention, these dye amine compositions are preferably such that the amine has one or more alkyl or alkylene chains having at least 20 carbon atoms. It will be seen in the following examples that the sulfonated derivatives promote good fluidity and flow stability of otherwise dense and/or thixotropic systems and also promote dispersion rates.

These are of particular value for the production of high pigment content dispersions with good rheological properties when used together with the urethane compounds claimed in DE-A-2350454.

It is a water-insoluble compound that contains urethane groups and no significant proportion of basic amino groups. These urethane compounds preferably have the following formula: (wherein R6 and R8 represent a group obtained from a monohydroxyl compound and R7 represents an organic bridge group) or the following formula: (wherein R9 and RIO represent a group obtained from a monoisocyanate compound). represents a group, R
7 represents the meaning as described above.

). Preferred solvents for such dispersions include aromatic and aliphatic hydrocarbons. Next, the present invention will be further explained with reference to Examples.

In the examples, 0 parts and 1% represent 1 part by weight and 1% by weight, respectively, unless otherwise specified. A part by weight has the same relation to a part by volume as a kilogram to a liter.

The table accompanying the example shows the properties of the composition containing the treated pigment of that example.

Example 1 Pigment-form β-copper phthalocyanine was treated with Lisapol (Li
ssapOl)NX (anonylphenol/ethylene oxide condensate) by high-speed stirring.
Dispersed in 0(1) part of water.

The following formula ■A: 8 parts of the compound represented by was added and stirred.

Adjust the pH to 5 by adding dilute hydrochloric acid or sodium hydroxide solution.
．． Adjusted to 0. ROsinAmine
) Compound 7 of the following formula, known as D:
．． Two parts were added in triplicate in the form of a 0.2 molar acetate aqueous solution.

The slurry was stirred three more times, then filtered to separate the clear liquid, washed with water to remove salt until the pH became neutral, and dried at 50°C. 103 parts of a blue pigment composition was obtained.

Example 2 The product 3CB of Example 1 was mixed with white spirit 5? in a 112' vessel containing 318 inch steatite balls (250 fIf). and 18 parts of urethane compound (1) for 1 hour.

The urethane compound (2) was prepared according to German Published Application No. 2350454 by mixing 3 moles of tolylene diisocyanate (a commercially available mixture of 2,4- and 2,6-isomers), 2 moles of ethylene glycol and 2 moles of oleyl alcohol in 80% methyl ethyl ketone. The reaction was carried out at ℃ for 1 hour, and the methyl ethyl ketone was distilled off. The produced fluid dispersion is ZahnCUp NO. The run-off time for No. 3 was 8j seconds, and it maintained its fluidity over time.

2.33 parts of this dispersion was added to white paint 7W with the following composition.
with stirring at low speed (up to 500 r'Pm). (Betsukosol P.47O is 70% in white spirit
% long oil soya alkyd. ) Example 3
A paint colorant was prepared from the product of Example 1 by charging the following materials to a 112 liter container.

Grind these for a while, then P. Add 47O4O parts and knead for 3 minutes, then add P. 37 parts of 47O and 3.84 parts of desiccant solution were added.

The mixture was kneaded for an additional 30 minutes and removed.

7 parts of this colorant were used to make a blue paint by the method of Example 2(a). b The procedure of Example C above was followed except that the product of Example 1 was replaced by 16 parts of untreated β-phthalocyanine blue pigment.

Example 4 One (1) part of the compound represented by the formula VA in Example 1 was stirred in 300 g of water.

The pH was adjusted to 5.0 with dilute hydrochloric acid or sodium hydroxide. 90 parts of the compound of formula (1) in the form of an aqueous 0.2 molar acetate solution were added over 30 minutes. The slurry was stirred for an additional 30 minutes and then filtered to separate the clear liquid.
Rinse with water until pH is neutral to remove salt, then 50°C.
and dried.

A blue powder of 18 cents was obtained.

Example 5 Product 3 of Example 1 was converted into untreated β-copper phthalocyanine 2
Example ? except that 5.7 parts and 4.3 parts of the product of Example 4 were substituted. I repeated the method.

Example 6 The procedure of Example C was repeated, except that 16 parts of the product of Example 1 were replaced with 13.7 parts of untreated beta-copper phthalocyanine and 2.3 parts of the product of Example 4.

