JPS5933621B2 - coated pigment - Google Patents

Description

[Detailed description of the invention] Pigments can be used in paints, printing inks, paints, textile printing, and synthetic resins.
It is used for purposes such as coloring rubber etc.

The pigment must be uniformly and finely dispersed in the vehicle, synthetic resin, rubber, etc., and therefore the pigment must be in the form of a fine powder. However, powdered pigments can seriously contaminate the working and living environments due to the scattering of colored dust during manufacturing, especially during crushing and packaging, and when mixed with vehicles, synthetic resins, rubber, etc. It becomes a problem. Furthermore, since powdered pigments contain a large amount of air, they have poor compatibility with vehicles, synthetic resins, rubbers, etc., resulting in poor dispersibility and reduced work efficiency.

Furthermore, when water-insolubilized pigments are obtained in the form of a slurry, such as synthetic organic pigments, and are made into powder pigments by washing, filtering, drying, and pulverizing, the pigment particles coagulate into hard particles called secondary particles. Because the particles are growing, it requires a great deal of effort in kneading to make the particles finer when mixed with a vehicle or the like.

Under the above circumstances, problems such as the hue of the printed matter becoming unclear, the gloss of the coating film becoming poor, and the coloring power of synthetic resins being reduced are unavoidable.

Various proposals have been made in the past for the purpose of solving such problems.

For example, methods include coating pigment particles with various polymeric compounds or wax, treating the surface of the pigment with a surfactant to prevent agglomeration during drying, and mixing oily substances such as vehicles with pigment paste to remove water. A method has been proposed in which the pigment is replaced with an oily substance and the pigment is coated with an oily substance.

However, although the pigment surface is based on the common goal of covering the pigment surface with some kind of coating material to solve the problems of scattering and dispersion, it has not been possible to find a suitable material for the coating material, so it has been differentiated depending on the application. We had no choice but to choose different coating materials.

Furthermore, since the properties of coating materials vary, treatment methods must also be limited. The present inventors have discovered a new coating material that solves the drawbacks of both conventional powder pigments and coated pigments that are improved thereon, and have accomplished the present invention.

The present invention provides coating with a coating agent containing as a main component one or a mixture of two or more of the compounds represented by the following formulas (a) and b), or a mixture of these and other non-volatile organic compounds. A coated pigment is provided.

(In the formula, Arl, Ar2, Ar3 represent the same or different benzene rings or alkylbenzene rings, and R1
, R2 is the formula CnH2n (where n is 2 or 3 and represents the same or different species) and has a molecular weight of 300 to 4.
12 compounds.

(In the formula, Arl, Ar2, and Ar3 represent the same or different benzene rings or alkylbenzene rings, and R is a straight chain or branched hydrocarbon group having 4 to 7 carbon atoms) with a molecular weight of 300 to 412 compound.

Pigments that can be used in the present invention include all organic and inorganic pigments, and representative ones include azo pigments,
With pigments such as phthalocyanine, quinacridone, anthraquinone, dioxazine, indigothioindigo, perinone-perylene, isoindolenine, titanium oxide, cadmium, lead, oxidized frome, and carbon black. be.

The coating material used in the present invention contains one or more of the compounds shown in a) or (b) above as a main component.

Typical compounds are exemplified by compounds belonging to formula (a): (1) α-methylbenzyl-α- in which Arl is a phenyl group, Ar2 is a phenylene group, Ar3 is a methylphenyl group, and R1 and R2 are ethylidene groups; Methyl (methino(ha)benzyrubenzene (molecular weight 300), (6)A
α where rl is a phenyl group, Ar2 is a phenylene group, Ar3 is a dimethylphenyl group, and R1 and R2 are ethylidene groups
-Methylbenzyl-α-methyl(dimethyl)benzyl-
Benzene (molecular weight 314), (1U) Arl is a phenyl group, Ar2 is a phenylene group,
α-Methylbenzyl-α-methyl(methylethyl)benzyrubenzene (molecular weight 328), (1V
) Arl is a phenyl group, Ar2 is a phenylene group, Ar3
is an isopropylphenyl group, R1 and R2 are ethylidene groups, α-methylbenzyl-α-methyl(isopropyl)benzyl-benzene (molecular weight 328), (V) Ar,
is a phenyl group, Ar2 is a dimethylphenylene group, Ar3
is a phenyl group, and R1 and R2 are ethylidene groups, bis(
α-Methylbenzyl)-xylene (molecular weight 314), (
Bis(α・α″-dimethylbenzyl) where Arl is a phenyl group, Ar2 is a methylethylphenylene group, Ar3 is a phenyl group, and R1 and R2 are 2 and 2 monosubstituted propane.
-Methyl-ethylbenzene (molecular weight 356), (VIO
Ar1 is a methylphenyl group, Ar2 is a phenylene group,
α-methyl(methyl)benzy-α・α7-dimethyl(methylethyl)benzy-benzene (molecular weight 356), where Ar3 is a methylethyl phenyl group, R1 is an ethylidene group, and R2 is a 2.2-monosubstituted propane; b) Ar1 is a methylphenyl group, Ar2 is a methylphenylene group, Ar3
is a methylphenyl group, and R1 and R2 are ethylene groups (molecular weight 328), (substitutes) Ar1, Ar2, Ar3
is an alkylbenzene ring having 8 carbon atoms, R1 and R2 are ethylene groups (molecular weight 370), (X) Ar1, A
r2, Ar3 are alkylbenzene rings having 9 carbon atoms R1, R
A compound in which 2 is an ethylene group (molecular weight 412).

