JP2002146223A - Colorant for plastic and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for decreasing the warp or distortion of a molded plastic article colored with a colorant containing an organic pigment as the main coloring component. SOLUTION: The colorant for plastic used here contains an organic pigment and an organic pigment derivative represented by formula [1] (wherein P is an organic pigment residue; X is SO2-, CO-, CH2- or CH2NHCOCH2; R1 and R2 are each H or an alkyl provided at least one of them is a 12-30C alkyl; M is one equivalent of a mono- to trivalent cation; (m) is 0-2; and (n) is 1-3). The colorant containing an organic pigment and an organic pigment derivative represented by formula [1] is used for coloring a thermoplastic resin to give a colored molded plastic article decreased in warp or distortion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for controlling the shape of a molded product obtained by molding a plastic, and more particularly, to a method for molding a plastic colored using a coloring agent containing a pigment as a main coloring component. The present invention relates to a method for improving molding shrinkage distortion such as warpage or deformation of a product.

[0002]

2. Description of the Related Art Dyes and pigments are used for coloring plastics. Dyes are generally called oil colors and, unlike pigments, are dissolved in a solvent, so that they can be obtained with excellent dispersibility and high color tone with high transparency. In general, the coloring of polyolefins is only considered with pigments. Dyes are never used because they cause bleed and bloom.

[0003] Pigments are provided for coloring in the state of being dispersed in plastics with fine particles insoluble in water or a solvent. Pigments are roughly classified into organic pigments and inorganic pigments. Conventionally, plastic coloring includes price, heat resistance, weather resistance, color resistance, migration resistance,
Cadmium-based and chromium-based heavy metals with excellent dimensional stability
Lead-based inorganic pigments have been used. However, problems in the production of these pigments, problems in use, effects on the human body after being formed, problems of waste are highlighted, and inorganic pigments containing heavy metals, especially cadmium, have been shunned.
Organic pigments are often used. Among the organic pigments, for coloring plastics, those called high-grade organic pigments having excellent light resistance, heat resistance, and migration resistance are often used.

[0004] Condensed polycyclic organic pigments represented by quinacridone, phthalocyanine, diketopyrrolopyrrole, dioxazine, isoindolinone, perylene, etc., have light resistance, heat resistance, migration resistance, clear hue, high coloring power, etc. However, when it is used for coloring crystalline plastics such as polyolefins and PET, it has a large nucleation effect, which affects the crystallinity of plastics, such as increasing the crystallization temperature and reducing spherulites. This causes a phenomenon in which the shrinkage and shrinkage balance (molding shrinkage ratio) of the colored plastic change, and the plastic molded product appears to be warped, deformed, or dimensionally changed, which has been a problem in molding processing. Warping and deformation have been fatal to molded articles such as containers, plastic pallets, caps and bottles.

As a method of improving the molding shrinkage distortion of a plastic molded product, there is a method of using a mold in which warpage, deformation, and dimensional change are taken into account. However, since the shrinkage of a molded article greatly differs depending on the type of resin, coloring agent, additive, molding conditions, and the like, it is difficult to design a mold in consideration of molding shrinkage distortion, and it is necessary to make many corrections. In addition, the molding maker, molding temperature, injection pressure, injection time, injection speed,
The molding shrinkage strain is improved by changing the processing conditions such as the cooling time. However, also in this case, since the shrinkage differs depending on the type and color of the resin, the colorant, the additive, and the size and shape of the molded product, it is difficult to set the processing conditions for estimating the warpage and deformation. Also needed to be fixed. In many cases, the molding cycle is lengthened to lower the productivity.

As another method for improving the molding shrinkage distortion, a crystallization agent (a nucleating agent, a nucleating agent or a crystallization accelerator) is added. The function of the crystallization agent is to reduce the influence of pigments on shrinkage by rapidly forming fine crystals by blending a large number of components serving as crystal nuclei. Alternatively, an apparent difference in shrinkage is eliminated by adding a crystallization agent that shrinks in a direction different from the shrinking direction of the pigment. It is known that the use of a crystallization agent can shorten the molding cycle and increase rigidity and transparency. As the crystallization agent, for example, metal carboxylate such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′- Acetal types of sorbitol, such as acid phosphate metal salts such as methylene bis (4,6-di-tert-butylphenyl) phosphate, and dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol are used. However, the effect on molding shrinkage strain was insufficient.

[0007] Therefore, the best way is to modify the pigments used as colorants so that they do not act as crystal nuclei. Modifying the pigment crystal form, particle size and shape, modifying the pigment surface by adding pigment derivatives (organic dye derivatives) with various substituents introduced into the pigment skeleton,
BACKGROUND ART The surface of a pigment is modified by subjecting the pigment to a surface treatment with a resin, a silane coupling agent, or the like.

Methods for changing the crystal form, particle size and shape of the pigment are described in JP-A-04-376232, JP-A-57-155242, JP-A-56-99245, and the like. However, no sufficient effect has been obtained. Further, changes in the crystal form, particle diameter, and shape of the pigment affect the original physical properties of the pigment, such as hue, dispersibility, coloring power, heat resistance, and light resistance.

