WO2004065503A1

WO2004065503A1 - Process for producing processed pigment composition and processed pigment composition obtained by the process

Info

Publication number: WO2004065503A1
Application number: PCT/JP2003/000609
Authority: WO
Inventors: Masato Yanagi; Mitsuharu Hino; Mayumi Ogura; Yasushi Uehara; Takuya Fujino; Shinichi Azuma
Original assignee: Toyo Ink Mfg. Co., Ltd.
Priority date: 2001-08-01
Filing date: 2003-01-23
Publication date: 2004-08-05
Also published as: JP2003041179A; JP3903753B2

Abstract

A process for producing a processed pigment composition which comprises treating an aqueous suspension of an organic pigment with a water-insoluble resin in an oligomer region having flowability at ordinary temperature. The pigment thus treated has satisfactory transferability from an aqueous phase to a resinous phase, and has high crystal stability after the phase transfer. It has excellent resolubility after drying.

Description

Method for producing additive pigment composition and additive composition protected by the method

Technical field

The present invention is applied to pigments for plastics and plastics, printing

A method for producing a pigmented composition having excellent suitability as a power liner or other raw material for a coloring material, and a method for producing the same.

The present invention relates to the obtained additive composition.

Background Art Using hanging materials as coloring materials for various industrial materials, wet cake pigments containing water are used, and are used in the fields of inks, plastics, and sock colorants. Was used. Jet cake pigments are disclosed in Japanese Patent Publication No. 7-1 885.

No. 75 As described in this patent publication No. 8 — 60068, it contains resin and solvent with a molecular weight of several tens to hundreds of thousands and is processed by steel. Pigmentation is a common method.

The face as a color material; ^ is expected to be stable and easy to handle without agglomerating fine particles. In order to solve the above problem, there has been proposed a processed pigment in which a finely dispersed material is included by a dispersion stabilizer such as a resin to suppress the aggregation of the materials.

However, when the aqueous suspension of the wet cake pigment is subjected to a phase conversion treatment from an aqueous phase to a resin phase with a normal resin, the resin is added to the resin in order to improve the flowability and phase conversion efficiency. The addition of solvents becomes indispensable, raising concerns about the need to control the solids content after treatment and the impact of volatile solvents on the working environment.

In the case of completely evaporating the solvent after the treatment, there was a problem that it took a long time to re-dissolve in the solvent such as ink.

Further, in the treatment with a solvent alone and the treatment with a resin having a high solvent content, there have been problems such as the formation of solidification after the pigment is converted into a resin phase.

The present invention has been made in view of such problems, and efficiently converts a pigment from an aqueous phase to a resin phase with a lower concentration of solvent and preferably without solvent than before. Provided is a method for producing a pigment composition which is compatible with each other, has a high phase inversion stability, and is excellent in resolubility after drying, and a pigment composition using the method. It is here.

Accordingly, the present inventors have conducted intensive studies, and as a result, treated an aqueous suspension of an organic pigment with a water-insoluble resin in the oligomer region, which has fluidity at room temperature, to obtain a pigment. Water phase Therefore, the phase inversion from the resin phase to the resin phase is good, and the stability of the phase inversion is high. The present inventors have found an additive composition that can be obtained, and have led to the present invention.

That is, the present invention relates to the following items 17

The first invention is a MR material characterized in that an aqueous suspension of an organic pigment is treated with a water-insoluble resin having a molecular weight of 200,000, which has fluidity at room temperature. The method of the composition

The second invention is a water-insoluble resin molecule

Is 2 0 0 2 0

The method according to the first aspect of the invention, which is characterized in that the value is 0.

A third invention is the method for producing a pigment composition according to the first or second invention, wherein the water-insoluble resin has a crosslinking reactivity.

The fourth invention is a method for producing a self-added pigment composition according to any one of the claims, which is characterized in that the water-insoluble '14 resin has a radial crosslinking property.

The fifth aspect of the invention is characterized in that the water-insoluble resin has an ultraviolet crosslinking property. 4 to 4 are methods for producing a pigment composition described in any one of the inventions.

