JP4525191B2 - Pigment compositions and their use in plastics - Google Patents

Description

  The present invention relates to a pigment composition for coloring, and in particular, to a colorant containing a phthalocyanine pigment as a main coloring component and a plastic molded product colored thereby with less warpage and deformation.

  Phthalocyanine pigments used as plastic colorants have characteristics such as light resistance, heat resistance, migration resistance, clear hue, high coloring power, etc., but partially crystalline such as polyolefin and polyethylene terephthalate. When used for coloring a thermoplastic resin, it affects the crystallinity and crystallization direction of the resin during molding, resulting in warping and deformation of the plastic molded product. The reason for this is thought to be because the phthalocyanine pigment acts as a resin crystallization agent.

  In order to improve the warping and deformation of plastic molded products, molding manufacturers are optimizing by changing processing conditions such as molding temperature, injection pressure, injection time, injection speed, and cooling time. However, since the shrinkage varies depending on the type of resin, colorant, additive, and size and shape of the molded product, it is difficult to set processing conditions that predict warpage and deformation. Moreover, the molding cycle was lengthened and the productivity was often deteriorated.

  As another method for improving warpage and deformation, a powerful crystallization agent (crystal nucleating agent, nucleating agent or crystallization accelerator) is added. The addition of the crystallizing agent has the effect of rapidly producing fine crystals by blending many components serving as crystal nuclei, and apparently has the effect of reducing the influence on shrinkage by the pigment. In addition, it is known that the molding cycle can be shortened by using a crystallization agent, and the advantage that rigidity and transparency are increased. Examples of the crystallization agent include carboxylic acid metal salts such as sodium benzoate, aluminum 4-tert-butylbenzoate and sodium adipate, sodium bis (4-tert-butylphenyl) phosphate, sodium-2,2′- Acid phosphate metal salts such as methylenebis (4,6-ditert-butylphenyl) phosphate, sorbitol acetal types such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol are used. However, the effect was insufficient for warpage and deformation.

  In addition, methods for modifying pigments so that they do not function as crystal nuclei are also being studied. Pigment derivatives (organic) with various substituents introduced into the pigment skeleton, changing the crystal form, particle size, and shape of the pigment. The pigment surface is modified by adding a pigment compound), and the pigment surface is modified by subjecting the pigment to a surface treatment with a resin or a silane coupling agent.

  Methods for changing the crystal form, particle size, and shape of the pigment are described in Patent Document 1, Patent Document 2, Patent Document 3, and the like. However, sufficient effects are not obtained. In addition, changes in the crystal form, particle diameter, and shape of the pigment affect the original properties of the pigment such as hue, dispersibility, coloring power, heat resistance, and light resistance.

  As a method for improving warpage and deformation of a phthalocyanine pigment, a method described in Journal of Japan Colorant Association (2003) Vol. 76, page 97, that is, a method of introducing a specific number of halogens into a phthalocyanine skeleton is described. Yes. Although this method improves the warpage and deformation, characteristics such as high coloring power and high sharpness inherent to the phthalocyanine pigment are lost, and the hue is greatly changed.

  As a surface modification method using a so-called pigment derivative in which a substituent is introduced into a pigment structure for the purpose of improving warpage and deformation, phthalimidomethyl derivatives are described in Patent Documents 4 and 5. Although the warpage and deformation are somewhat improved by this invention, it is not sufficient, and when a necessary amount is added for improving the warpage, the color transfer property is deteriorated, and it has not been put into practical use.

As surface modification methods for pigments other than pigment derivatives, surface treatment with organic silane or organic titanium and surface coating of the pigment with a thermoplastic resin are performed. Patent Document 6 describes that a pigment surface is modified with a polymer by coexisting a sulfonic acid having an organic pigment residue and a polymer composed of a water-soluble polymer ammonium salt. However, the effect was insufficient.
Japanese Patent Laid-Open No. 04-376232 JP 57-155242 A JP 58-125752 A Japanese Patent Publication No.53-7185 Japanese Patent Laid-Open No. 03-12432 JP 05-194873 A

  The present invention provides a pigment composition and a colorant that solves warpage and deformation in a molded article without impairing the excellent properties of the phthalocyanine as a colorant when a plastic is colored with phthalocyanine.

