JP2000063699A - Pigment composition and resin-coloring composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a green pigment which does not generate toxic substances such as dioxins or heavy metals at all or generates them only in very small amts. when disposed e.g. by incineration, is excellent in chroma and light resistance, and is low in cost and to provide a resin compsn. which has such properties and is usable for many applications. SOLUTION: The green pigment compsn, is prepd, by mixing a yellow pigment contg. no halogen atom with a blue pigment contg. no halogen atom. The green resin-coloring compsn. is prepd. by mixing a yellow resin compsn. prepd. by dispersing a yellow pigment contg. no halogen atom in a synthetic resin with a blue resin compsn. prepd. by dispersing a blue pigment contg. no halogen atom in a synthetic resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a halogen-free green pigment composition and a halogen-free green polymer resin coloring composition.

The halogen-free green pigment composition according to the present invention is used as a so-called coloring material such as paints, gravure inks, offset inks, plastics, electrostatic color toners and cosmetics, among others.
It is extremely practical.

[0003]

2. Description of the Related Art To date, various pigments have been used as green pigments. For example, C.I. I. Pigme
nt Green 7 is clear and has excellent weather resistance
It is used for various purposes, but its structure contains about 50 chlorine.
It is included as a percentage. In addition, C.I. I. Pigment
Green 36 also contains a lot of bromine and chlorine. Therefore, it is said that dioxin may be generated depending on incineration conditions when incinerating a polymer resin colored product using this pigment or a product printed or coated with the polymer resin colored product.

C.I. I. Pigment Green
n 8 has low saturation even when it does not contain halogen,
It has the disadvantage of poor weather resistance.

C. I. Pigment Green 1
The triphenylmethane system represented by is a heavy metal salt and has a problem at the time of disposal.

C. I. Pigment Green 1
Chrome green represented by C.7, C.I. I. Pigme
Cobalt green and the like typified by nt Green 19 also contain heavy metals and have problems in disposal.

C. I. Pigment Green 5
Dibromoviolanthrone which is 4, contains bromine,
It is also expensive.

As described above, a green pigment composition containing no heavy metal in its structure and containing no halogen is rare and, in reality, very few.

[0009]

However, the present inventors have earnestly started research in view of the various drawbacks and difficulties in the above-mentioned conventional techniques. Therefore, an object of the present invention is to provide a green pigment composition using a halogen-free coloring pigment and a halogen-free green polymer resin coloring composition.

[0010]

Therefore, the present inventors have
In view of the circumstances as described above, as a result of resolving the drawbacks or difficulties of the prior art and solving them, as a result of repeated studies, by using a yellow pigment not containing a halogen atom and a blue pigment not containing a halogen atom, the weather resistance is improved. An excellent halogen-free green polymer resin coloring composition can be provided, and the present invention has been completed here.

That is, the present invention provides the following inventions. 1. A green pigment composition obtained by mixing and blending a halogen-free yellow pigment and a halogen-free blue pigment.

2. A green resin coloring composition obtained by mixing a yellow resin composition in which a yellow pigment containing no halogen atom is dispersed in a synthetic resin and a blue resin composition in which a blue pigment containing no halogen atom is dispersed in a synthetic resin.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The blue pigment containing no halogen atom used in the present invention is not particularly limited, but a blue organic pigment containing no halogen in its structure such as copper phthalocyanine, metal-free phthalocyanine and titanyl. Examples thereof include phthalocyanine, iron phthalocyanine, nickel phthalocyanine, aluminum phthalocyanine, tin phthalocyanine, cobalt phthalocyanine, sulfonated copper phthalocyanine, triphenylmethane blue, disazo blue, indanthrene blue and indigo blue. Among these, copper phthalocyanine is preferable from the viewpoint of economic resistance and various resistances such as weather resistance.

The yellow pigment containing no halogen atom is not particularly limited, but monoazo yellow, benzimidazolone yellow, flavanthrone yellow, azomethine yellow, anthraquinone yellow containing no halogen atom in its structure is used. , Isoindoline yellow, disazo yellow, metal complex pigments, azo lake, iron oxide, condensed polycyclic system and the like. Of these, yellow organic pigments containing no halogen atom are preferable.

The blending ratio of the blue pigment containing no halogen atom and the yellow pigment containing no halogen atom needs to be a proportion necessary for coloring the target green color. This blending ratio cannot be unequivocally stated because it varies depending on the type of the halogen atom-free blue pigment used and the type of the halogen atom-free yellow pigment, the dispersion conditions, the amount and type of other additives, etc. About 1 to 5 parts by weight of a halogen atom-free blue pigment is suitable for about 0.1 to 5 parts by weight of a halogen atom-free yellow pigment.