Japanese Patent Publication No. 53-7185 and Japanese Patent Laid-Open Publication No. 03-12432 disclose a method of surface modification using a so-called pigment derivative in which a substituent is introduced into a pigment structure for the purpose of improving molding distortion. Derivatives are described. According to the present invention, although the molding distortion is somewhat improved, it is not sufficient, and the color transferability is deteriorated, so that it has not been put to practical use.

As a method for modifying the surface of a pigment other than the pigment derivative, a surface treatment with an organic silane or an organic titanium, and a surface coating of the pigment with a thermoplastic resin are performed. JP-A-05-194873 describes that a sulfonic acid having an organic pigment residue and a polymer composed of a water-soluble high-molecular ammonium salt coexist to modify the pigment surface with a polymer. However, none of the effects were sufficient. Further, the molding shrinkage distortion in a molded article when coloring a plastic using an organic pigment, particularly a condensed polycyclic organic pigment, is not solved by any of the above methods,
It was a big problem.

[0011]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have been able to use an organic pigment and a coloring agent composed of an organic dye derivative represented by the general formula [1]. By doing, the excellent light resistance of the organic pigment,
The inventors have found that warpage and deformation of a plastic molded product can be reduced without losing heat resistance, migration resistance, and the like, and have completed the present invention.

[0012]

Means for Solving the Problems The present invention relates to a colorant for plastics containing an organic pigment and an organic dye derivative represented by the following general formula [1]. General formula [1]

[0013]

Embedded image

[0014] (wherein, P is an organic pigment residue, X is _{-SO 2 -, - CO -,} - CH 2 - or -CH ₂ NHC
OCH ₂ —, R ₁ and R _{2 each} represent a hydrogen atom or an alkyl group (at least one of R ₁ and R ₂ represents an alkyl group having 12 to 30 carbon atoms); ,
m represents a number of 0 to 2, and n represents a number of 1 to 3. Further, the present invention relates to a method for improving the molding distortion of a plastic molded product, which comprises adding an organic dye derivative represented by the general formula [1] when mixing and coloring an organic pigment with a plastic.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The organic dye derivative represented by the general formula [1] contained in the coloring agent used in the present invention comprises an organic dye residue represented by P and hydrogen represented by R ₁ and R _2. atom or an alkyl _{group, -SO 2 N -, - CON} -, - CH 2 N
-, or having a bond structure via the -CH ₂ NHCOCH ₂ N-.

The organic dye residue represented by P in the general formula [1] includes phthalocyanine, anthraquinone, insoluble azo, azo lake, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, Anthanthrone, indanthrone, flavanthrone, perylene, perinone, thioindigo and the like.

In the general formula [1], R ₁ and R ₂ are a hydrogen atom or an alkyl group, provided that at least one of R ₁ and R ₂ is an alkyl group having 12 to 30 carbon atoms. When the length of the alkyl group is short, that is, when there is no at least one alkyl group having 12 or more carbon atoms, a sufficient effect of suppressing the molding shrinkage strain cannot be obtained. If at least one of R ₁ and R ₂ is an alkyl group having 12 or more carbon atoms, the effects of the present invention can be obtained. In order to have a higher effect and reduce the amount of use, preferably, when both R ₁ and R ₂ are alkyl groups having 12 or more carbon atoms, or R ₁ ,
It is preferred that at least one of R ₂ is an alkyl group having 16 or more carbon atoms. On the other hand, when the number of carbon atoms is 30 or more, the amount of the organic dye residue is relatively small with respect to the alkyl group, the effect per unit weight is reduced, and the amount used is undesirably large. The alkyl group of R ₁ and R ₂ is preferably a saturated linear alkyl group, but may have a branched structure or an unsaturated structure. Examples of R ₁ and R ₂ include a dodecyl group (lauryl group), a tetradecyl group (myristyl group),
Hexadecyl group (palmityl group), octadecyl group (stearyl group), docosyl group (behenyl group), cis-9
An octadecyl group (oleyl group);

In the general formula [1], n represents the number of substituents to which R ₁ and R ₂ are bonded per molecule, and is 1 to 3. n is at least 1, and it is necessary that R ₁ and R ₂ have at least one substituent bonded thereto.

In the general formula [1], M represents one equivalent of a cation having a valence of 1 to 3, and specifically, a hydrogen atom, sodium, potassium, calcium, barium, manganese, nickel, cobalt, strontium, aluminum, or the like. Metal cations and ammonium cations shown below. Dimethyl ammonium, trimethyl ammonium, diethyl ammonium, triethyl ammonium,
Hydroxyethylammonium, dihydroxyethylammonium, diethyl-hydroxyethylammonium, dimethyl-hydroxyethylammonium, 2-ethylhexylammonium, di-2-ethylhexylammonium, pyridinium, piperidinium, dimethylaminopropylammonium, morpholinium, laurylammonium, stearylammonium Oleyl ammonium, dimethyl dilauryl ammonium, trimethyl lauryl ammonium, trimethyl stearyl ammonium, hexyl ammonium, 1,2-dimethylpropyl ammonium, butyl ammonium, isobutyl ammonium, butoxypropyl ammonium, decyloxypropyl ammonium, and the like.