(但し、式中Ｐは銅フタロシアニン骨格を表し、Ｙは水素もしくはハロゲン原子を表し、ｎは１〜４の整数を表す。) The present invention relates to 1 to 45% by weight of halogenated phthalocyanine having 50 to 95% by weight of phthalocyanine, 1 to 9 halogen atom substituents and 2.0 to 4.0 average substituents, and the following general formula (1) or The present invention relates to a pigment composition comprising 0.1 to 10% by weight of a phthalocyanine derivative represented by the general formula (2).
General formula (1)
P- (X) m
(In the formula, P represents a copper phthalocyanine skeleton, X represents an alkyl group having 12 to 18 carbon atoms, an alkoxy group having 12 to 18 carbon atoms, —SO ₂ NHR, —SO ₂ NR ₂ , —NR ₂ , —CONR _2. , -CONHR, -SR (R represents an alkyl group or alkenyl group having 12 to 18 carbon atoms), and m represents an integer of 1 to 4.)
General formula (2)

(Wherein, P represents a copper phthalocyanine skeleton, Y represents a hydrogen or halogen atom, and n represents an integer of 1 to 4.)

  Furthermore, the present invention is a colorant for plastics comprising the above pigment composition.

  Furthermore, the present invention is a powdery colorant comprising the above pigment composition and an aliphatic carboxylic acid metal salt or an aromatic carboxylic acid metal salt.

Furthermore, this invention is a coloring agent obtained by mix | blending 0.1-300 weight part of said pigment compositions with 100 weight part of plastics .

  Furthermore, the present invention is a colorant in which the plastic is a polyolefin.

  According to the present invention, it is possible to reduce warpage, deformation, and dimensional change of a molded product while maintaining the vivid hue and color development characteristics of phthalocyanine. Defective products due to warping and deformation of the molded product are reduced, and productivity can be improved.

  Furthermore, the present invention is a molded article obtained by blending the above-described colorant with plastic.

Hereinafter, embodiments of the present invention will be described in detail.
The phthalocyanine used in the present invention is a metal-free phthalocyanine or a metal phthalocyanine such as copper phthalocyanine and aluminum phthalocyanine, and the presence or absence of the central metal, the type, etc. are not particularly limited.

Phthalocyanine structure of the general formula (1) and general formula (2) in the present invention (P) is Ru copper phthalocyanine der.

  The method for producing a halogenated phthalocyanine used in the present invention may be a generally known method for producing a halogenated phthalocyanine. The halogen atom has 1 to 9 substituents and an average substituent number of 2.0 to 4. If it is 0, there is no restriction in particular. As a production method, a halogen phthalic acid previously introduced with a halogen atom substituent is used to synthesize a crude halogenated phthalocyanine, or a halogen is introduced in a state where the crude phthalocyanine is aluminum chloride or a molten salt of aluminum chloride and sodium chloride. The so-called aluminum chloride method, and a method of synthesizing a crude halogenated phthalocyanine using a halogenated phthalonitrile, are mentioned. Among them, the halogenated phthalocyanine obtained by the aluminum chloride method has a better warping improvement effect than other methods. It is more preferable. The average number of halogen substituents is determined by controlling the amount of halogen introduced. The amount of halogen to be introduced varies depending on the production method, apparatus, and reaction conditions. When the amount of halogen is small, the average number of halogen substituents is small, and when the amount of halogen is large, the number of average halogen substituents is large. When the amount of halogen to be introduced is too small, it is not preferable with respect to the effect of improving the warp, and when it is too large, the effect of improving the warp and the hue are deteriorated. An amount such that the average number of halogen substituents is 2.0 to 4.0 is preferred.

  The halogenated phthalocyanine may be used as it is, but in order to eliminate the function as a nucleating agent, it is preferable to make the crystal form amorphous, for example, conventionally known treatment by acid pasting method using sulfuric acid, etc. It can be done by the method.

  In the present invention, the form of the halogenated phthalocyanine is not limited, and the halogenated phthalocyanine can be used in a powder form or a water paste form by a colorant or a masterbatch production method.