The particle size of each of these pigments is not particularly limited, and the specific surface area by the nitrogen adsorption method is 0.01 to 1
Any of 100 m ² / g can be used, but in the case of a toner for developing an electrostatic image or a color filter as described later, a finer one, preferably a specific surface area of 20 to 80 m
^In many cases, a material having a content of about ² / g exhibits excellent characteristics.

In addition to paints, it is also suitable for printing inks, resin colorants, color filters and the like.

The pigment composition of the present invention is used together with a dispersion medium and the like.
A pigment dispersion is obtained by dispersing with a known disperser.

If necessary, various auxiliaries and stabilizers such as a dispersion wetting agent, an anti-skinning agent, an ultraviolet absorber and an antioxidant may be used.

The varnish for offset ink is used as a polymer resin component, for example, a resin such as rosin-modified phenol resin, petroleum resin, alkyd resin or a drying oil-modified resin thereof, and if necessary, linseed oil, tung oil, soybean oil. Etc. and a solvent such as n-paraffin, isoparaffin, aromatech, naphthene, α-olefin, etc., and the mixing ratio thereof is resin: vegetable oil: solvent = 20 to 50 parts by weight. The range of 0 to 30 parts, 10 to 60 parts is preferable. Moreover, the varnish containing an acrylic ester is mentioned.

If necessary, an ink solvent, a drier,
It is also possible to properly mix known additives such as a leveling improver and a thickener.

Vehicles for gravure printing inks and flexographic printing inks usually contain additives such as resins, solvents and plasticizers. The resins include acrylic resins, nitrocellulose resins, polyamide resins and urethane resins. The resin may be one or more selected from resins, vinyl acetate resins, rosin resins and the like.

As the solvent, one or more solvents selected from water, aromatic hydrocarbons, esters, ketones, alcohols and the like can be mentioned. Specifically, water, toluene,
Xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isopropyl alcohol, methanol, ethanol and the like can be mentioned.

The vehicle for paint usually contains a resin, a solvent, an additive, etc., but if the resin is irrespective of whether it is curable or not, whether it is a one-component type or a two-component type,
Examples thereof include alkyd resin, modified alkyd resin, acrylic resin, alkyd-melamine resin, acrylic-melamine resin, phenol resin, polyamide resin, epoxy resin, urethane resin and vinyl acetate resin.

As the solvent, one or more solvents selected from water, aromatic hydrocarbons, esters, ketones, alcohols and the like can be mentioned. Specifically, water, toluene,
Xylene, ethyl acetate, butyl acetate, methyl butyl ketone, methyl ethyl ketone, isobutyl alcohol, normal butanol, cyclohexanone and the like can be mentioned.

As the resin for plastics, poly (meth) acrylate, polystyrene, ABS resin, AS resin, polyolefin such as polyethylene and polypropylene, polyamide, polyacetal, polycarbonate,
Examples thereof include polyesters such as PET and PBT, thermoplastic resins (plastics) using modified polyphenylene ether, and the like, but are not limited thereto.

As the resin for the color filter, polyester resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl carbazole resin, polystyrene resin, polyvinyl acetate resin, acrylic resin, methacrylic resin, silicone resin, alkyd resin, melamine resin, melamine- Examples thereof include alkyd resin, phenol resin, polyamide resin, polyurethane resin, polyimide resin, epoxy resin, phenoxy resin, styrene-butadiene copolymer, and styrene-maleic anhydride copolymer. Further, a resin precursor capable of producing these resins by the action of heat, light, electron beam or the like can also be used.

Examples of the solvent include hydrocarbons such as toluene, xylene and mineral spirit, acetone,
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as tetrohydrofuran, dioxane, monoglyme, diglyme, anisole, methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cyclohexanol, 2-methoxy. -1-
Alcohols such as propanol, 2-butoxy-1-propanol, etc., esters such as ethyl acetate, propyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, 2-methoxy-1-propyl acetate, 2-butoxy-1-propyl acetate, etc. , Dimethylformamide, amides such as N-methylpyrrolidone, water, and the like, and a mixture of two or more of these solvents can also be used.

If desired, additives such as surfactants, dispersants, defoamers and leveling agents may be added.