In the general formula [1], m represents the number contained in one molecule of the sulfonic acid group represented by SO ₃ M, and is 0 to 2. m is preferably 0, but a sulfonic acid group is often included in the synthesis process, and m is 1 to 2, that is, even if one or two sulfonic acid groups are included, the molding distortion of the present invention is reduced. The effect of reducing the size is sufficient.

The method for producing the organic dye derivative represented by the general formula [1] used in the present invention is as follows:
_{SO 2 Cl, -COCl, -CH 2} Cl or -CH ₂ N
HCOCH ₂ Cl substituents are introduced, and water, alcohol,
In a reaction solvent such as acetone, dioxane, glycols such as ethylene glycol and diethylene glycol and ethers thereof, and N, N-dimethylformamide,
In some cases, it is reacted with a long-chain alkylamine (in the present invention, a monoalkylamine or a dialkylamine having at least one alkyl group having 12 or more carbon atoms) in the presence of an alkali such as an organic amine, caustic soda, and sodium carbonate. Generally, a method of removing the solvent is used.
In the case of azo pigments, a method of reacting a diazo component or a coupler component with a monoalkylamine or a dialkylamine in advance and then coupling the same is industrially advantageous.

The long-chain alkylamine used in the production of the general formula [1] is a monoalkylamine or a dialkylamine having at least one alkyl group having 12 or more carbon atoms. Examples of the compound include monoalkylamines such as laurylamine, palmitylamine, stearylamine, aralkylamine, behenylamine, and oleylamine.Dialkylamines include dilaurylamine, dimyristylamine and dipalmitylamine , Distearylamine, stearyllaurylamine, stearylmyristylamine, stearylpalmitylamine, palmityllaurylamine, myristyllaurylamine, myristyllaurylamine and the like. These monoalkylamines and dialkylamines having a long-chain alkyl group are synthesized from natural fats and oils and are commercially available as a mixture containing a plurality of compounds. As an example of a commercial product,
Farmin 80, Farmin 86T, Farmin O, Farmin D86 (all manufactured by Kao Corporation), Armin 1
6D, Armin 18D, Armin T, Armin O, Armin 2C, Armin 2HT (all manufactured by Lion Corporation).

The organic pigment constituting the colorant used in the present invention includes a phthalocyanine pigment, an insoluble azo pigment, an azo lake pigment, an anthraquinone pigment, a quinacridone pigment,
Examples include dioxazine pigments, diketopyrrolopyrrole pigments, anthrapyridine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perinone pigments, perylene pigments, and thioindigo pigments. Among them, phthalocyanine, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, flavanthrone, perinone, perylene, isoindolinone, quinophthalone When the thermoplastic resin is colored without using the organic dye derivative of the general formula [1] according to the present invention, the molded article has a large molding shrinkage distortion and is represented by the general formula [1]. By using an organic dye derivative together with a pigment, the effect of reducing the molding distortion of a molded article is extremely exerted.

The present invention is characterized in that a colorant comprising an organic pigment and an organic dye derivative represented by the general formula [1] is used, and the organic pigment has excellent heat resistance, light resistance, and migration resistance. The amount of the organic dye derivative represented by the general formula [1] should be suppressed to a sufficient amount to reduce molding distortion, and the organic pigment is usually used as a main component as a coloring component in a coloring agent. become.

The amount of the organic dye derivative represented by the general formula [1] is 2 to 30 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the organic pigment.
It is preferable to use it in the range of 20 parts by weight. If the amount is too small, the effect of reducing the molding distortion is not sufficient, and if it is too large, a change in hue, heat resistance, light resistance, and migration resistance may appear.

Since the organic dye derivative of the general formula [1] used in the present invention has a hue derived from the organic dye used as the organic dye residue, it is preferable to use an organic dye derivative having a hue similar to the pigment used. Is industrially advantageous because the change in hue is small. The method of mixing the organic pigment and the organic dye derivative represented by the general formula [1] is not particularly limited, but may be a method of mixing each powder with a mixer, a method of stirring and mixing as a slurry of water or an organic solvent, and a method of mixing three. There are a method of kneading the medium with a roll or two rolls and a method of adding an organic dye derivative in a pigmentation step such as kneading or solvent treatment for producing an organic pigment. Preferably, a method of mixing in a slurry state using an organic solvent is advantageous for exhibiting a sufficient effect.

The present invention is characterized in that a plastic is colored using a coloring agent composed of an organic pigment and an organic coloring matter derivative represented by the general formula [1]. Other organic pigments, inorganic pigments, waxes and derivatives thereof, heavy metal deactivators, alkali metals, alkaline earth metals or zinc metal soaps, Antistatic agents consisting of talcite, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc., flame retardants such as halogen-based, phosphorus-based or metal oxides, ethylene bisalkylamides Lubricants, antioxidants and UV absorbers, processing aids, fillers, etc.
Various additives for known polymers can be included. In order to satisfy the required quality and coloring workability,
The pigment is pre-dispersed with these components,
It is referred to as a powdery dry color, a granular bead color, a liquid paste color, or a liquid color.