A compound belonging to formula (5). As a substance, (b) 1-tolyl-1,3 diphenyl-butane (molecular weight 300) (self) 1-xylyl-1,3 diphenyl-butane (molecular weight 314) (Xll1) 1-methylethyl phenyl- 1,3-diphenylbutane (molecular weight 328) W
) 1,3,5-triphenylpentane (molecular weight 30
0) (XV) 1,3,5-triphenylhexane (
Molecular weight: 314) (XV]) 2,4,6-triphenylheptane (molecular weight: 328).

Next, some examples of methods for producing these compounds will be explained.

This is a method in which styrene, α-methylstyrene, or an alkyl substituted product thereof is reacted with benzene or an alkylbenzene in the presence of an acidic catalyst such as sulfuric acid or a cation exchange resin. Taking styrene and xylene as an example,
When an acidic catalyst is dispersed in xylene and styrene is successively added, 1-phenyl-1-dimethylphenylethane is initially produced, but as styrene continues to be added, more styrene is added and 1-phenyl-1-dimethylphenylethane is produced. (1) and (2) are produced, and some of the styrene is dimerized in advance and then reacts with xylene to produce (2).

When these mixtures are purified by vacuum distillation, the boiling point is 33
A viscous liquid with a temperature of 5-390°C and a viscosity of about 700 cst (100'F) is obtained. Similarly, with toluene and styrene (1). (b) A mixture mainly composed of C9 aromatic hydrocarbons and styrene that are purified and separated from platform formers, etc., is a compound with a molecular weight of 328 belonging to formulas (a) and (b) (arc (LV). A mixture of (e.g.) is obtained. In addition, in a similar reaction between this C9 aromatic hydrocarbon and a mixture of α-methylstyrene and vinyltoluene, (b), (to)
A mixture of compounds with a molecular weight of 328 is obtained. In addition, Hv can be obtained as a hydride of a trimer of styrene, or by thermally decomposing polystyrene, separating triphenyl alkenes from the product by vacuum distillation, and performing hydrorefining. ■, to ■, to obtain the compound of heli.

Furthermore, compounds such as (2), (2), and (x) can be produced by dehydrochlorinating benzene or alkylbenzene and dihalogenated paraffin, such as dichloroethane, which is an intermediate for vinyl chloride monomer, using a Friedelkratz catalyst. can do.

Formulas (a) and (b) other than those exemplified above (0)
Compounds belonging to the above can also be easily produced according to the various exemplified methods described above.

Of course, the types of raw materials and reaction methods exemplified above are expressed by the formula (a
) and (5) are not limited to these.
If the molecular weight of the coating compound of formula (a) or (b) is too high, it may become solid or the coating effect may not be exhibited. On the other hand, if the molecular weight is too low, it will have a low boiling point and will volatilize during the drying process. Use a compound with a predetermined molecular weight because it will be easier to clean.

However, even if some compounds are solid at room temperature, they can be used as a mixture as long as they are liquid. For example, when styrene and xylene are reacted in the presence of a sulfuric acid catalyst, a mixture of formulas (a) and (b) is obtained as a liquid product, and although the solid product can be separated by careful fractionation, it is possible to separate the solid product as a liquid product. You can use it if you have it. The type and amount of the coating agent of the present invention can be appropriately selected and used depending on the type of pigment and use. The amount of coating agent used is at least the minimum amount necessary to effectively coat the pigment particles and achieve the desired purpose, but if it is too large, the coating agent may flow out of the coated pigment or fluidize the pigment. te1
~300% by weight, preferably 5-200% by weight, more preferably 10-120% by weight.