As the resin for color toner, for example,
Styrene; vinyltoluene; α-methylstyrene; styrene and its derivatives such as aminostyrene; methacrylic acid; methylmethacrylate; ethylmethacrylate; methacrylic acid esters such as butylmethacrylate; acrylic acid; methylacrylate; ethylacrylate; butylacrylate; 2 -Acrylic acid esters such as ethylhexyl acrylate, butadiene; dienes such as isoprene, acrylonitriles, maleic acid; maleic anhydride; maleic acid esters, vinyl ethers, vinyls such as vinyl acetate, ethylene; olefins such as propylene, Homopolymers or copolymers of these monomers, polyesters, polyamides, polyurethanes can be used alone or in a mixture. If necessary, known components such as a salicylic acid metal salt, a metal-containing azo compound, a charge control agent such as niglycine or a quaternary ammonium salt, a low molecular weight polypropylene, a low molecular weight polyethylene, an offset preventing agent such as a wax, and the like may be added. It can be added.

The ratio of the pigment composition in the above pigment dispersion is
70% by weight or less is preferable, and a range of 0.01 to 50% by weight is particularly preferable. The rest is a dispersion medium.

Since the dispersion conditions differ depending on the dispersion medium and the disperser, the dispersion temperature and the dispersion time are not limited, but the dispersion temperature is room temperature to 240 ° C., preferably room temperature to 150 ° C., the dispersion time is within 120 hours, preferably Within 5 hours.

These pigment dispersions are mixed with other additives, pigments and dyes, if necessary, and used as final paints, printing inks, plastics, color toners and recording materials.

Examples of the disperser for dispersing the pigment in these pigment dispersions include known dispersers such as a disper, a homomixer, a bead mill, a ball mill, a two roll, a three roll, a pressure kneader and an ultrasonic disperser. However, the present invention is not limited to these.

The colored resin composition of the present invention is, for example,
A yellow resin composition in which a yellow pigment containing no halogen atom is dispersed in a synthetic resin, and a blue resin composition in which a blue pigment containing no halogen atom is dispersed in a synthetic resin are mixed.

Colored resin composition prepared by incorporating the pigment composition of the present invention into the resin, or coloring obtained by incorporating the above two pigments of blue and yellow into the resin so as to become green. Any of the resin compositions can be used for known and commonly used applications. The specific preparation will be described below. Although one method will be described, it goes without saying that the same composition can be prepared by either of the former and latter methods. In the following uses, the composition can be prepared by appropriately selecting from the resins described above.

The composition for green heat-bake coating is prepared, for example, by adding one of the pigments containing no halogen atom to an organic solvent solution consisting of an alkyd resin or a (meth) acrylic resin (main ingredient).
A colored resin composition 1 was prepared by dispersing 0.1 to 30 parts by weight per 100 parts by weight of the main agent, and adding 5 to 50 parts by weight of melamine resin-based curing agent per 100 parts by weight of the main agent. A composition 2 is prepared in the same manner by using the other pigment not containing a halogen atom different from the above, and mixed so that they become green, whereby a composition for green heat baking coating is obtained. The composition thus obtained is applied to a heat-resistant plate-shaped substrate such as a metal plate, kept at room temperature if necessary, and then baked and cured at 100 to 200 ° C.

The thermoplastic resin compound for green injection molding is, for example, thermoplastic resin pellets or powders of polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, and both of the pigments containing no halogen atom, which become green. Dispersion is performed so that the total amount is 0.01 to 5 parts by weight per 100 parts by weight of the thermoplastic resin, and if necessary, a crystal nucleating agent such as aluminum stearate is added in an amount of 0.05 to 0.5 parts by weight per 100 parts by weight of the resin. Inorganic pigment such as titanium oxide is added by dry blending in an amount of 0.05 to 0.5 parts by weight per 100 parts by weight of the resin to prepare a thermoplastic resin compound for green injection molding. Keeping the residence temperature in the injection molding machine above the melting temperature of the thermoplastic resin, the components are retained so as to be uniform, and injected into a cooled mold for obtaining a molded product of a predetermined shape. , Get the desired molded product.

The composition for a green lithographic ink is, for example, a mixture of a rosin and a phenol resin, or a resin-type varnish made of an organic solvent solution of a rosin-modified phenol resin, and both pigments containing no halogen atom become green. like,
1 to 200 per 100 parts by weight of the above-mentioned resin is dispersed so that the total amount is 0.1 to 30 parts by weight per 100 parts by weight of the above-mentioned resin, and an inorganic pigment such as titanium oxide is added if necessary.
In addition, the composition for a green lithographic ink is prepared so as to be added in an amount of parts by weight. Desired printing is performed on a paper, a film or the like using this composition and dried at 30 to 80 ° C. to obtain a printed paper having a required design.

The composition for green gravure printing ink is prepared by, for example, adding a pigment containing no halogen atom to an organic solvent solution such as a nitrocellulose resin or a polyamide resin so that the pigment has a non-volatile content of 100. A total of 5 to 20 parts by weight is dispersed per part by weight to prepare a green gravure ink composition. The composition is subjected to desired printing on a film or the like and dried at 15 to 50 ° C. to obtain a printed film having a necessary design.