The sixth invention is directed to a pigment component in an aqueous suspension of an organic pigment. 0 Water-insoluble resin for villages 5 0 0

Parts or less are treated by mixing and mixing. The method for producing the additive composition according to any one of the above items 15 is characterized in that:

A seventh aspect of the present invention is a pigment composition obtained by the method for producing a pigment composition according to any one of the sixteenth aspects.

The aqueous suspension of an organic pigment used in the present invention refers to a non-in-produced aqueous suspension after synthesis, as well as a wet-washed pigment that has been filtered and washed. It is also possible to add water to the material and make it an aqueous suspension again.

Further, the aqueous suspension of the organic material used in the present invention may be added with a surface treatment agent, a surfactant dispersant, or a pigment conductor to make fine particles at the time of synthesis.

In addition, the concentration of the aqueous suspension of the organic pigment used in the present invention varies depending on the type of the organic pigment.

Not less than 100/0 and less than 100% good 3; less than 25 ri% or more and less than 50 weight% indicates that the phase is efficiently converted from the aqueous phase to the resin phase when treating the pigment. Based on water content

As the organic pigment used in the present invention, for example, u Azo pigments such as melamine-based and xanthene-based pigments, azo pigments such as soluble azo pigments, insoluble azo pigments and condensed azo pigments; Pigments, etc.

Examples of the dyeable rake pigments include, for example, pigment, o- (hereinafter abbreviated as PY) 18, PY100, PY1

0 4, Pigment Orient (hereinafter abbreviated as P o) 39, Pigment Red, (hereinafter abbreviated as PR) 81, PR 83, P

R 9 0 P R 16 9 P R 17 2 P R 17, P R 1

7 4, PR 19 3, Pigment n-hole Vh (hereinafter abbreviated as PV) 1 PV 2, PV 3 PV 4, PV 12 PV

27, PV 39, Pigmen h bule (hereinafter abbreviated as P B)

1, PB2, PB1 4 PB6 2 Pigment U-

(Hereinafter abbreviated as P G) 1 P G 2 P G 3 P G 4, P G

45, PBr3 etc.

Examples of the azo pigments include, for example, PR53 and PR5.

0, PR 49 PR 57 '1, PR 48: 1, PR 52:

1st azo pigment PR 1? P R 3 P 0 P R 2

1, PR 1 1 4, PR 5 PR 1 4 6, PR 1 7 0, P

〇 3 8 ゝ P R 1 8 7 P Y 1 P Y 3, P Y 1 67, P

Insoluble azo pigments of Y 15 4 P O 36, P Y 12 P Y 13 P Y 14, PR 144 P R 16 6, P R 2

14, PR 2 42, PY 93 PY 94 PY 95, etc. Condensed azo pigments and the like.

Examples of the phthalocyanine-based pigment include copper phthalocyanine, phthalocyanine lean, fast sky blue, and the like. Examples of the condensed polycyclic pigment include antiquinone pigments such as pγ24PY108, P P51PR166, PR177, and PB60. Molecule 2 having a flow ^m of at normal temperature in the present Description 0 0 1

Treatment of water-based material with water using a water-insoluble resin of 0000 When the molecular weight of this water-insoluble resin exceeds 100 000, the material is inverted from an aqueous phase to a resin phase. On the other hand, if the molecular weight is less than 200, the fe-phased material in the low molecular weight solvent or resin will grow and crystallize. ΓMoleculars

J is the average molecule used in the gel-pasm-link O-graphimetry.

Further, in the present invention, the value of T g (glass

4m8 of rigid resin with high <transition occupancy) does not cause phase inversion even if stirred and mixed for ft hours, so it needs to use a water-insoluble resin. J having a property refers to a field where the viscosity in a temperature range of 400 is in a state of 100 000 mPas or less, and of course, the viscosity is 100 000 mPa • S or less. Resin or resin with viscosity exceeding 100 mPas Dissolve non-fluid resin to reduce the viscosity of the entire resin to 10

It is possible to use a composite resin in a state of 0 0 0 mPa * s or less. The viscosity in the present invention is a value measured using a single-type viscometer.

The molecular weight having fluidity at room temperature used in the present invention is 200.