One preferred form of the colorant comprising an organic pigment and an organic dye derivative represented by the general formula [1] used in the present invention is a powdery colorant containing a pigment called a dry color at a high concentration. It is. In the case of dry color, generally, a metal salt of an aliphatic carboxylic acid or a metal salt of an aromatic carboxylic acid is used as a dispersing agent in an amount of 1 to 100 parts by weight based on 100 parts by weight of the organic pigment and the organic dye derivative of the general formula [1] in total.
0 parts by weight. Examples of aliphatic carboxylic acid metal salts or aromatic carboxylic acid metal salts include aliphatic carboxylic acids such as caprylic acid, oleic acid, and stearic acid, and aromatic carboxylic acids such as phthalic acid and benzoic acid. And as the metal, lithium, calcium,
Magnesium, zinc and the like. Although dry color is in powder form and has poor workability, it is the most economical in terms of cost because it has a high pigment concentration and contributes to coloring in a small amount, and is often used for coloring polyolefins. When providing for molding,
For 100 parts by weight of plastic, dry color is 0.1%.
001 to 10 parts by weight are used. After the plastic pellets and the dry color are uniformly mixed in advance by a mixer or the like, they are subjected to molding.

In the present invention, the plastic to be colored is softened by heating and cured again by cooling, and is a homopolymer of ethylene, propylene, butylene, styrene and / or divinylbenzene, or a block or random copolymer or Terpolymers, especially α-olefins such as HDPE, LDPE, polypropylene and polystyrene. Examples of other useful plastics are polyesters such as polyethylene terephthalate, polyamides such as nylon 6, nylon 66, and thermoplastic ionomers. The method of the present invention has a high effect on these crystalline plastics, and in particular, α
-For polyolefins such as olefins, homopolymers, copolymers of ethylene, propylene and butylene,
Has a remarkable effect.

As the polyolefin resin, MFR
(Melt flow rate, ie, melt viscosity) is 0.00
When the MFR is less than 0.001, the melt viscosity of the colored resin composition is too high, so that the molding processability is poor or a well-edged mark or a flow mark is formed on a molded product. On the other hand, if the MFR exceeds 30, there is a concern that the mechanical properties of the molded article may be reduced. In particular, when high-density polyethylene is used, the MFR is 0.005 to 10,
When low-density polyethylene, polypropylene, or polybutene is used, the MFR is preferably 0.005 to 20.

The present invention is characterized in that a plastic is colored using a coloring agent containing an organic pigment and an organic dye derivative represented by the general formula [1]. A pellet-shaped colored resin composition obtained by coloring a plastic with a coloring agent may be manufactured, and then subjected to molding using the colored pellet-shaped colored resin composition.

The coloring resin composition is composed of a plastic and a coloring agent composed of an organic pigment, an organic dye derivative represented by the general formula [1]. It may be in the form of pellets (colored pellets) to be directly used for molding, or may be a pellet-like colorant called a master batch containing a pigment at a high concentration. And
In the case of a masterbatch containing a pigment at a high concentration, the masterbatch concerned may be diluted with a plastic and subjected to molding to obtain a molded product.

Comparing the masterbatch and the colored pellets, there is no great difference in the processing steps and the like, and the masterbatch is slightly more expensive than the colored pellets because the pigment contains a high concentration, but in the case of the masterbatch, it is inexpensive. Since a molded article is obtained by diluting 0.5 to 200 times with a simple plastic, compared to obtaining a molded article with colored pellets when compared with a final molded article, a method of obtaining a molded article by diluting with a plastic using a master batch is preferable. However, it is preferable because it is inexpensive.

Among the colored resin compositions, in the case of so-called colored pellets to be directly used for molding, it is preferable to contain 100 parts by weight of plastic and 0.001 to 10 parts by weight of the coloring agent of the present invention. If the amount of the coloring agent is less than 0.001 part by weight, only a very pale color can be obtained. Also, 1
If the pigment is contained in an amount of more than 0 parts by weight, the mechanical properties of the molded article may be impaired.

In the case of a pellet colorant (master batch) containing a pigment at a high concentration in the colored resin composition, 100 parts by weight of plastic and 0.1% of the colorant of the present invention are used.
It is preferred that the content be from 200 to 200 parts by weight. If the amount of the coloring agent is less than 0.1 part by weight, it has no significance as a master batch, and if the amount of the coloring agent exceeds 200 parts by weight, granulation of the master batch becomes difficult. In the case of a masterbatch containing a pigment at a high concentration, the masterbatch may be diluted with plastic and used for molding to obtain a molded product. As plastic used for dilution,
The same plastics as those used for obtaining the pellet-shaped colored resin composition containing a pigment at a high concentration can be exemplified. The final molded article preferably contains 100 parts by weight of a plastic and 0.001 to 10 parts by weight of a coloring agent as in the case of pellets which are directly used for molding without requiring dilution.