Example 7 10 parts of crude copper phthalocyanine were ground with 20 parts of inorganic salt until the phthalocyanine was in pigment form.

6 parts of mixture N (92 parts of dicopper phthalocyanine) was added to 9 (1) parts of isopropanol and heated under reflux conditions for 4 hours. 9 (1) parts of water and 8 parts of the compound of formula VA of Example 1 were added to the mixture and the isop a/manol was distilled off.

The pH was adjusted to 5.0 with the desired acid, and 7.2 parts of the compound represented by formula (1) was added in three parts in the form of a 0.2 molar acetate aqueous solution.The slurry was stirred for three more parts, and then The clear liquid was separated by filtration, washed with water until neutral to remove salts, and dried at 50C.

One part of a blue pigment composition was obtained.

Substantially similar results were obtained when the compounds of formulas VA and 1 in this example were replaced by adding 152 parts of the product of Example 4 before, during, or after the isopropanol treatment step.

Example 8 Part (9) of the product of Example 1 was replaced by the product of Example 7 (
9) Example using part? I repeated the method.

The display of the paint of the said example is NO. The samples were prepared on an A5tralux card using a No. 7 wired laboratory applicator bar (K-Bar).

Comparative observations regarding fluidity, tinting strength and color are shown in Tables 1 and 2. The results showed improved properties of paint compositions using the pigment compositions of the present invention in contrast to results using untreated phthalocyanine.

Example 9 The beads and mill were charged with the following ingredients:

Mixing was carried out for 4 hours until the viscosity of the mixture increased.

Then added the next ingredient. Mixing was continued for a further 6 hours at room temperature.

The resulting dispersion was NO. 3 Zahn Cup
The run-off time in the cup was 1 hoe and it retained this fluidity over time. A blue decorative alkyd paint was prepared from this dispersion according to the method later in Example 2(a).

A second dispersion prepared by the method of this example, replacing 25.7 parts of crude copper phthalocyanine and 4.3 parts of the product of Example 4 with 30 parts of crude copper phthalocyanine, retained its fluidity. The viscosity increases significantly over the dispersion mixed with the product of Example 4.

Example? A long oil alkyd decorative paint made from this dispersion by the method described in the following section had 10% less tinting strength and a reddish tinge than the corresponding paint with the addition of the product of Example 4. Example 10a A 0.5 liter ball mill was charged with the following ingredients.

．． - Knead 16
The mixture was stirred for an hour and then n parts of phenol varnish and 28 parts of toluene were added to 100 parts of the millpigment with stirring.
In this way, a gravure ink with a pigment content of 6% and a pigment:binder ratio of 1:5 was obtained.

* Phenol varnish consists of the following ingredients: (Arcinol RL.3O is an esterified pentaerythritol modified phenolic resin.)b Example 1011 was repeated except that the product of Example 1 was replaced with an equal weight of untreated beta-copper phthalocyanine pigment.

Example 11 55 parts of hydrocarbon solvent $P3 (Shell-Mex) and Example 2 in a 0.5 liter container containing 25 (2) a318 inch steatite balls and (8) parts of the product of Example 1. The mixture was kneaded with 15 parts of urethane compound (1) for a period of time.

The resulting dispersion was NO. The run-off time in the Tourn Cup for No. 3 was 9 seconds and maintained this fluidity over time. This dispersion solution was added to the phenol varnish (1) part while stirring, and then the hydrocarbon soluble βBP3.
20 parts were added.

While stirring, after one powder, an ink with a pigment content of 6% was taken out. b Example 11a was repeated except that the product of Example 1 was replaced with an equal weight of untreated β-copper phthalocyanine pigment.

Illustrations were made on newsprint from the inks of Examples 10a-11b.

Table 3 shows the comparative observation results regarding fluidity, tinting power and gloss.
and 4. Example 12 Eight parts of compound ■A were converted to the following formula ■: CUPC(SO2NHCH2CH2OH)2(SO3H
) Example 1 was repeated except that 8 parts of the compound represented by 2 were substituted and 72 parts of compound (1) was replaced by 5.4 parts of compound (2).

Example 13 Example 4 was repeated except that the compound represented by formula VA was replaced with an equivalent amount of the compound represented by formula 1 of Example 12, and the compound 9 represented by formula 1 (B was replaced by a tin moiety). I gave it back.