Examples of the water-insoluble resin of 100 to 100 include various resins used in applications such as paints, inks, coloring agents for plastics, printing, coloring, and the like. It must be compatible with various resins, solvents and other additives, and do not impair the physical properties of the resulting product.

In addition, the lowering the molecular weight of the resin is better for dissolving or dispersing the pigment that has been processed into a solvent or a binder resin such as an ink or a pigment. Considering the effects such as the suppression of crystal growth, the more preferable molecular weight of the water-insoluble resin is 200 200

Is 0

Examples of water-insoluble resins such as: ン変 X フ X 樹脂樹脂樹脂樹脂、、, 変性変性マ石油非非 7 7 7 7 Resin, melamine resin, ketone resin, pinyl chloride 'vinyl acetate copolymer. Resin, butyral resin, chlorinated polypropylene mouth pyrene resin, acryl resin, polyester resin, polyester resin Rear amide resin, polyester resin Resin, styrene / maleic acid resin, natural resin, phenolic resin, urethane resin, pinyl chloride resin, epoxy resin phenolic resin, etc. The combination of the above resin components makes it possible to design a resin having a desired glass transition point by considering the copolymer composition, and to control the fluidity. Because it is possible, it is optimal for the present invention.

Further, the water-insoluble resin used in the present invention is preferably a resin having a cross-linking-reactive, that is, a resin having a cross-linkable functional group. Physically, an isocyanate is used as a cross-linking agent. When a epoxy such as a resin having a functional group having active hydrogen, that is, a resin having a hydroxyl group, a hydroxyl group or an amino group is used as a crosslinking agent. And a resin having a hydroxyl group, an ano group, a thiol group, and the like.In addition, as the crosslinkable functional group, an ethylenically unsaturated double bond having a radial crosslinkability It is possible to cure using a heat-polymerizable initiator and an ultraviolet-curable initiator, respectively, and it is possible to crosslink the resin alone when using an electron beam. . More specifically, the following resins can be exemplified.

As a resin having a hydroxyl group, UT-200 (viscosity: 250 000 m) of S Kori Goma of Soken Chemical Co., Ltd.

P a S (at 25), solids: more than 98%, molecular weight 200 0), UT-3100 (viscosity: 300 to 4 s (25 ° C), solid content: 9.9% or more, molecule

U M B-100 1 (viscosity: 200-400

5), solid content: more than 99%, molecular weight 85

2000 (viscosity: 20000 to 2500 mPa · s (25 ° C.), solid content: at least 9.9%, molecular weight: 1100).

As a resin having a lipoxyl group, CB—300 (viscosity • 1500

500 mPa • s (25.C), solids-9.9 / or more, molecular weight 250 000), CBB-301 (viscosity • 180 000-21)

0 0 0 mPa • s (at 25), solids • 9.9 ^^, molecular weight 2600), CBL.E;-310 (viscosity • 2500-2

800 mPa · s (25 ° C), solid content of 9.9% or more, molecular weight of 260,000, etc.

As a resin having a radial cross-linking property, it can be used as an acrylic resin.

U-relet, ethoxylate-t-det U-method π-prototype (measurement) Evening) U-reset, proxy-required glycerin U (me) Evening rehearsal U, u-re-estreak U-relet, Pentae V-Slot h V ラ V V V V V V タタタタタタタタタタタタタ Others include BASF's Accu-based sesame seeds-Laromer system U-Daisel's E becry 1 series Beamuse V system manufactured by Shizukawa Chemical Co., Ltd.

U's Toa Gosei Co., Ltd.'s pi Xus U U's Showa Takanashi Co., Ltd.'s lipoxy series says Honka Co., Ltd.'s power charad, Shi U-z, Kyoeisha Chemical Co., Ltd.'s U Resin such as U-size

It is possible to use the resins listed among the resins having a run-through ability as the resin having an ultraviolet property, but the suppression of the oxygen inhibition effect during polymerization is relatively large. If you like it,

The stirring mixer according to the present invention is a machine capable of stirring and mixing an aqueous suspension of an organic pigment and a water-insoluble resin. That is, the material in the aqueous suspension is kneaded in a stirring mixer. Any machine can be used as long as the phase can be changed into the resin from the phase, and there is no limitation.