The coating agent used in the present invention has excellent affinity with pigments, particularly organic pigments, due to its chemical structure, so that an effective coating can be obtained even in a small amount, and scattering of pigment powder can be reliably prevented.

The coating used in the present invention may also include a printing ink vehicle,
It does not harm paint vehicles and has excellent compatibility, so it does not impair the gloss and color tone of printed surfaces and coatings, and it also has excellent drying properties, improving work efficiency.

Even when coloring polymeric materials such as resins or rubber, the coating agent used in the present invention has excellent compatibility, so pigments can be dispersed very easily, improving work efficiency.

Furthermore, the coating material used in the present invention includes polyvinyl chloride,
Urethane resin, epoxy resin, acrylic resin, A
It has the effect as a plasticizer, softener, and extender oil for BS resins, SBR, NBR, chloroprene rubber, chlorinated rubber, etc., so it is not suitable for BS resins, SBR, NBR, chloroprene rubber, chlorinated rubber, etc. It has the advantage of omitting the use of harmful plasticizers.

The coating material of the present invention is mainly composed of one type or a mixture of two or more of the compounds represented by formulas (a) and (b) above, but depending on the use of the pigment and the requirements for the properties of the coated pigment. Components consisting of other nonvolatile organic compounds may be used in combination as appropriate.

Components that can be used in combination can be selected from a variety of sources, including animal oils, vegetable oils, mineral oils, synthetic organic liquids, resins, oligomers, etc., and may be used singly or as a mixture of components of printing ink vehicles and paint vehicles, plasticizers such as resins and rubbers, etc. Any component that can be used as a softener, extender oil, etc. is preferable in consideration of compatibility with the intended use.

For ink use, drying properties can be adjusted as desired by combining the present coating agent with a paraffin fraction having a high boiling point, preferably liquid paraffin having a boiling point of 250° C. or higher.

The amount added is 10 to 80 wt%, preferably 20 to 60 wt%, based on the coating material. Although various methods can be employed to produce the coated pigment of the present invention, typical methods are described below.

Adding a coating agent to an aqueous suspension of organic pigment primary particles obtained during synthesis of an organic pigment while stirring in the presence of a surfactant, and coating the organic pigment primary particles with the coating agent, A method of obtaining a coated pigment by subsequent dehydration and drying is preferred. When using this method, the pigment is coated in the state of primary particles without causing secondary particles due to agglomeration of primary particles during the drying process when using a normal powder pigment manufacturing method.
Excellent dispersion in printing ink vehicles and paint vehicles. As a result, excellent color tone can be obtained even if the pigment concentration is reduced. Another advantage of this method is that during dehydration (washing), the coated pigment particles become coarse particles due to aggregation, making it easy to separate them from the aqueous phase, and washing and drying are also easy. be.

Furthermore, since the pigment is coated with primary particles,
Grinding process becomes unnecessary. Another method is to suspend powdered pigment obtained by a conventional manufacturing method in water, add a coating agent, and stir to adsorb and coat the pigment particles with the coating agent, followed by dehydration, washing, and drying. Alternatively, a method of kneading a powder pigment and a coating material may be used.

The coated pigment of the present invention does not cause the problem of pigment powder scattering in any of the manufacturing process, shipping process, and usage process.

Because the pigment is coated with a material compatible with printing ink vehicles, paint vehicles, etc., instead of an air layer, it has excellent dispersibility and compatibility with vehicles, etc., and the stirring time in the premixing process is reduced to 30 minutes compared to conventional methods. Compared to the above, it takes just 2 to 3 minutes to blend in evenly, and the working time can be greatly shortened.

In the kneading process, since it is extremely soft compared to conventional powder pigments, it can be kneaded easily, the pressure and number of times required to be kneaded are greatly reduced, and a tenfold improvement in work efficiency per unit time is achieved.

Since the coating material is suitable as a plasticizer, softener, etc. for polymeric materials, it has excellent dispersibility in resins, rubbers, etc.

The embodiments and effects of the coated pigment of the present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Example 1 As a coating agent, ortho-xylene and styrene were used at a molar ratio of 1
: 2, in the presence of a 95% sulfuric acid catalyst (weight ratio of 1 to 3 hydrocarbons) at 15°C and precision distillation from the fraction obtained in the distillation range of 340 to 385°C. The above compound is a compound belonging to the above formulas (a) and (b) with an average molecular weight of 314. ), (V). (A viscous liquid, which is a mixture whose main component is a compound of XlO, was used.

Carmine 6B was used as a pigment and coating treatment was carried out in the following manner.