The yield was 165 parts. Example 14 Example 1, except that product 3(2) of Example 1 was replaced by 25.7 parts of untreated β-copper phthalocyanine blue and 4.3 parts of the product of Example 13. was repeated.

Example 15 Part (9) of the product of Example 1 was converted to the product (9) of Example 12.
The example was repeated except that the parts were replaced.

Example 16 Example 101 was repeated except that the product of Example 1 was replaced by an equal weight of the product of Example 12.

Example 17 Example 11a was repeated except that the product of Example 1 was replaced by an equal weight of the product of Example 12.

Example 18 The following formula (2): (In the formula, CuPc represents the above meaning, C2OH29 represents a dehydroabiethyl residue, and x+y is about 2.5.

) by treating crude copper phthalocyanine with chlorosulfonic acid at 110 to 113°C for 5.5 hours,
It was then prepared by pouring into an ice/salt/water mixture. The filtered and washed breath cake was further reslurried in ice/salt/water and treated with rosin amine (ROsin, An).
llne) D acetate solution was added dropwise to adjust the pH to 5.0. After being kept at 80-85°C for 1 hour, sufficient amount of hydrochloric acid was added to eliminate the blue bleed, the slurry was filtered, washed with water to remove salt, and dried at 60°C.

Example 19 The following ingredients were stirred at high speed for three times.

Twenty-five centimeters of the stirred slurry was transferred to a 1'2 liter ball mill and kneaded for 1 m.

The ω part of the milled pigment was mixed with 77.4 parts of medium and 12.4 parts of toluene.
The final ink (pigment content: 6%) was obtained by diluting with 6 parts. Example 19a was repeated except that compound (b) was used and the amount of untreated beta-copper phthalocyanine pigment was reduced to 7.

Illustrations were made on newsprint with the pigments of Examples 19a and b.

Comparative observations regarding fluidity, tinting strength and gloss are shown in Table 4. Example 20 Example, except that 8 parts of the product (8) of Example 1 were replaced by 25.7 parts of untreated β-copper phthalocyanine and 4.3 parts of compound ■. was repeated.

Example 21 Example C was repeated, except that 16 parts of the product of Example 1 were replaced with 13.7 parts of untreated beta monocopper phthalocyanine and 2.3 parts of compound II.

Illustrations with the pigments of Examples 10-21 were made as described above. Comparative observation results are shown in Tables 1-4. Examples n-25 Pigments of various pigment:dye ratios were prepared according to the method of Example 1, with the amount of rosin amine D adjusted to an amount that substantially neutralized the sulfonic groups of the dye.

Examples from these pigments? Dispersions and decorative alkyd paints were produced by the method described in the following. The crude products and results are listed in Table 5. It can be seen from this table that a pigment:dye ratio of 94:6 provides an excellent balance of dispersion fluidity and tinting power. Examples 26 and 27 (where x represents 1 and 1.5.

) A pigment was produced by the method of Example 1. The amount of dianamine D used was adjusted to substantially neutralize the free sulfonic groups of the dye.

Examples from these pigments? Dispersions and decorative alkyd paints were produced by the method described in the following. The results were compared in Table 6. It can be seen from the table that when sulfonamide groups are present in the dye, paints with the strongest tinting strength are obtained when compounds having 1 to 1.5 sulfone groups are used. Example 28 Surrounding substituted chlorine atoms 1. Substantially α-type copper phthalocyanine with a heel weight of 1% and the compound of Example 18 with a heel weight of 1% thereof were kneaded and blended into a glycerol coconut oil alkyd resin solution in a xylene/butanol solvent using a ball mill, and then Unmodified isobutylated melamine-formaldehyde (M
/F) Add the resin solution so that the pigment:binder ratio is 1:
6.6 to make the pigment amount 5.9%.

The resulting dispersion was measured using a Hegmann gauge.
The reading of ZahnjCUp is 8:7:7, and ZahnjCUp NO. The reading at 4 was 11 seconds. A dispersion prepared with the same pigment amount and pigment:binder ratio without the addition of compound ■ has a dispersibility of 8:5:3, is thixotropic, cannot be poured without stirring and Ta. Blue Alkydo M/F paints prepared by mixing these dispersions with white Alkydo M/F paints have similar tinting strength when baked.