In the colored resin composition, other organic pigments, inorganic pigments, other thermoplastic resins and waxes that do not impair the effects of the present invention or cause no hygiene problems.
Derivatives thereof, heavy metal deactivator, alkali metal, alkaline earth metal or zinc metal soap, hydrotalcite, nonionic surfactant, cationic surfactant,
Antistatic agents composed of anionic surfactants, amphoteric surfactants, etc., flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylenebisalkylamide, antioxidants and ultraviolet absorbers, processing aids , Fillers, various additives for known polymers, and the like.

When the colored resin composition is obtained, it is preferable to pre-process the colorant with a dispersant such as polyethylene wax before kneading the colorant and the plastic. As a method of pre-processing, there are a method in which a colorant and a dispersant are simply blended and mixed in a mixer, and a method in which a colorant and a dispersant are blended and pulverized after melt-kneading, but in terms of uniform dispersibility of the colorant. The latter type of processing method in which melt kneading is performed is preferred.

In the present invention, a molding method for obtaining a molded product by molding a plastic is not particularly limited. Regardless of the molding method, such as injection molding, blow molding, inflation molding, T-die extrusion molding, engel molding, vacuum molding, etc., the effect of suppressing the warpage and deformation of the colored molded product can be obtained.

The method of coloring a plastic using the organic pigment of the present invention and a coloring agent comprising the organic dye derivative represented by the general formula [1] improves the warpage, deformation, and dimensional stability of the colored molded product. The mechanism by which this is done is not always clear. However, when a long-chain alkylamine having no organic dye residue is used, or when only a salt of an organic dye sulfonic acid and a long-chain alkylamine is used, the effect of suppressing molding shrinkage distortion of a molded product is reduced. No effect was observed, and only when an organic dye derivative represented by the general formula [1] having an organic dye residue and a long-chain alkyl group in the molecule was used, an effect of reducing molding shrinkage strain was obtained.

【Example】

Hereinafter, a synthesis example of the organic dye derivative represented by the general formula [1] will be described.

<Synthesis Example 1> Synthesis of Compound (a) 100.0 parts of chlorosulfonylcopper phthalocyanine obtained by chlorosulfonating copper phthalocyanine (CIPigment Blue 15) by an ordinary method (an average of 1.2 chloroforms per molecule) The slurry containing a sulfonyl group) was reslurried in 800.0 parts of isopropyl alcohol to obtain a dialkylamine 8 having an alkyl group having 14 to 18 carbon atoms.
8.0 parts (trade name Farmin D86, carbon number 14: 4
%, Carbon number 16: 30%, carbon number 18: 66%, manufactured by Kao Corporation) and 50.0 parts of dimethylaminoethanol, and reacted at 80 ° C. for 2 hours. Then, filtration, washing with water,
Drying yielded 176.0 parts of compound (a).

<Synthesis Example 2> Synthesis of Compound (b) 100.0 parts of chloromethyl copper phthalocyanine obtained by chloromethylation of copper phthalocyanine (CIPigment Blue 15) by an ordinary method (an average of 2.0 chloro compounds per molecule) (Containing a methyl group) was slurried in 700.0 parts of isopropyl alcohol, and the carbon number was 14-20.
79.3 monoalkylamine having an alkyl group (trade name: Farmin 80, carbon number 14: 1%, carbon number 16: 6%, carbon number 18: 92%, carbon number 20: 1%, manufactured by Kao Corporation) And 30.0 parts of triethylamine, and reacted at 80 ° C. for 6 hours. Next, the alcohol was distilled off, followed by filtration, washing with water and drying to obtain 143 parts of the compound (b).

<Synthesis Example 3> Synthesis of Compound (c) Unsubstituted quinacridone (CIPigment Violet 19: product name)
A paste containing 50.0 parts of chlorosulfonylquinacridone (containing 2.0 chlorosulfonyl groups per molecule) obtained by chlorsulfonating Lionogen Red 5700 (manufactured by Toyo Ink Mfg. Co., Ltd.) by a conventional method was used. And re-slurry to 1.0 part, carbon number 14
57.4 parts of a monoalkylamine having an alkyl group of 20 to 20 (trade name: Farmin 80, manufactured by Kao Corporation) and 30.0 parts of triethylamine were mixed and reacted at 80 ° C. for 2 hours. Then, after distilling off the alcohol, filtration, washing with water,
Drying yielded 96.8 parts of compound (c).

<Synthesis Example 4> Synthesis of Compound (d) Unsubstituted quinacridone (CIPigment Violet 19: product name)
A paste containing 86.6 parts of chlorocarbonylquinacridone (containing 2.0 chlorocarbonyl groups per molecule) obtained by subjecting Lionogen Red 5700 (manufactured by Toyo Ink Mfg. Co., Ltd.) to carbonyl chloride by a conventional method is obtained by adding 1-ethoxy. Re-slurried in 400 parts of 2-propanol to obtain a dialkylamine having an alkyl group having 8 to 18 carbon atoms (trade name: Armin 2C, 8: 8% carbon number, 10: carbon number:
90.4%, carbon number 12: 47%, carbon number 14: 18%, carbon number 16: 8%, carbon number 18: 10%, 140.4 parts, manufactured by Lion Corporation), dimethylaminoethanol 50.0
Were mixed and reacted at 100 ° C. for 6 hours. Next, this was filtered, washed with water, and dried to obtain 182.0 parts of compound (d).