The method of controlling the additive composition according to the present invention is as follows.

n Organic pigment slurries immediately after formation U Slurling — slurries that have been pulverized and dispersed by, for example — If <is an aqueous suspension of dry slurries such as u sla u — α machine Add the water-insoluble resin, then stir and mix and knead.o The amount of the water-insoluble resin is 500,000 per 100 parts by weight of the pigment in the aqueous suspension of the organic material. Parts or less are preferred, and 100,000 parts are more preferred.The kneading temperature is set at 0800 from the viewpoint of the crystallinity of the material and the deterioration of the resin. C is preferred

It is more preferable that the temperature is 260 ° C. At the beginning of the phase inversion process, the eight components consisting of material, water, and resin are muddy water.

Despite the fact that the kneading is continued, the separation into the resin phase and the aqueous phase in which the pigment has been incorporated is continued, and it is confirmed that the aqueous phase has become transparent. Assuming that the time until the resin phase and the aqueous phase are separated and the aqueous phase becomes transparent is the phase inversion time, it is preferable that the time is shorter from the viewpoint of production efficiency.

方法 It is possible to efficiently convert the fine pigment component dispersed in the aqueous suspension in the aqueous phase to the resin phase, and further to the resin phase. After the phase inversion process, the water in the aqueous phase is drained (1: drainage) and heated or heated under reduced pressure as necessary. Then, the processed pigment composition of the present invention in which the pigment is dispersed in the resin can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example In the table, “Γ” indicates all parts by weight, and Γ% j indicates “% by weight”.

Example 1

3 3 ン Π 方方 3 5 方 5 方方方 5 5 方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方方A force V puller solution was obtained. The copper solution and the terazo solution are force-coupled, and the azo pigment (P

An aqueous suspension having a content of Y 12) of 4% was obtained. The obtained aqueous suspension of the raw material was filtered through a filter, washed with water and dehydrated to obtain a jet cake having a material content of 25%. V Cake 100

50 parts of U-Rufu resin (viscosity: 12 mPas (25 ° C), resin component: 99% or more, molecular weight: 246.3)

-The primary wastewater from the phase inversion from the aqueous phase to the resin phase at 60 ° C using a da is removed by decantation, and then: And dehydrated under vacuum to obtain pigment 1 (solid content: 10075 parts) in which PY 12 was dispersed in a shale U-phthalate resin.

Example 2

1-Nano-4-Methylbensen 2 Srillefonic acid 9

Five parts were analyzed, and after cooling, a diazo component was obtained according to a conventional method. Using 95 parts of β-oxinaphthoic acid, a V-Plas solution was obtained according to a conventional method. With this force, The azo component was subjected to force-punching to obtain a dye. To this was added 21 parts of resin and the pH was adjusted to 11.0. Then, 300 parts of a 35% aqueous chloric acid solution was added, and the mixture was raked to obtain the azo pigment (PR57 • 1). An aqueous suspension having a content of 3% was obtained. The obtained aqueous suspension of the unpurified pigment was filtered by a filter press, washed with water and dehydrated to obtain a pigment content of 2

A 2% check was obtained. This cake cake 1 0

For the 0 part, SK-U Sesame UMB manufactured by Soken Kagaku Co., Ltd. was used as the acrylic resin (viscosity: 200,000 mPa • s (solid content: 25 ° C: 9 9 % Or more, molecular weight 8 50) 10

0 parts were added, and the phase of the pigment component was converted from the aqueous phase to the resin phase at 60 using an 11-to-1 solution. At this time, the primary wastewater is removed by a softener, followed by vacuum dehydration as a secondary wastewater, and a pigment containing PR-57 dispersed in the acrylic resin. 2 (solid content 100%) 122 parts were obtained.