Example 29 The product of Example 1 was compounded by ball milling into a hydroxyacrylic resin in a solvent with a 4:1 ratio of xylene (n-butanol), followed by a pigment amount of 6% and a pigment:
Diluted with unmodified isobutylated M/F resin in n-butanol solvent to a binder ratio of 1:5.

The resulting dispersion was very fluid with a Hegman gauge reading of 8:7:7, and Tourn Cup No. 4, it was 8 seconds. In contrast, similar dispersions made from untreated beta-copper phthalocyanine pigments were thixotropic and discrete. A blue acrylic paint was produced by mixing these dispersions with a white acrylic paint.

The paint obtained from the pigment of Example 1 was found to be greener with similar tinting strength compared to the paint obtained from the pigment not treated in this way. Example 30 The pigment of Example 26 was blended into a nitrocellulose varnish by ball mill kneading, followed by the addition of a mixture of nitrocellulose and maleic acid condensate varnish to give a pigment amount of 11.3% at a pigment:binder ratio of 1:1.38. Diluted to 7%.

The resulting dispersion was found to have superior fluidity, tinting strength, and gloss compared to similar dispersions prepared from untreated beta-copper phthalocyanine pigments.

Example 31 95 parts of substantially α-type copper phthalocyanine containing 1.8% w/w of chlorine atoms bonded to the surroundings were prepared by using a nonylphenol/ethylene oxide condensate [Synperonic (Sy
rlperOnic)NX,. I. C. Manufactured by I company] 0.2
It was added as a powder to 25(1) parts of water containing 1 part of water and dispersed with high speed stirring.

5 parts of a compound represented by formula VA(CuPC(SO3FI)2) was added in the form of a breath cake and stirred for 1 minute. P
H was adjusted to 4.5 with a dilute aqueous sodium hydroxide solution, and 6 parts of dimethyldi(dodecyl)quaternary ammonium chloride was dissolved in 200 parts of water and uniformly injected over 3 volumes with thorough stirring. Stir the slurry three more times,
The product was separated from the clear liquid by filtration, washed to remove salts until the pH was neutral, and dried at 50-60°C. The pigment composition of this example was compounded by ball milling into a hydroxy-acrylic resin in xylene di-n-butanol solvent 4:1, followed by unmodified isobutylated melamine/form, anodized human resin in n-butanol. Pigment amount 6
% and a pigment:binder ratio of 1:5. The initial millstone dispersions were fluid in contrast to similar dispersions made from alpha-copper phthalocyanine pigments that were not treated with dyes and amines that were thixotropic and injectable only after stirring. It was produced by mixing a white acrylic paint from a diluted dispersion of blue acrylic paint. The paints obtained from the pigments of this example are about 10% more tinted than the paints obtained from pigments not treated in this way, and also have improved resistance to agglomeration. Example 32 95 parts of the pigment β-copper phthalocyanine in the form of a breath cake were dispersed in 30 g of water with high speed stirring.

5 parts of a compound of formula VACCUPC(SO3H)2] were introduced with stirring and the pH was adjusted to 5.0 with dilute sodium hydroxide solution. The following formula ■: [In the formula, Rll and R
12 represents a methyl group, and R13 represents a soybean oil residue.

] [Kemamine]
T-9972C1 Hiyumco Chemical Products (H
Manufactured by umkOChemicalPrOducts)
41 parts were added in three portions in the form of a 0.1 molar acetate aqueous solution. Stirring was continued for three more times, and the product was separated from the clear liquid by filtration, washed with water until the pH was neutral to remove salts, and dried at 50-60°C. 103.1 parts of a blue pigment composition was obtained.

The pigment composition is mixed into the nitrocellulose varnish by ball milling, followed by addition of a mixture of nitrocellulose and maleic acid condensate varnish to dilute to a pigment amount of 11.7% with a pigment:binder ratio of 1:1.38. did. The resulting dispersion was found to have approximately 5% more tinting strength and superior fluidity and gloss compared to a dispersion similarly prepared from untreated β-copper phthalocyanine pigment.Example 33 Pigment β-copper Phthalocyanine 9, formula ■C♂C (SO3H
) x (in the formula, X represents 1.2.