The toner for developing a green electrostatic image is, for example, styrene- (meth), which may be linear or partially crosslinked.
To 100 parts by weight of resin pellets or powder of an acrylic acid-based copolymer resin or a polyester resin resin containing an aromatic ring, both of the pigments not containing a halogen atom having a specific surface area of 20 m ² / g or more are green, 0.5 to 3 parts by weight of a positive or negative charge control agent such as a nigrosine compound or a chromium complex salt, and a low molecular weight such that the total amount becomes 0.5 to 10 parts by weight per 100 parts by weight of the resin and on the same basis. 1 to 3 parts by weight of waxes such as polyolefin and montanate are mixed and melt-kneaded at a temperature exceeding the softening point of the resin to obtain a uniform kneaded product, which is then pulverized and classified to have an average particle size of 7
A green toner for developing an electrostatic image is prepared from a colored resin particle powder having a particle size of ˜15 μm. 0.3 to 5 parts by weight of a fluidity improver such as hydrophobic silica is externally added to 100 parts by weight of the toner to obtain a green electrostatic image developing toner. This toner is used as it is in the non-magnetic one-component developing method, or is mixed in such a manner that 0.5 to 5 parts by weight of this toner is mixed with 100 parts by weight of a carrier which may be resin-coated, such as ferrite or magnetite, and a two-component developer. Used as. This toner is particularly useful as a monocolor toner for flash fixing and heat fixing.

The UV curable composition for a green color filter is prepared, for example, in an organic solvent solution of an UV curable resin composed of an alkali-soluble or solvent-soluble (meth) acrylic resin such as poly (meth) acrylate of an epoxy resin,
Both of the pigments having a specific surface area of 20 m ² / g or more and containing no halogen atom are photopolymerized on the same basis so that the total amount becomes 0.5 to 10 parts by weight per 100 parts by weight of the resin so as to become green. 0.05 to 3 parts by weight of the initiator is mixed to obtain an ultraviolet curable composition for a green color filter having a viscosity of 0.001 to 5 mPa · s. This composition was dropped onto a glass substrate on which a black matrix had been formed, and the composition was applied over the entire surface by a spin coater. Only a necessary portion was exposed to ultraviolet rays through a photomask, and a non-exposed portion was patterned by development. A green pattern is formed and a protective film is formed on it to form a color filter (color resist method). In addition to this, it can be applied to manufacturing such as an etching method, a printing method, an electrodeposition method, an electrophotographic method, and a transfer method.

The green enamel lacquer composition is, for example, a room temperature-curable composition which can be dried at room temperature and comprises a mixture of a (meth) acrylic resin, an alkyd resin, or a hydroxyl group-containing (meth) acrylic resin and a polyfunctional isocyanate. In a solution of an organic solvent such as the above, both of the pigments containing no halogen atom are changed so as to become green, and the non-volatile component 100 is added.
A total of 5 to 30 parts by weight per part by weight is dispersed to prepare a green enamel lacquer composition. This composition is applied to the surface of a base material and dried at around room temperature, and a curable material accelerates curing at 50 to 100 ° C. as necessary to obtain a base material having a required design.

The present invention includes the following inventions. 1. A green pigment composition obtained by mixing and blending a halogen-free yellow pigment and a halogen-free blue pigment.

2. A green resin coloring composition obtained by mixing a yellow resin composition in which a yellow pigment containing no halogen atom is dispersed in a synthetic resin and a blue resin composition in which a blue pigment containing no halogen atom is dispersed in a synthetic resin.

3. A composition for green heat-baking paint, which comprises a yellow pigment containing no halogen atom, a blue pigment containing no halogen atom, an alkyd resin main agent, and a melamine resin-based curing agent.

4. A yellow pigment not containing a halogen atom, a blue pigment not containing a halogen atom, at least one thermoplastic resin selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate, and polybutylene terephthalate, and an inorganic pigment as necessary,
A thermoplastic resin compound for green injection molding containing a crystal nucleating agent.

5. A yellow pigment not containing a halogen atom, a blue pigment not containing a halogen atom, a resin type varnish consisting of a rosin and a phenol resin, or a rosin-modified phenol resin, and an inorganic pigment and an organic solvent as required, Composition for green lithographic printing ink.

6. A composition for a green gravure printing ink, which comprises a yellow pigment containing no halogen atom, a blue pigment containing no halogen atom, a nitrocellulose resin or a polyamide resin, and an organic solvent if necessary.