  The halogenated phthalocyanine used in the practice of the present invention can be used in an amount of 1 to 45% by weight in the pigment composition, and considering the hue, it is more preferable to use 5 to 20% by weight. When the ratio of the halogenated phthalocyanine is low, the effect of improving the warp is not sufficient and is not preferable. On the other hand, when the amount is too large, the vivid hue of the phthalocyanine is lost.

  The phthalocyanine derivative represented by the general formula (1) or the general formula (2) can obtain an effect of improving warpage when used alone, but for that purpose, it is contained in an amount of 10 to 20% by weight in the pigment composition. When a necessary amount is added for improving warpage, the sharpness and hue are deteriorated, and therefore it is not practically preferable to use it alone.

  The phthalocyanine derivative used in the present invention is desirably contained in the pigment composition in an amount of 0.1 to 10% by weight, more preferably 0.1 to 4% by weight. If the amount of the phthalocyanine derivative is too small, it is not sufficient for the effect of improving the sharpness and warpage, and conversely if it exceeds 10% by weight, the hue becomes unclear.

  When the halogenated phthalocyanine and the phthalocyanine derivative represented by the general formula (1) or (2) constituting the pigment composition of the present invention are used together with the pigment, the halogenated phthalocyanine or the phthalocyanine derivative is used alone. The effect of reducing the warpage and deformation of the molded product is much greater than that obtained.

  The mixing method of phthalocyanine and halogenated phthalocyanine and the phthalocyanine derivative represented by general formula (1) or general formula (2) is not particularly limited. Halogenation in pigmentation processes such as kneading and solvent treatment, mixing with a mixer such as water, stirring and mixing as a slurry of water or organic solvent, mixing with a medium with three or two rolls There is a method of adding phthalocyanine and a phthalocyanine derivative represented by the general formula (1) or (2). Preferably, a method of mixing in a slurry state using an organic solvent is advantageous for exhibiting a sufficient effect.

  In addition to the pigment composition, the colorant for plastics of the present invention may contain other organic pigments, inorganic pigments, waxes, or the like, as other components, as long as they do not impair the effects of the present invention or have no sanitary problems. Charging consisting of derivatives, heavy metal deactivators, alkali metal, alkaline earth metal or zinc metal soaps, hydrotalcite, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc. Inhibitors, flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylene bisalkylamide, antioxidants and ultraviolet absorbers, processing aids, fillers, various additives for known polymers, etc. Can be included. In order to satisfy the required quality and workability of coloring, pigment is dispersed in advance with these components, and it is said to be powdery dry color, granular bead color, liquid paste color, or liquid color. Is.

  One preferable form of the colorant of the present invention is a powdery colorant containing a pigment called dry color at a high concentration. In the case of dry color, an aliphatic carboxylic acid or an aromatic carboxylic acid and a phthalocyanine and a halogenated phthalocyanine, and a total of 100 parts by weight of the phthalocyanine derivative represented by the general formula (1) or the general formula (2) 1 to 1000 parts by weight of these metal salts are contained as a dispersant. Examples of aliphatic carboxylic acids or aromatic carboxylic acids and metal salts thereof include caprylic acid, oleic acid, stearic acid and the like as aliphatic carboxylic acids, and phthalic acid and benzoic acid as aromatic carboxylic acids. In addition, examples of the metal include lithium, calcium, magnesium, and zinc. Although the dry color is powdery and has poor workability, it has the highest pigment concentration and contributes to coloring in a small amount, so it is the most economical in terms of price and is often used for coloring polyolefins. When used for molding, 0.001 to 10 parts by weight of a dry color is used with respect to 100 parts by weight of the plastic for molding. The plastic pellets and dry color are uniformly mixed in advance with a mixer or the like, and then subjected to molding.

  In the present invention, the plastic to be colored is a partially crystalline resin that softens by heating and cures again by cooling, in particular, a homopolymer of ethylene, propylene, butylene, styrene and / or divinylbenzene, or Block or random copolymers or terpolymers, in particular α-olefins such as HDPE, LDPE, polypropylene and polystyrene. Examples of other useful resins are polyesters such as polyethylene terephthalate, polyamides such as nylon 6, nylon 66, and thermoplastic ionomers. The colorant of the present invention has a high effect on these crystalline thermoplastic resins, and is particularly remarkable for so-called polyolefin resins such as α-olefin, ethylene, propylene and butylene homopolymers and copolymers. Has an effect.