) and 3.55 parts of the compound represented by soybean oil amine.
Example 32 was repeated using 45 parts. When incorporated into a nitrocellulose varnish, the flow and color properties were substantially similar to the product of Example 32. Example ? 175 parts of crude copper phthalocyanine were ground with 23 parts of inorganic salt, 1.6 parts of nodiethylaniline and 0.8 parts of glycerol monooleate until the phthalocyanine was in pigment form.

103 parts of this mixture, corresponding to 90 m of copper phthalocyanine, were added to 6 (1) parts of isopropanol and heated under reflux conditions for 5112 hours with good stirring.

Four parts of a compound of the formula VACUPC(SO3H)2 in the form of a breath cake were added and reflux continued. After one sieve, the formula ■ (in the formula, Rl3 represents a methyl group, Rll,
Rl2 represents hydrogenated tallow residue.

) [Kemami-Ne
)T. 97Ol, manufactured by Hyumko Chemical Products] was added as a hot isopropanol solution. Furthermore, after the turmoil,
60 g of water was added and the isopropanol was removed by distillation. Stirring is stopped, the pigment composition is separated from the clear liquid, and the pH is
The salts were removed by washing until the temperature became neutral, and then dried at 50-60C. The yield was 99.1 parts. By the method of Example 10, a gravure printing ink with a pigment amount of 6% and a pigment:binder ratio of 1:5 was produced by ball milling the pigment composition of this example in a phenolic resin varnish with a toluene solvent.

Compared to a similar ink made from untreated beta-copper phthalocyanine, the ink made from the product of this example is a very free-flowing millbase, 15% stronger, cleaner and more vivid. It was hot. Example 35 Formula V: CuPc(SO3H)x (in the formula, x represents 2.4).

) and 5 parts of hydrogenated beef tallow amine.
．． Example 34 was repeated using 4 parts. The gravure printing ink obtained from this composition was about 10% stronger and a more fluid millbase than the corresponding ink made from untreated beta-copper phthalocyanine. Example 36a Formula VA: CuPc(S
Compound 2, represented by O,H)2, was stirred in 2 parts of isopropanol and the temperature was raised to reflux.

Formula ■ (in the formula, Rl3 represents a methyl group, Rll, Rl2
represents hydrogenated beef tallow residue. ) amine 29
2 parts were dissolved in 2(1) parts of hot isopropanol and added over 5 minutes. After refluxing for 3 times, add 40 liters of water for 6 times,
At the same time, isopropanol was distilled off at the same rate. Stirring was stopped, and the blue-green reaction product was separated from the clear liquid by filtration, washed with warm water, and dried at 60°C, yielding 48.1 parts. b 175 parts of crude copper phthalocyanine was ground by the method of Example 34.

This mixture 103 corresponds to copper phthalocyanine 9(2)
part, isopropanol 600f! l) and heated under reflux conditions for 51175!1 f with good stirring. Product 1 of part a of this example was added as a solution in hot isopropanol and reflux was continued for 30 minutes. 600 parts of water was injected and the isopropanol was removed by distillation, after which stirring was stopped. 5. The pigment composition is separated from the clear liquid,
Wash to remove salt until pH is neutral, 50-60
Dry at °C.

The yield was 99.3 parts. The gravure printing ink prepared from the product of part b of this example by the method of example () has similar properties to the ink obtained from the product of example 34. Example 37 corresponds to 95 parts of copper phthalocyanine ground mixture 10
Example 36b was repeated using 8.6 parts with 5 parts of the product of Example 36a.

When the pigment composition thus obtained was incorporated into a gravure printing ink medium, it was 10-15% more tinting power than the corresponding ink obtained from untreated beta-copper phthalocyanine.
Example Copper phthalocyanine 9(2), substantially of the α-type, containing 1.8% w/w chlorine atoms bound to the feather envelope, was added as a powder to 5(4) parts of isopropanol and stirred until refluxed. Heated.

4.8 parts of a compound represented by the formula (2) A: CuPc(SO3H)2 in the form of a breath cake was added, and the mixture was refluxed for one minute.
Then 5.1 parts of technical di(dodecyl)methylamine were added as a solution in hot isopropanol. After one milliliter, 50 g of water was added and the isopropanol was removed by distillation.