Compounds (e) to (o) shown in Table 1 were synthesized according to Synthesis Examples 1 to 4. Table 1 shows the synthesized organic dye derivatives (a) to (e).

[0046]

[Table 1]

Hereinafter, the obtained organic dye derivatives (a) to (e) represented by the general formula [1] and the coloring agent and the coloring resin composition containing the organic pigment will be described with reference to Examples and Comparative Examples. explain. In the examples, “parts” means “parts by weight”.

Evaluation of warpage and deformation is performed by a mold for shrinkage evaluation (10.0 in the flow direction and the direction perpendicular thereto) using an injection molding machine.
150mm long, 120m wide with 0cm marked line
m, a molded plate prepared using a mold for forming a plate having a thickness of 3 mm) is stored in a thermostatic chamber for 3 days, and then the shrinkage in the flow direction (MDS) and the shrinkage in the vertical direction (T
DS), and the shrinkage difference ratio (SD
R). Injection molding was performed continuously at a molding temperature of 220 ° C and a mold temperature of 40 ° C.
Fourth to nineteenth sheets were used. MDS (%) = ((mold size in flow direction−mold size in flow direction) / (mold size in flow direction)) × 100 TDS (%) = ((mold size in right angle direction−right angle direction) Molded product dimensions) / (Mold dimensions in right angle direction)) × 100 SDR (%) = ((MDS-TDS) / (MDS)) ×
100 Evaluation of the difference in shrinkage (SDR) is based on the difference in shrinkage of a colored plate obtained by adding only a plastic and without adding a pigment and an organic dye derivative to a colorless molded plate (hereinafter referred to as a natural plate). Is evaluated in comparison to
It is considered to be better to show an equivalent value. Normally, the numerical value as a guide is that if the shrinkage difference ratio of the colored molding plate is ± 5 with respect to the natural plate, the molding shrinkage such as warpage or deformation is good, and if it is within ± 10, it is slightly inferior. , ± 2
If it is 0 or more, it is evaluated as bad. For the evaluation of the warpage and the deformation, visual evaluation was also performed simultaneously with the evaluation of the shrinkage difference ratio. The criteria for visual evaluation are that if the degree of warpage and deformation is the same as compared to a colorless molded plate made of only plastic without adding pigment and organic dye derivative (hereinafter referred to as a natural plate), the effect of the pigment ○ as not seen
Those with severe warpage and deformation were rated X, and those with warpage and deformation more than those of the natural plate but the difference was small were rated △.

Example 1 α-type copper phthalocyanine pigment (CIPigmentBlue 15: 1, trade name Lionol Blue 7110)
-V, manufactured by Toyo Ink Mfg. Co., Ltd.), 100 parts of compound (a) and 400 parts of methanol were mixed and stirred at 50 ° C. for 1 hour. After cooling to room temperature, the mixture was filtered, washed with water and dried, and then pulverized with a sample mill. 10.0 parts of this pulverized material and 6.7 parts of calcium stearate were mixed well to obtain a dry color. Next, 2.0 parts of this dry color and a high-density polyethylene resin (product name Hizex)
2208J (Mitsui Chemicals Co., Ltd.) 1000 parts and several drops of an adhesive were tumbled and sufficiently mixed, then molded into a plate using an injection molding machine, and the warpage and deformation were evaluated. Compared with the natural plate, the shrinkage difference ratio shows a close value,
Visually, the warpage and deformation were almost the same.

Comparative Example 1 A molded plate was prepared in the same manner as in Example 1 except that the compound (a) was not added.
Compared with the natural plate, the value of the shrinkage difference ratio was large, and the warpage and deformation were large visually.

Comparative Example 2 In Synthesis Example 1, an organic dye derivative was synthesized using octylamine instead of distearylamine. Using this compound, a molded plate was prepared in the same manner as in Example 1. Compared with the natural plate and Example 1, the shrinkage difference ratio was large, and warping and deformation were large visually.

<Example 2> The procedure of Example 1 was repeated, except that 20 parts of the compound (a) was replaced with 10 parts of the compound (b). Warpage and deformation were comparable to the natural plate.

Example 3 Dimethyl quinacridone pigment (CIPigment Red 122: trade name Lionogen Magenta 5)
790 (manufactured by Toyo Ink Mfg. Co., Ltd.), 100 parts of compound (c) and 400 parts of methanol were mixed and stirred at 50 ° C. for 1 hour. After cooling to room temperature, the mixture was filtered, washed with water and dried, and then pulverized with a sample mill. 10.0 parts of the pulverized product, 5.0 parts of calcium stearate, and 5.0 parts of zinc stearate were mixed well to obtain a dry color. Next, 2.0 parts of the dry color, 1000 parts of a high-density polyethylene resin (product name: Hizex2208J, manufactured by Mitsui Chemicals, Inc.), and several drops of an adhesive were tumbled and sufficiently mixed, and then mixed with Example 1 using an injection molding machine. Similarly, it was injection-molded into a plate and evaluated similarly. Compared with the natural plate, the shrinkage difference ratio showed a near value, and the warpage and deformation were visually the same.