  As polyolefin resin, the thing of MFR (melt flow rate, ie, melt viscosity) 0.001-30 is preferable. If the MFR is less than 0.001, the melt viscosity of the colored resin composition is too high, so that moldability may be deteriorated, or a weld mark or a flow mark may be generated in the molded product. On the other hand, when the MFR exceeds 30, there is a concern that the mechanical properties of the molded product may be deteriorated. In particular, when high density polyethylene is used, the MFR is preferably 0.005 to 10, and when low density polyethylene, polypropylene, or polybutene is used, the MFR is preferably 0.005 to 20.

  The colorant of the present invention may be a pellet-like colorant called a so-called master batch which is composed of a pigment composition and a plastic and contains a pigment in a high concentration. In the case of a master batch containing a pigment at a high concentration, the master batch may be diluted with plastic and used for molding to obtain a molded product.

  Comparing the masterbatch with the colored pellets, the processing steps are not much different, and the masterbatch is a little more expensive than the colored pellets because it contains a higher concentration of pigment. Since a molded product is obtained by diluting 0.5 to 200 times, it is cheaper to obtain a molded product by diluting with plastic using a masterbatch than to obtain a molded product with colored pellets when compared with the final molded product. This is preferable.

  In the case of a masterbatch, it is preferable to contain 100 parts by weight of plastic and 0.1 to 300 parts by weight of the pigment composition of the present invention. When the pigment composition is less than 0.1 parts by weight, there is no meaning as a master batch, and when the pigment composition is contained in an amount of more than 300 parts by weight, granulation of the master batch becomes difficult. And in the case of the masterbatch which contains a pigment in high concentration, the masterbatch should just be diluted with a plastic, and it may use for shaping | molding and a molded article may be obtained. Examples of the plastic used for dilution include the same plastics used in obtaining a pellet-shaped masterbatch containing a high concentration of pigment. The final molded product preferably contains 100 parts by weight of plastic and 0.001 to 10 parts by weight of a colorant, as in the case of pellets that are directly subjected to molding without requiring dilution.

  The master batch does not impair the effects of the present invention, or other organic pigments, inorganic pigments, other plastics, waxes, derivatives thereof, heavy metal deactivators, alkali metals, alkaline earths as long as there is no sanitary problem. Metal or zinc metal soap, hydrotalcite, nonionic surfactant, cationic surfactant, anionic surfactant, antistatic agent composed of amphoteric surfactant, halogen-based, phosphorus-based or metal oxide, etc. Flame retardants, lubricants such as ethylene bisalkylamides, antioxidants and ultraviolet absorbers, processing aids, fillers, various additives for known polymers, and the like.

  When obtaining the colorant of the present invention, it is preferable to pre-process the pigment composition with a dispersant such as polyethylene wax before kneading the pigment composition and the plastic. There are two methods of pre-processing: one in which a colorant and a dispersant are blended in a mixer, and one in which a pigment composition and a dispersant are blended and pulverized after melt-kneading. Thus, the latter type of processing method in which melt kneading is performed is preferable.

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

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not specifically limited to an Example. In the examples, parts and% represent parts by weight and% by weight, respectively, unless otherwise specified. The number of halogen substituents of the halogenated phthalocyanine obtained in the production example was measured by mass spectrum (JMS-DX303HF manufactured by JEOL Datum).

For evaluation of warpage and deformation, a mold for shrinkage evaluation was created with an injection molding machine (a plate with a length of 150 mm, a width of 120 mm, and a thickness of 2 mm with a marking line of 10.00 cm in the injection direction and its vertical direction) Molds), and the molded plate is stored in a thermostatic chamber for 3 days, and the shrinkage difference calculated by the ratio of the shrinkage rate in the injection direction and its vertical direction, and the warpage and deformation are visually observed. The degree was evaluated. Twenty sheets were continuously injection-molded at a molding temperature of 220 ° C. and a mold temperature of 40 ° C., and six of the fourteenth to nineteenth sheets were used for evaluation. After the molded plate was stored in a temperature-controlled room for 24 hours or more, the distance between the standards was measured with a precision caliper, and the shrinkage rate in the injection direction and the vertical direction was determined from the measured distance. Thereafter, the shrinkage difference rate calculated by the ratio between the injection direction and the shrinkage rate in the vertical direction, and the degree of warpage and deformation were visually evaluated. In addition, the calculation formula of the shrinkage difference rate is as Formula 1. In general, when the difference between the shrinkage difference between a molded plate made of pigment and resin and a plate molded only with resin (hereinafter referred to as natural) is within 10%, it is called a low shrinkage pigment or a low shrinkage pigment composition.
Shrinkage difference rate = (shrinkage rate in the injection direction−shrinkage rate in the vertical direction) / shrinkage rate in the injection direction