Stop stirring, separate the pigment composition from the clear liquid, wash with warm water until pH becomes neutral to remove salt,
Dry at °C. The yield was 99.1 parts. The pigment composition of this example was compounded with a hydroxy-acrylic resin by the method of Example 31 to produce a highly fluid millbase. The blue acrylic paint obtained from this millbase was 5-10% more tinted than the paint obtained from the alpha monocopper phthalocyanine pigment that had not been treated with dyes and amines. Example 39 a Formula ■ (In the formula, Rl3 represents a methyl group, Rll, Rl
2 represents a dodecyl group.

Example 36 using 21.7 parts of amine represented by
A phthalocyanine dye-amine composition was produced by method a). The procedure of the example was repeated by adding the product 1 of part a of this example instead of adding the dye b and the amine separately.

A coating material with substantially similar application properties to that obtained from the pigment composition of Example 38 was obtained. Example 40 A substantially α-type copper phthalocyanine (Sy) part chlorinated on the outside to 1.8% w/w
Using 0.5 part of nperOnic) NX (1. manufactured by C.I.), it was dispersed in 15 (1) parts of water by high speed stirring.

With good stirring, add the product of Example 39a 1Cif
I, was added in one drop as a hot isopropanol solution. After one more powder was stirred, the pigment composition was collected through p-filtration, washed, and dried. Long oil sawyer (SOy) based on decorative paint system
a) When formulated in a pentaalkyd resin, the product of this example has about 25% more tinting power than an equivalent weight of untreated α-1 copper phthalocyanine pigment and also has substantially improved resistance to agglomeration. Ta.

Example 41 Chlorine atoms substituted in the outer circle 1. Copper Phthalocyanine Co., Ltd., containing substantially α-1 type Copper Phthalocyanine Co., Ltd., was blended with the product of Part a of Example 39 into a glycerol coconut alkyd resin solution in a xylene/butanol solvent by ball milling. Then, an unmodified isobutylated melamine formaldehyde resin solution was added to obtain a pigment:binder ratio of 1:6.
．． 6 to a pigment amount of 5.9%.

The resulting dispersion had a Hegman gauge reading of 8:7112.
:7112 and the flowability measured with Tournkatup NO4 was 9 seconds. A similar milled pigment dispersion prepared from 100 parts of alpha-1 copper phthalocyanine pigment was thixotropic;
It could be injected only after stirring. The paint which was then diluted and produced by the above procedure had a Hegman gauge reading of 8:5:3. However, it still showed thixotropy. By mixing these diluted dispersions with white alkydo M/F paint,
A blue Alkydo M/F paint was produced.

A coating containing the product of Example 39a is
The coloring strength was 10% stronger and the color was redder and brighter than that obtained by omitting the product. Example 36a142a
Similar results were obtained using dye compositions of and 43a.
Example 42 Formula (1) (wherein the groups Rll and Rl2 each represent an eicosanyl or docosanyl group, and Rl3 represents a methyl group.

Example 3 using 32.6 parts of amine represented by
A phthalocyanine dye composition was produced by method 6a. The halogen-free substantially α-1 type copper phthalocyanine pigment 9(2) used in Example 39 was prepared by the method of Example 31 together with part w of the product of part a of this example to form a hydroxy-acrylic resin. It was blended into. The resulting diluted fluid dispersion had a Hegman gauge reading of 8:7112:7 and a Tourn Cup NO. The reading of 4 was W seconds. A similar dispersion prepared from one (1) part of untreated alpha-copper phthalocyanine pigment was thixotropic, poorly dispersible at the millstone stage, and remained so even after dilution with resin. The acrylic paint obtained from the dispersion containing the dye composition is untreated α
It was about 20% more tinted than that obtained from the copper phthalocyanine dispersion, and was also cleaner and had better agglomeration resistance. Using the method of this example, Examples 36a, 3S and 43
Substantially similar results were obtained using the dye composition of a.

υExample 43 Breath cake formula ■A: Compound 20f represented by CuPc(SO3H)2! I) was stirred in 600 parts of water and the pH was adjusted to 5.0 with dilute sodium hydroxide solution.