7. A yellow pigment containing no halogen atom, a blue pigment containing no halogen atom, and styrene-
A green electrostatic image developing toner containing a (meth) acrylic acid-based copolymer resin or a polyester resin containing an aromatic ring, and optionally a charge control agent, wax, and hydrophobic silica.

8. It contains a yellow pigment that does not contain halogen atoms, a blue pigment that does not contain halogen atoms, an alkali-soluble or solvent-soluble UV-curable (meth) acrylic resin, and optionally a photopolymerization initiator and an organic solvent. , A UV curable composition for a green color filter.

9. A yellow pigment containing no halogen atom, a blue pigment containing no halogen atom, and a (meth) acrylic resin or alkyd resin that can be dried at room temperature or a mixture of a hydroxyl group-containing (meth) acrylic resin and a polyfunctional isocyanate are required. A composition for a green enamel lacquer containing an organic solvent according to the above.

[Examples] The present invention will be described in more detail below with reference to Examples, Comparative Examples and Test Examples.
It is not limited to these examples. In the following examples, "part" and "%" are based on weight unless otherwise specified.

[0054] Production example 1 In a 100 ml glass bottle   Blue pigment containing no halogen atoms     Fastogen Blue 5380 (C.I.Pigment Blue 15: 3) 4.0 copies   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 16.0 parts   Solvent (xylene / normal butanol = 75/25) 10.0 parts   Glass beads 3mm φ 80 parts

Weigh and 1 with paint conditioner
Time dispersed. In this dispersion

[0056]   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 30.2 parts   Super Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals) 19.8 parts

Then, the mixture was added and mixed again with a paint conditioner for 10 minutes to prepare a blue enamel. (Alkyd / melamine nonvolatile content ratio = 7/3)

Similarly, in a 100 ml glass bottle.   Yellow pigment containing no halogen atoms     Symuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 4.0 copies   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 16.0 parts   Solvent (xylene / normal butanol = 75/25) 10.0 parts   Glass beads 3mm φ 80 parts

Weigh and 1 with a paint conditioner
Time dispersed. In this dispersion

[0060]   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 30.2 parts   Super Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals) 19.8 parts

Then, the mixture was added and mixed again with a paint conditioner for 10 minutes to prepare a yellow enamel. (Alkyd / melamine nonvolatile content ratio = 7/3)

As the white paint, white enamel was prepared so that the pigment content was 30%. Titanium white is Taipaque R-93
0 (made by Ishihara Sangyo Co., Ltd.) was used.

Yellow pigment paint 7 containing no halogen atom
To 3 parts, 3 parts of a blue pigment paint containing no halogen atom were uniformly mixed.

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. It was left at room temperature for about 1 hour and baked and dried in a dryer at 140 ° C. for 15 minutes to obtain a color sample. The colorimetry of this color sample is as follows and shows the green color gamut.

[0065]       L * 43.5 C * 35.7 H * 170.1

(Accelerated light resistance test) The above-mentioned color development sample was
Accelerated weather resistance tester: Using an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.), an accelerated light resistance test for 16 hours was performed. The color difference between the test piece before the accelerated test and the painted piece after the test was measured. The color difference was 0.7 and the light resistance was good.

[0067] Comparative Example 1   Green pigment containing halogen atoms     Fastogen Green S (C.I.Pigment Green 7) 4.0 copies   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 16.0 parts   Solvent (xylene / normal butanol = 75/25) 10.0 parts   Glass beads 3mm φ 80 parts

Weigh and 1 with a paint conditioner
Time dispersed. In this dispersion

[0069]   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 30.2 parts   Super Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals) 19.8 parts

Then, the mixture was added and mixed again with a paint conditioner for 10 minutes to prepare a green enamel. (Alkyd / melamine nonvolatile content ratio = 7/3)

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. It was left at room temperature for about 1 hour and baked and dried in a dryer at 140 ° C. for 15 minutes to obtain a color sample. The colorimetry of this color sample is as follows and shows the green color gamut.

[0072]       L * 43.3 C * 37.8 H * 175.1

An accelerated light resistance test was conducted in the same manner as in Example 1 to measure the color difference between the test piece before the accelerated test and the coated piece after the test. The color difference was 1.8 and the light resistance was good.

Production Example 2 A paint was prepared in the same manner as in Example 1.

1.5 parts of a blue pigment paint containing no halogen atom was uniformly mixed with 8.5 parts of a yellow pigment paint containing no halogen atom.

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. It was left at room temperature for about 1 hour and baked and dried in a dryer at 140 ° C. for 15 minutes to obtain a color sample. The colorimetry of this color sample is as follows and shows the green color gamut.