Example 3

Toyo Ink's copper phthalocyanine copper bleed is refined by a conventional ash-sticking method, filtered, rinsed and dehydrated by a full press. A type cake (PB15) with a pigment content of 30% was obtained. The cake was 100% of the UH cake. Π A meter create (viscosity 9

0 mP as (25 ° C) Resin component: More than 99%, molecular cost 3 3 8) 100 parts were added, and the pigment phase was subjected to a phase inversion process from the aqueous phase to the resin phase at 60 ° C using a planetary mixer: The wastewater is removed by decantation, and then the next wastewater is subjected to vacuum dehydration, and PB15 is dispersed in the trimethylol pulp V methacrylate resin. L-Feed 3 (solid content: 100%) to obtain 130 parts. Example 4

In the same manner as in Example 1, a jet cake having an azo pigment (PY12) content of 25 was obtained. Acrylic resin was added to 100 parts of the No. 1 jet part of Soken Chemical Co., Ltd.

S K u U Sesame U T — 3 0 0 (viscosity: 3 0 0 0 4 0 0

0 mPa • s (25 ° C), solids: ≥99%, molecular weight 2

(0000) 50 parts was added, and a phase inversion process from a water phase to a resin phase was performed at 60 ° C using a kneader. The next waste water is removed by force protection and vacuum dehydration is performed as secondary waste water, and PY 12 is dispersed in the acrylic resin. 75 parts (4 (solid content: 100%)) were obtained. Example 5

In the same manner as in Example 1, a wet cake having an azo pigment (PY12) content of 25% was obtained. Nozzle

― In contrast to 100 parts, Nippon Kayaku Co., Ltd.'s urethane clarity HO U sesame force ARAD U X — 222 (viscosity: 45

0 mPas (50 ° C), solid content: 99% or more, molecular weight 720 parts) was added, and the phase was converted from the aqueous phase to the resin phase at 60 C using a kneader. The next effluent is removed by a T-force station, and then the next effluent is subjected to vacuum dehydration to obtain a pigment 5 in which PY12 is dispersed in the resin (solid content 100 %) 75 parts were obtained.

Comparative Example 1

In the same manner as in Example 1, a wet cake having an azo pigment (PY12) content of 25% was obtained. For 100 parts of this Vh proof, add toluene (viscosity: 0.6 mPa •

Add 50 parts of S (25C), molecular weight 92.1), and use the -D to convert the pigment phase from the water phase to the oil phase with 60X: 0. The primary waste water is removed by decantation and vacuum dewatering is performed as the next waste water, and the pigment 6 in which PY 12 is dispersed in h is 6 (solid content 35%)

70 parts were obtained o (Because it azeotroped with water, it was less than the charge) Comparative Example 2

In the same manner as in Example 1, the content of the azo pigment (P Y 12) was 2> 0 /

Obtained the / o key stroke. In contrast to the 100 parts of this jerk, purple light UV-200 manufactured by Nihon Gosei Kagaku Co., Ltd.

0 0 B (viscosity-5.5 0 0 0 m P a 's (at 60) t molecule

250 000) 50 parts were added, and the phase was converted from the aqueous phase to the resin phase at 60 ° C using a boiler. Except for the next session, Vacuum dehydration was performed using water to obtain 75 parts of a pigment 7 (solid content: 100%) in which Ρ12 was dispersed in the resin.

The pigment obtained 17 obtained above is evaluated in the following items.

(Evaluation)

1 • Phase inversion

The time required for the resin phase in which the pigment has been incorporated to separate from the aqueous phase and for the aqueous phase to become transparent (until the primary wastewater is obtained) ) Was measured as the phase inversion time, and the phase inversion time was evaluated as the better phase inversion property. The shorter the phase inversion time, the better the production efficiency. Table 1 shows the results.

2-solubility

Each of the pigments 17 obtained in Examples 1, 2, 3, 4, 5 and Comparative Examples 1 and 2 was used as a binder-resin solution. Using the resin BR-187 with 40% toluene solution, the concentration of the solid content becomes 10%.