16.8 parts of the soybean oil amine used in Example 32 was added in three parts in the form of an acetate aqueous solution. Continue stirring for 3 more times,
The product was separated by filtration, washed and dried to yield 36.1 parts of a blue-green dye composition. ] Chlorine content 47.1%
A nitrocellulose ink was prepared from untreated Phthalocyanine Green Pigment Powder 905 and 10 parts of the product of Part a of this Example by the method of Example 32.

When compared with a similar ink prepared from untreated Phthalocyanine Green Pigment 10, the ink formulated with the dye composition was found to have the same tinting strength but better flowability and considerably better gloss and transparency. did. ;Mi Example 44 150 parts of Greeno pigment powder, a pigment phthalocyanine with a chlorine content of 47 A%, was mixed with highly efficient stirring. Ton 8 (
4) and the temperature was increased to reflux.

After 1st mistake, Example 4? 15 parts of the product was added as a slurry in acetone and reflux was continued for one additional hour, then 8 parts of water was added as a slurry in acetone.
00 parts were added and the acetone was distilled off.

A mixture of 15 parts of concentrated hydrochloric acid and 15 parts of water was then added uniformly over a period of 2 minutes. After three millings, stirring was stopped, and the product was separated from the clear liquid by filtration, washed with warm water, and dried at 50-6 ml.

The yield was 18.tau. When incorporated into a nitrocellulose medium by the method of Example 32, the product of this example has comparable coloring properties but significantly superior milling pigment flow compared to a similar dispersion prepared from untreated phthalocyanine green. has. Example 45 18 parts of pigmented β-copper phthalocyanine powder prepared by conventional salt milling method followed by solvent treatment in isopropanol were mixed with 2 parts of the product of Example 42a, 80 parts of toluene and 1 CM of steatite balls. 28 containing 250 parts
Added to the glass shear in the volumetric section.

Seal the shell and store the contents 1fi1! The mixture was kneaded for f hours. A sufficiently fluid dispersion liquid was obtained. In contrast, Example 4
A similar dispersion made in the absence of product 2a could not be run. A dispersion containing the product of Example 42a was stirred and added to a phenolic resin medium in toluene solvent to produce an ink with a pigment:binder ratio of 1:5 and a pigment content of 6%. It is regarded.

). This ink was found to be similar in flow and colorability to the ink of Example 34 with excellent gloss and clarity. The product of Example 42 was converted into Examples 36a139a and 4
Substantially similar results were obtained by substituting the product of 3a.

Example 46 175 parts of crude copper phthalocyanine was ground by the method of Example 34.

103 of this mixture corresponding to (1) part of copper phthalocyanine
66 SynperO-Nic NX33O. Two parts were used and dispersed by high speed stirring. Formula ■A: CUPC(SO
5.7 parts of the compound represented by 3H)2 were added in the form of a breath cake and stirred once. The pH was adjusted to 5.0 with dilute sodium hydroxide and trimethyl-hydrogenated beef tallow quaternary ammonium chloride [Kemamine Q. 97O38, HumkOChemical
49% quaternary ammonium salt supplied by PrOductO) was uniformly injected in three doses with good stirring. The slurry was stirred three more times, and the product was separated from the clear liquid, washed to remove salts until the pH became neutral, and dried at 50-60°C. The gravure printing inks made from this product according to the method of Examples were 5 to 10% more tinted and very fluid millbases than the corresponding inks made from untreated beta-copper phthalocyanine.

Example 47 Compound 4 represented by formula VA: CuPc(SO3H)2
．． The procedure of Example 46 was repeated using 7 parts and 5.3 parts of dimethyl-benzyrudecylammonium chloride in the form of a 20% aqueous solution.

The gravure printing ink obtained from the product of this example by the method of Example 34 is 10% more tinted than the corresponding ink obtained from untreated beta-copper phthalocyanine and has excellent gloss and transparency. was.

Example 48 A portion of crude copper phthalocyanine and 8 parts of phthalimide were ground in a ball mill until the proportion of α-1 type phthalocyanine was within the range of 45 to 75%.

22.5 parts of 50% potassium hydroxide aqueous solution and hydrogenated Wood resin [Staybelite, Hercules Powder Company]
POwderCO. ) was stirred at 50° C. with 10 αμ of water until a smooth dispersion was obtained.