[0077]       L * 49.1 C * 43.1 H * 157.1

An accelerated light resistance test was conducted in the same manner as in Example 1 to measure the color difference between the test piece before the accelerated test and the coated piece after the test. The color difference was 1.1 and the light resistance was good.

Comparative Example 2 Fastogen Green 2YK (C.
I. Pigment Green 36) to Fastogen Green S (CIPigment
A paint was prepared in the same manner except that it was used instead of Green 7).

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. It was left at room temperature for about 1 hour and baked and dried in a dryer at 140 ° C. for 15 minutes to obtain a color sample. The colorimetry of this color sample is as follows and shows the green color gamut.

[0081]       L * 48.1 C * 42.1 H * 158.9

An accelerated light resistance test was conducted in the same manner as in Example 1 to measure the color difference between the test piece before the accelerated test and the coated piece after the test. The color difference was 1.5 and the light resistance was good.

[0083] Example 3 Polypropylene (Mitsubishi Noblen MA-4) 100 parts Symuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 0.035 copies Fastogen Blue GB-7H (C.I.Pigment Blue 15: 3) 0.015 copy Titanium oxide (Taipaque R-680 manufactured by Ishihara Sangyo Co., Ltd.) 0.32 parts Aluminum stearate 0.13 parts

Injection molding was carried out with the composition of the above at a molding temperature of 220 ° C. to obtain a heat resistant reference plate. The molding temperature was raised to 280 ° C and the residence time at 280 ° C was set to 10 minutes. The color difference from the reference plate was 1.7, and the heat resistance was good.

[0085] Comparative Example 3 Polypropylene (Mitsubishi Noblen MA-4) 100 parts Fastogen Green SO (C.I.Pigment Green 7) 0.05 parts Titanium oxide (Taipaque R-680 manufactured by Ishihara Sangyo Co., Ltd.) 0.32 parts Aluminum stearate 0.13 parts

Injection molding was carried out with the composition of (1) at a molding temperature of 220 ° C. to obtain a heat resistant reference plate. The molding temperature was raised to 280 ° C and the residence time at 280 ° C was set to 10 minutes. The color difference from the reference plate was 1.0.

[0087] Comparative Example 4 Polypropylene (Mitsubishi Noblen MA-4) 100 parts Fastogen Green MY (C.I.Pigment Green 36) 0.05 parts Titanium oxide (Taipaque R-680 manufactured by Ishihara Sangyo Co., Ltd.) 0.32 parts Aluminum stearate 0.13 parts

Injection molding was carried out at a molding temperature of 220 ° C. with the composition of (1) to prepare a heat resistant reference plate. The molding temperature was raised to 280 ° C and the residence time at 280 ° C was set to 10 minutes. The color difference from the reference plate was 1.5.

[0089] Example 4 Symuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 0.42 copies Fastogen Blue 5380 (C.I.Pigment Blue 15: 3) 0.18 copies Resin-type varnish (rosin-modified phenolic resin organic solvent solution) 1.4 parts

Weigh out, mix evenly on a Hoover Mahler, apply a weight of 150 lbs and perform 100 spin dispersion. After opening the Hoover Mahler and collecting the ink in the center, disperse 100 times more. The same operation was repeated once more to prepare a primary color ink.

To the washed Hoover Mahler, Primary color ink 0.11 part Titanium oxide (Taipaque R-550 manufactured by Ishihara Sangyo Co., Ltd.) 1.5 parts Resin varnish 1.1 parts

Weigh and weigh 100 pounds to 100
The rotation was repeated twice to create a light color ink.

The light-colored ink was placed on the color-developed paper and the color was spread with a pulling spatula. This one had a green color.

[0094] Example 5   To 100 ml polybin   Symuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 2.8   Fastogen Blue 5380 (C.I.Pigment Blue 15: 3) 1.2 copies   NC gravure resin (nitrocellulose resin main component) 26.0 parts   Mixed solvent 10.0 parts   Steel beads 1/8 inch φ 150 parts

Put it in, and use paint conditioner 30
Disperse for minutes. (Mixed solvent: toluene / ethyl acetate / isopropyl alcohol = 4/4/2)

The resulting NC gravure ink was applied onto an acetate film with a 0.15 mmφ bar coater. This one showed green.

[0097] Example 6   Styrene-acrylic acid copolymer manufactured by Sanyo Kasei Co., Ltd.     Heimer SBM100 100 parts   As a yellow pigment that does not contain halogen atoms     Synuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 3.5 copies   As a blue pigment that does not contain halogen atoms     Fastogen Blue 5380 (C.I.Pigment Blue 15: 3) 1.5 parts

After kneading with an extruder, pulverization and classification are performed to obtain a green toner having an average particle size of 10 μm. Then, 100 parts of this toner is mixed with 1.0 part of hydrophobic silica to obtain a toner containing hydrophobic silica. Obtained.