Example 4 Dimethylquinacridone Pigment (CIPigmentRed 122: Trade Name Lionogen Magenta 5
790 (manufactured by Toyo Ink Mfg. Co., Ltd.), 10 parts of the compound (d) pulverized by a sample mill, 55 parts of calcium stearate and 55 parts of zinc stearate were thoroughly mixed with a powder mixer to obtain a dry color. Next, 1.0 part of this dry color, high-density polyethylene resin (product name Hiz
ex2208J (Mitsui Chemicals Co., Ltd.) 1000 parts and several drops of an adhesive were tumbled and sufficiently mixed, and then injection-molded into a plate using an injection molding machine in the same manner as in Example 1, and evaluated in the same manner. Compared to the natural plate, the difference in shrinkage, warpage and deformation were almost the same.

Comparative Example 3 A molding plate was prepared using an injection molding machine in the same manner as in Example 4 except that the compound (d) was not added. Compared with the natural plate, Example 3 and Example 4, the shrinkage difference ratio was large, and the warpage and deformation were large.

<Comparative Example 4> In Synthesis Example 3, an organic dye derivative was synthesized using octylamine instead of stearylamine. Using these compounds, a dry color was prepared in the same manner as in Example 4, and then a molded plate was prepared. Compared with the natural plate, Example 3 and Example 4, the shrinkage difference ratio was large, and the warpage and deformation were large.

Comparative Example 5 In Synthesis Example 3, an organic dye derivative was synthesized using dioctylamine instead of stearylamine. Using these compounds, a dry color was prepared in the same manner as in Example 4, and then a molded plate was prepared. However, the amount of the organic dye derivative used was 20% by weight based on the organic pigment. Compared with the natural plate, Example 3 and Example 4, the shrinkage difference ratio is large,
Warpage and deformation were large.

Example 5 β-type copper phthalocyanine pigment (CIPigmentBlue 15: 3, trade name Lionol Blue 733)
100 parts, manufactured by Toyo Ink Mfg. Co., Ltd.), 20 parts of compound (e) pulverized by a sample mill, and 110 parts of polyethylene wax (molecular weight 4300, softening point 110 ° C., density 0.92 g / cm ³ ) were mixed and melted. After kneading, the mixture was pulverized to obtain a processed pigment. 4 parts of this processed pigment and high density polyethylene (MFR: 0.06 g / 10 min, density: 0.952 g /
cm3) and then melt-kneaded to obtain a pelletized master batch. Next, this master batch 5
Part, high-density polyethylene resin (product name Hizex220)
8J (manufactured by Mitsui Chemicals, Inc.), 100 parts were mixed, injection-molded into a plate in the same manner as in Example 1 using an injection molding machine, and evaluated in the same manner. Compared with the natural plate and Example 1, the shrinkage difference ratio showed a close value, and the degree of warpage and deformation was almost the same visually.

Example 6 Dimethylquinacridone pigment (CIPigmentRed 122: trade name Lionogen Magenta 5)
790 (manufactured by Toyo Ink Mfg. Co., Ltd.), 10 parts of compound (c) and 400 parts of isopropyl alcohol were mixed and stirred at 80 ° C. for 1 hour. After the solvent was distilled off, the residue was filtered, washed with water, dried, and pulverized by a sample mill. 100 parts of the pulverized treated pigment and 100 parts of polyethylene wax (molecular weight 4300, softening point 110 ° C., density 0.92 g / cm ³ )
Were mixed, melt-kneaded and pulverized to obtain a processed pigment. 5 parts of this processed pigment and high density polyethylene (MFR: 0.06 g)
/ 10 minutes, density: 0.952 g / cm3), and then kneaded with a melt to obtain a pelletized master batch. Next, after mixing 5 parts of this master batch and 100 parts of a high-density polyethylene resin (product name: Hizex2208J, manufactured by Mitsui Chemicals, Inc.), the mixture was injection-molded into a plate using an injection molding machine in the same manner as in Example 1, and evaluated in the same manner. . Compared with the natural plate and Example 1, the shrinkage difference ratio showed a close value, and the degree of warpage and deformation was almost the same visually.