A slurry of carmine 6B with a concentration of 6 wt% synthesized in the aqueous phase (rosin calcium was added to the pigment at 14 wt% during insolubilization).
% added) was stirred at 80°C, then the coating agent was heated and pressurized at a weight ratio of 1 to 2 parts of the pigment, and was injected into the slurry from an injection nozzle.The coating was completed in a few minutes. did.

This was vacuum filtered, washed with water, and dried to remove moisture to obtain a coated pigment. No pigment scattering occurred during this manufacturing process. An offset ink was produced using this coated pigment as a raw material (the following parts are by weight).

100 parts of rosin modified phenolic resin, 80 parts of linseed oil,
20 parts of 30 parts of Nisseki No. 5 Solvent (manufactured by Nippon Oil Co., Ltd.)
A resin varnish was prepared by uniformly mixing at 0° C. for 30 minutes. Using three rolls, the mixture was kneaded at the following mixing ratio to form an ink, and the tack value of the ink was adjusted to 12±0.5 in Ink-0 Meter value (1/).

No scattering of pigment is observed during kneading, and it is extremely easy to knead during kneading. Only one pass is required at a roll pressure of 20k9/ml, and the pigment is dispersed in a very short time, and the flow on the rolls is excellent. was. When printed on paper according to the usual method, both the gloss and color tone were excellent. According to the present invention, not only the working efficiency of ink formation is greatly improved, but even though the coating agent is added to the ink components, the ink is No deterioration in performance was observed, and on the contrary, improved results were obtained. Comparative Example 1 In place of the coated pigment of Example 1, a powdered pigment of Carmine 6B obtained by a conventional manufacturing method was used, and ink was printed using a typical conventional offset ink formulation.

The same resin varnish as in Example 1 was used.

Using three rolls, the following mixing ratio was kneaded to form ink according to a conventional method, and the tack value of the ink was adjusted to 12 ± 0.5 using the Ink-0-Meter value (') as in Example 1. did.

During kneading, the pigment was significantly scattered, and in order to obtain the desired dispersion of the pigment, the inter-roll pressure was 45k9/Cd, and the mixture was passed three times, so it took a longer time than in Example 1.

The glossiness of the printed matter was inferior to that of Example 1.

Example 2 As a coating material, a C8 aromatic fraction (ortho-xylene 32.
8%, metaxylene 37.6%, paraxylene 19.6%
%, ethylbenzene 10.0%) and styrene in the presence of a sulfuric acid catalyst, the formula 0 has an average molecular weight of 314.
1). (V). [Yes]? A coated pigment was obtained in the same manner as in Example 1 using a compound and a mixture of these compounds in which the dimethylphenyl group was substituted with an ethylphenyl group and the dimethylphenylene group was substituted with an ethylphenylene group, and an offset ink was prepared and printed. , the same results as in Example 1 were obtained.

Example 3 Carmine 6B powder pigment obtained by a conventional method was dispersed and suspended in water to obtain a suspension in water with a concentration of 6 wt%, and this was treated under the same conditions as in Example 1. A coating agent was added to obtain a coated pigment.

Claims (1)

[Scope of Claims] 1. A coating agent containing as a main component one or a mixture of two or more compounds represented by the following formula (a) or (b), or a mixture of these and a non-volatile organic compound. Coated coated pigment. (a) Ar_1-R_1-Ar_2-R_2-Ar_3
(In the formula, Ar_1, Ar_2, Ar_3 represent the same or different benzene rings or alkylbenzene rings, and R_1, R_2 represent the same or different types with the formula CnH_2_n (however, n is 2 or 3)) Compound (b) with a molecular weight of 300 to 412 ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Ar_1, Ar_2, Ar_3
(represents the same or different benzene ring or alkylbenzene ring, and R is a straight or branched hydrocarbon group having 4 to 7 carbon atoms) having a molecular weight of 300 to 412. 2 In formula (a), Ar_1 is a phenyl group, Ar_
2 is an alkylphenylene group, Ar_3 is a phenyl group, R
Claim 1 in which _1 and R_2 are ethylidene groups
Coated pigments as described in section. 3 In formula (a), Ar_1 is a phenyl group, Ar_
2 is a phenylene group, Ar_3 is an alkylphenyl group, R
Claim 1 in which _1 and R_2 are ethylidene groups
Coated pigments as described in section. 4 The compound of formula (b) is 1-alkylphenyl-1.
A coated pigment according to claim 1 which is 3-diphenylbutane. 5. The coated pigment according to claim 1, wherein the nonvolatile organic compound is liquid paraffin.