The mixture was mixed in a non-composition ratio to 2, and the mixture was stirred for 10 minutes with the first solution.The dispersity value (unit: m) of each coating solution was measured using the first solution and the ground medium. The smaller this value is, the more the solubility is shown, and if the dissolution is insufficient, the degree of dispersion becomes large. Table 2 shows the solubility of the pigment in the binder-resin solution evaluated from the dispersion value of each coating solution. 3. Hue evaluation

As described in 2. above, each coating solution prepared in the evaluation of solubility was sandwiched between two 50-im thick transparent polyethylene terephthalate films at a thickness of 500 zm, and the hue ( L, a, and b) were measured by reflection using a colorimeter ZE-20000 manufactured by Nippon Denshoku Industries Co., Ltd. Table 3 shows the results. table 1

Processed pigment Inversion time Example 1 Processed pigment 15 minutes

Example 2 Processed pigment 27 minutes

Example 3 Processed pigment 3 minutes

Example 4 Processed pigment 4 7 minutes

Example 5 Processed pigment 56 minutes

Comparative Example 1 Processed pigment 6 minutes

Comparative Example 2 Processed pigment 7 30 minutes

Table 2

Composition of coating liquid Dispersion Processing face Number of copies 40% BR-(m) Material 8 7 Solution part

number

Example Working face 30.00.02 25.0.0.07.5

1 charge 1 lower working example kaloe face 5.5.4.52 25.0.0.07.5

Example 2 Machined face 4 3 .3 3 2 25.0 .0 07.5 or less 3 3 Example 3 Caroje face 30.0 .0 2 2 5 .0 0 77.5 or less 4 .4 Example Processed face 3 0 0 0 2 2 5 .0 0 7 .5 to 5 materials 5 lower Comparative example Kalo face 2 8.0 0 2 2 5 .0 7 .5 to 1 material 6 lower Comparative example Kaloe face 3 0 .0 0 2 2 5 .0 0 Table 3

(Phase inversion)

As shown in Table 1, -JX-, -K-A-Face, 1, 2, 3,-, 4-, 1-5,

The phase inversion time of No. 6 was 10 minutes or less, and good phase inversion was obtained. On the other hand, processed pigments treated with high molecular weight resin 7 _T that took 3 0 minutes of time to phase inversion

(Solubility)

As shown in Table 2, processed pigment 1 2 3 4 5

The dispersity value of 6 is judged to be good dispersibility. A value of 7.5 m or less was obtained. It can be seen that the solubility is good.

Pigments treated with high-resin resin

As for the dispersity value of 7, a spot of about several m was visually observed, and it was not sufficiently dissolved in the binder-resin solution.

(Hue value)

As shown in Fig. 3, comparing pigments 1 56 using the same cake cake pigment, only pigment 6 has a large L value, which is a measure of transparency. It was known that the cause of the opacity, which was an opaque hue, was due to the crystal growth of the pigment. Despite the fact that crystal growth was promoted under the solvent X ring with the solvent, addition pigment 7 was too difficult to measure due to the unevenness of the formed coating film. Was

According to the present invention, when an aqueous suspension of an organic material is treated using a water-insoluble resin in a ligoma region having fluidity at normal temperature, the phase inversion of the pigment from the aqueous phase to the resin phase is achieved. A pigment composition having good crystal stability after phase inversion and high resolubility in a binder resin or the like after drying; and The production method can be provided.

The foregoing is a preferred embodiment of the present invention, and many changes and modifications can be made without departing from the spirit and scope of the invention. It will be appreciated by those skilled in the art.

Claims

The scope of the claims

1. A processed pigment composition characterized in that an aqueous suspension of an organic pigment is treated with a water-insoluble resin having a molecular weight of 200 to 100000, which has fluidity at normal temperature. Manufacturing method.

2 刖 The non-aqueous resin has a molecular weight of 2000

Method for producing the product described in Item 1

3. The method according to claim 1, wherein the water-insoluble tree is characterized by

Method of producing the second product.

4. The process for producing a pigment-added composition according to any one of claims 1 to 3, wherein the water-insoluble resin has a radial crosslinkability.

(5) The method of the additive composition according to any one of (1) to (4), wherein the water-insoluble resin has an outer line and a frame jss.- property.

6. 100 parts by weight of pigment in aqueous suspension of the organic pigment The method for producing a processed pigment composition according to any one of claims 1 to 5, wherein the water-insoluble resin (500 parts by weight or less) is treated by a stirring and mixing device. A processed pigment composition obtained by the method for producing a processed pigment composition according to any one of claims 1 to 6.