Example 7 100 parts of diketopyrrolopyrrole pigment (CIPigmentRed 254: trade name Irgazine DPP Red BO manufactured by Ciba Specialty Chemicals)
15 parts of compound (j) pulverized by a sample mill, 115 parts of polyethylene wax (molecular weight: 4200, softening point: 118)
° C, density 0.93 g / cm ³ ), melt-kneaded and pulverized to obtain a processed pigment. 4 parts of this processed pigment and high density polyethylene (MFR: 0.06 g / 10 min, density: 0.9
After mixing 100 parts of 52 g / cm3), the mixture was melted and kneaded to obtain a pelletized master batch. Next, 5 parts of this master batch and a high-density polyethylene resin (product name Hize)
x2208J (Mitsui Chemicals, Inc.) 100 parts were mixed, melt-kneaded, and pelletized colored pellets (DP2)
I got Next, using this colored pellet (DP2),
It was injection-molded into a plate by an injection molding machine in the same manner as in Example 1, and evaluated in the same manner. Natural plate and Example 1
The shrinkage difference ratio showed a near value as compared with, and the warpage and deformation were almost the same visually.

Examples 8 to 20 As shown in Table 2, using the various pigments and the organic dye derivatives obtained in the synthesis examples, using the addition amounts shown in Table 2, Examples 8 to 10 As in Example 1, Examples 11 to 14 prepared dry colors in the same manner as Example 4, and Examples 15 to 17 prepared master batches in the same manner as Example 5;
In No. 20, a colored pellet was prepared in the same manner as in Example 7, and then a molding plate was injection-molded with an injection molding machine to evaluate warpage and deformation. Compared with the natural plate, the shrinkage difference ratio showed a close value, and the warp and deformation were visually comparable to the natural plate. In these examples, it was found that the plates prepared in the same manner without adding the organic dye derivative had a large shrinkage difference ratio and a large degree of warpage and deformation as compared with the natural plate. .

[0062]

[Table 2]

<Examples 21 to 27> Examples 21 to 2
No. 7 was obtained by replacing the high-density polyethylene resin in Examples 1, 3, 5, 7, 9, 10, and 17 with a polypropylene resin (trade name: Grand Polypro B761QD, manufactured by Grand Polymer Co., Ltd.), and similarly performing injection molding and evaluation. Plates were made and evaluated.

<Comparative Examples 6 and 7> Comparative Examples 6 and 7 are the same as Examples 21 and 22 except that the organic dye derivative was not added.
Otherwise, a molded plate was prepared and evaluated in the same manner.

Table 3 shows Examples 21 to 27 and Comparative Examples 6 to
7 shows the results. The shrinkage difference rates of the molded plates of Comparative Examples 6 and 7 were smaller than those in the case where the high-density polyethylene resin was used, but were larger than the natural. In contrast,
The shrinkage difference ratios of Examples 21 to 27 were not different from the natural shrinkage difference ratios, and the warpage and deformation in visual evaluation were almost the same as those of natural, and the effect of the organic dye derivative was recognized.

[0066]

[Table 3]

[0067]

EFFECT OF THE INVENTION According to the present invention, warpage of a molded article while maintaining properties of an organic pigment such as light resistance, heat resistance, and migration resistance,
Deformation and dimensional change can be reduced. Defective products due to molding shrinkage distortion such as warpage and deformation of molded products are reduced, and productivity can be improved.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 5/5398 C08K 5/5398 C08L 23/00 C08L 23/00 F term (Reference) 4F070 AA12 AA13 AC45 AC50 AC55 AE04 FA03 FB03 4J002 BB031 BB121 BB171 EG028 EG038 EG048 EG078 EQ016 EU026 EU036 EU056 EU116 EU236 EW167 FD096 FD097

Claims (8)

[Claims] 1. A colorant for plastics containing an organic pigment and an organic dye derivative represented by the following general formula [1]. General formula [1] (Where P is an organic dye residue, X is -SO ₂ -,-
CO -, - CH ₂ - or -CH ₂ NHCOCH ₂ -,
R ₁ and R _{2 each} represent a hydrogen atom or an alkyl group (at least one of R ₁ and R ₂ represents an alkyl group having 12 to 30 carbon atoms); M represents one equivalent of a cation having 1 to 3 valences; ~ 2
And n represents the number of 1-3. ) 2. The colorant according to claim 1, wherein the plastic is a polyolefin. 3. The colorant according to claim 1, wherein the organic pigment is a condensed polycyclic organic pigment. 4. A powdery colorant comprising the colorant according to claim 1 and a metal salt of an aliphatic carboxylic acid or a metal salt of an aromatic carboxylic acid. 5. A masterbatch obtained by blending the colorant according to claim 1 with a plastic at a high concentration and molding it into a pellet. 6. A method for improving molding distortion of a plastic molded product, which comprises adding an organic pigment derivative represented by the following general formula [1] when mixing and coloring an organic pigment with a plastic. General formula [1] (wherein, P is an organic dye residue, X is-
_{SO 2 -, - CO -,} - CH 2 - or -CH ₂ NHCO
CH ₂ —, R ₁ and R ₂ represent a hydrogen atom or an alkyl group (R ₁ ,
At least one of R ₂ represents an alkyl group having 12 to 30 carbon atoms. ), M is one equivalent of a cation having 1 to 3 valences, and m is 0
The number of ２2, n represents the number of 1１〜３3. ) 7. The method according to claim 6, wherein the plastic is a polyolefin. 8. The method according to claim 6, wherein the organic pigment is a condensed polycyclic organic pigment.