[0099] Example 7   In a glass container,   As a yellow pigment that does not contain halogen atoms     Synuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 1.4 copies   As a blue pigment that does not contain halogen atoms     Fastogen Blue 5380 (C.I.Pigment Blue 15: 3) 0.6 copy   Made by Dainippon Ink and Chemicals, Inc. as a UV curable acrylic resin     Unidick S5-122 4.0 copies   2-Butoxy-1-propanol 94.0 parts   Zirconia beads 0.4 mmφ 300 parts

[0100] was added and shaken for 2 hours with a paint shaker to prepare a green coating solution. The obtained coating liquid was used with a spin coater (1H-3D type: manufactured by Mikasa Co., Ltd.)
200r on a glass plate (7059: Corning Inc.)
It was applied at pm for 10 seconds and then at 2000 rpm for 30 seconds and irradiated with ultraviolet rays by a high pressure mercury lamp to obtain a green colored glass plate.

[0101] Example 8 In a 100 ml glass bottle   Blue pigment containing no halogen atoms     Fastogen Blue NK (C.I.Pigment Blue 15: 4) 4.0 copies   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 16.0 parts   Solvent (xylene / normal butanol = 75/25) 10.0 parts   Glass beads 3mm φ 80 parts

Weigh out 1 with a paint conditioner
Time dispersed. 30.2 parts of Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals), 19.8 parts of Super Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals)

Then, the mixture was added and mixed again with a paint conditioner for 10 minutes to prepare a blue enamel. (Alkyd / melamine nonvolatile content ratio = 7/3)

Similarly, in a 100 ml glass bottle, a yellow pigment containing no halogen atom, Symuler Fast Yellow 4GO (CIPigment Yellow 151) 4.0 part manufactured by Dainippon Ink and Chemicals, Inc. Beccosol J-524-IM-60 (large Made by Nippon Ink Chemical Co., Ltd.) 16.0 parts Solvent (xylene / normal butanol = 75/25) 10.0 parts Glass beads 3 mmφ
80 copies

Weigh out 1 with a paint conditioner
Time dispersed. In this dispersion

[0106]   Beccosol J-524-IM-60 (manufactured by Dainippon Ink and Chemicals) 30.2 parts   Super Beckamine J-820-60 (manufactured by Dainippon Ink and Chemicals) 19.8 parts

Then, the mixture was added and mixed again with a paint conditioner for 10 minutes to prepare a yellow enamel. (Alkyd / melamine nonvolatile content ratio = 7/3)

As the white paint, white enamel was prepared so that the pigment content was 30%. Titanium white is Taipaque R-93
0 (made by Ishihara Sangyo Co., Ltd.) was used.

Yellow pigment paint 7 containing no halogen atom
To 3 parts, 3 parts of a blue pigment paint containing no halogen atom were uniformly mixed.

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. It was left at room temperature for about 1 hour and baked and dried in a dryer at 140 ° C. for 15 minutes to obtain a color sample. The colorimetry of this color sample is as follows and shows the green color gamut.

[0111]       L * 44.6 C * 36.5 H * 167.3

[0112] Example 9 In a 100 ml glass bottle Yellow pigment containing no halogen atom, manufactured by Dainippon Ink and Chemicals, Inc.     Symuler Fast Yellow 4GO (C.I.Pigment Yellow 151) 2.8 Blue pigment containing no halogen atoms     Fastogen Blue NK (C.I.Pigment Blue 15: 4) 1.2 copies Acrydic A-181 (acrylic resin; made by Dainippon Ink and Chemicals) 16.0 Xylene 10.0 parts Glass beads 3mm φ 80 parts

Weigh out 1 with a paint conditioner
Time dispersed. In this dispersion

50.0 parts of Acridic A-181 (manufactured by Dainippon Ink and Chemicals, Inc.) was added and mixed again with a paint conditioner for 10 minutes to prepare a green enamel.

As for the white paint, white enamel was prepared so that the pigment content was 30%. Titanium white is Taipaque R-93
0 (made by Ishihara Sangyo Co., Ltd.) was used.

The mixing ratio of the organic pigment and titanium white is 1: 1.
The paint was made so that it would be and spread with a 6 mil applicator. The sample was left standing at room temperature for about one night and dried to obtain a color sample.
The colorimetry of this color sample is as follows and shows the green color gamut.

[0117]       L * 46.8 C * 38.9 H * 166.6

Example 10 As a yellow pigment containing no halogen atom, Symuler Fast was used.
In place of Yellow 4GO (CIPigment Yellow 151), Clariant Novoperm Yellow F2G (CIPigment Yell
ow 194) was used according to Example 8. This color sample shows the green color gamut.