Example 36 in 18.7 parts of N,N-dinoethylaniline
9.2 parts of the product was stirred and then added to the resin dispersion and stirred at high speed until a smooth and stable emulsion was formed. The pulverized copper phthalocyanine mixture 1
(1) part and 2 (1) parts of water at 50° C. were added to the emulsion with high speed stirring and stirring continued until the average particle size of the pigment in the emulsion was less than 1 micron by microscopic examination. A solution of 5 parts of calcium chloride in 45 CH of water at 50°C was added, resulting in the emulsion becoming unstable and the resin precipitating.

Three times the pigment slurry was stirred and a solution prepared by dissolving 70.8 parts of concentrated hydrochloric acid in 6 parts of water at 50°C was added to obtain a final pH value of 1.0 to 1.5. The pigment composition is collected by filtration, washed with water until the filtrate does not contain salt and has a neutral pH, and finally
Dry at 0-60°C.

The gravure printing ink obtained from this pigment composition by the method of Example 34 is slightly more tinted than the ink of Example 34 and has similar millflow properties.

Claims (1)

[Claims] 1 Phthalocyanine pigment and the following formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, P
c represents a phthalocyanine residue, R is a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, an aryl group,
an aralkyl group or a dehydroabiethylamine residue, and R_1 represents a hydrogen atom or a cyclic or acyclic alkyl group having 1 to 22 carbon atoms, an aryl group or an aralkyl group, and an alkyl group represented by R and R_1; The cycloalkyl group, aryl group or aralkyl group may optionally be substituted with one or more hydroxyl groups, X represents a number from 1 to 4, and y represents a number from 0 or 1 to 3. The sum of X and y represents 1 to 4. ) and a sulfonated phthalocyanine dye represented by the above formula, when y represents 0 to 3, a sufficient amount of the following formula II to substantially neutralize the free sulfone group: ▲ mathematical formula, chemical formula, table, etc. There is ▼ dehydroabiethylamine represented by (II), and when y represents 0, the following formula III: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) or the following formula IV: ▲ Numerical formulas, chemical formulas, tables, etc. etc.▼(IV) (R_2 in the formula
, R_3 and R_4 each represent an alkyl group or an alkylene group, R_5 represents an alkyl, alkylene or aralkyl group, B^(^-^) represents an anion species, and the cation moiety of a tertiary amine or quaternary ammonium salt has a total number of carbon atoms of 20 to 60, and the group R_2
, R_3, R_4 and R_5 have a continuous backbone of at least 12 carbon atoms. ) A pigment composition comprising a sulfonated phthalocyanine derivative formed from a tertiary amine or a quaternary ammonium salt represented by: 2 Phthalocyanine pigment and the following formula I: ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, Pc
, R, R_1, X and y have the above meanings. ) and the following formula:
A patent claim consisting of a sulfonated phthalocyanine derivative formed from dihydroabiethylamine in an amount sufficient to neutralize substantially free sulfonic groups represented by ▲Mathical formula, chemical formula, table, etc.▼ The pigment composition according to item 1. 3. The pigment composition according to claim 2, wherein X represents 1 to 2.5 and y represents 0 to 3. 4 A phthalocyanine pigment, and a sulfonated phthalocyanine dye represented by the following formula: Pc(SO_3H)_X (wherein Pc and X represent the above meanings), and a sulfonated phthalocyanine dye represented by the following formula:
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, B^(^-^), R_2, R_3, R_4, and R
_5 represents the meaning as described above. 2. The pigment composition according to claim 1, comprising a sulfonated phthalocyanine derivative formed from a tertiary amine or a quaternary ammonium salt represented by: 5. The pigment composition according to claim 4, wherein X represents 1 to 2.5. 6. The pigment composition according to claims 1 to 5, wherein the sulfonated phthalocyanine is copper phthalocyanine. 7 Claim 1 in which the pigment is copper phthalocyanine
The pigment composition according to items 6 to 6. 8. The pigment composition according to claims 1 to 7, wherein the ratio of phthalocyanine pigment to sulfonated phthalocyanine dye is from 88:12 to 99:1 by weight. 9. The pigment composition according to claim 8, wherein the ratio of phthalocyanine pigment to sulfonated phthalocyanine dye is from 92:8 to 96:4 by weight. 10. The pigment composition according to claims 1 to 9, which also contains a urethane compound having two or more urethane groups and does not contain a significant proportion of basic amino groups.