[0119]       L * 42.9 C * 36.2 H * 159.8

Example 11 As a yellow pigment containing no halogen atom, Symuler Fast was used.
Instead of Yellow 4GO (CIPigment Yellow 151), Clariant made Hostaperm Yellow H6G (CIPigment Yel
Example 8 was followed except that low 175) was used. This color sample shows the green color gamut.

[0121]       L * 44.4 C * 37.2 H * 174.5

Example 12 As a yellow pigment containing no halogen atom, Symuler Fast was used.
Irgazine Yellow 5 manufactured by Ciba Specialty Chemicals Co. instead of Yellow 4GO (CIPigment Yellow 151)
Example 8 was followed except that GT (CI Pigment Yellow 129) was used. This color sample shows the green color gamut.

[0123]       L * 38.4 C * 24.3 H * 155.2

Example 13 As a yellow pigment containing no halogen atom, Symerer Fast was used.
Instead of Yellow 4GO (CIPigment Yellow 151), Clariant's Sandorin Yellow G (CIPigment Yellow)
Example 8 was followed except that 182) was used. This color sample shows the green color gamut.

[0125]       L * 41.3 C * 30.2 H * 158.8

Example 14 As a yellow pigment containing no halogen atom, Symuler Fast was used.
Instead of Yellow 4GO (CIPigment Yellow 151), Clariant made Sandorin Yellow 4G (CIPigment Yello
Example 8 was followed except that w 155) was used. This color sample shows the green color gamut.

[0127]       L * 43.1 C * 35.7 H * 160.9

Example 15 As a yellow pigment containing no halogen atom, Symuler Fast was used.
Instead of Yellow 4GO (CIPigment Yellow 151), BAS Paliogen Yellow L1560 (CIPigmen
Example 8 was followed except that t Yellow 108) was used.
This color sample shows the green color gamut.

[0129]       L * 42.1 C * 30.2 H * 170.4

Example 16 As a yellow pigment containing no halogen atom, Symuler Fast was used.
Instead of Yellow 4GO (CIPigment Yellow 151), BASF Palaiotol Yellow D 1155 (CIPigme
Example 8 was followed except that nt Yellow 185) was used.
This color sample shows the green color gamut.

[0131]       L * 42.5 C * 40.4 H * 152.6

Example 17 As a yellow pigment containing no halogen atom, Symuler Fast was used.
In place of Yellow 4GO (CIPigment Yellow 151), Clariant Novoperm Yellow H2G (CIPigment Yell
Example 8 was followed except that ow 120) was used. This color sample shows the green color gamut.

[0133]       L * 43.3 C * 35.7 H * 166.9

Example 18 As a blue pigment containing no halogen atom, Fastogen Blu was used.
Example 8 was followed except that aluminum phthalocyanine manufactured by Sun Chemical Co. was used instead of eNK (CI Pigment Blue 15: 4). This color sample shows the green color gamut.

[0135]       L * 50.0 C * 47.1 H * 158.8

Example 19 As a blue pigment containing no halogen atom, Fastogen Blu was used.
Example 8 was followed except that Chromofine Blue 5000P (CIPigment Blue 75) manufactured by Dainichiseika Co., Ltd. was used instead of e NK (CIPigment Blue 15: 4). This color sample shows the green color gamut.

L * 39.8 C * 21.6 H * 172.9 Example 20 As a blue pigment containing no halogen atom, Fastogen Blu was used.
Instead of eNK (CIPigment Blue 15: 4), Dainippon Ink and Chemicals Fastogen Super Blue 6070S (CIPigment Bl
Example 8 was followed except that ue 60) was used. This color sample shows the green color gamut.

[0138]       L * 40.0 C * 16.9 H * 168.9

[0139]

As described above, the pigment composition according to the method of the present invention is a green pigment composition containing no halogen atom, which is a combination of a yellow pigment containing no halogen atom and a blue pigment containing no halogen atom. is there. The paint, printed matter, and the like using the present invention can suppress the generation of dioxins due to the present composition by incineration of waste. In addition, the combination can sufficiently cope with light resistance and heat resistance.

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Claims (2)

[Claims] 1. A green pigment composition obtained by mixing and blending a yellow pigment containing no halogen atom and a blue pigment containing no halogen atom. 2. A green resin coloring obtained by mixing a yellow resin composition in which a yellow pigment containing no halogen atom is dispersed in a synthetic resin and a blue resin composition in which a blue pigment containing no halogen atom is dispersed in a synthetic resin. Composition.