  The standard for visual evaluation is “good”, warping because the effect of the pigment is not seen if the warpage and deformation are comparable compared to a colorless molded plate made of plastic alone (hereinafter referred to as “natural plate”). Those that were severely deformed were considered “bad”.

  Hue was measured by mixing 1 part of the pigment composition used in the examples, 1 part of zinc stearate, 1000 parts of polypropylene, and 50 parts of titanium oxide, and kneading each mixture with a single screw extruder. The obtained compound was molded by an injection molding machine to obtain a molded plate having a thickness of 2 mm. The reflectance of each of the obtained plates was measured using a color difference meter “KURABOColor-7E” (manufactured by KURABO) in an L * a * b * hue system. Comparative Example 1 using Lionol Blue FG-7351 (C.I. Pigment Blue 15: 3 manufactured by Toyo Ink Co., Ltd.) as the pigment composition was used as a standard for measuring the hue difference. The color difference from the standard was determined, and when ΔE was 3.0 or less and Δb was 2.0 or less, it was judged “good”, and otherwise “bad”.

  The color intensity was measured by mixing 1 part of a pigment composition, 1 part of zinc stearate, 1000 parts of polypropylene, and 50 parts of titanium oxide, kneading each mixture with a single screw extruder, and mixing the resulting compound. Molding was performed by an injection molding machine to obtain a molding plate having a thickness of 2 mm. Using the color difference meter “KURABOColor-7E” (manufactured by KURABO), the reflectance of each plate obtained was measured at 640 nm, and the Kubelka-Munk function (k / s) (k / s) ( Color development intensity) was determined. The color intensity was rounded off to the first decimal place.

  Synthesis examples of halogenated phthalocyanines are shown in Production Examples 1 to 4 below.

<Production Example 1>
200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a molten salt, and 40 parts of crude copper phthalocyanine was added, followed by heating to 180 ° C., and introduction of 8 parts of chlorine at a rate of 2 parts per hour for 3 hours. After introducing chlorine, the reaction mixture was poured into a large amount of water, washed with filtered water, dried and pulverized to obtain 46 parts of chlorinated copper phthalocyanine. The obtained chlorinated copper phthalocyanine was added to 300 parts of 98% sulfuric acid and stirred at 40 to 45 ° C. for 4 hours, and then the mixture was added to 2000 parts of water. After stirring at 80 ° C. for 2 hours, filtration, washing with water, drying and pulverization were carried out to obtain 45 parts of chlorinated copper phthalocyanine. The number of halogen substituents of chlorinated copper phthalocyanine was 1 to 6, and the average number of substituents was 3.2.

<Production Example 2>
200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a molten salt, and 40 parts of crude copper phthalocyanine was added, followed by heating to 180 ° C., and bromine was added dropwise at a rate of 3 parts per hour for a total of 18 parts. After dropping bromine, the reaction mixture was poured into a large amount of water, washed with filtered water, dried and pulverized to obtain 55 parts of brominated copper phthalocyanine. The obtained chlorinated copper phthalocyanine was added to 300 parts of 98% sulfuric acid and stirred at 40 to 45 ° C. for 4 hours, and then the mixture was added to 2000 parts of water. After stirring at 80 ° C. for 2 hours, filtration, washing with water, drying and pulverization were carried out to obtain 52 parts of brominated copper phthalocyanine. The number of halogen substituents of brominated copper phthalocyanine was 1 to 5, and the average number of substituents was 2.8.

<Production Example 3>
200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a molten salt, and 40 parts of crude copper phthalocyanine was added, followed by heating to 180 ° C., and introduction of 22 parts of chlorine at a rate of 2 parts per hour for 10 hours. After introducing chlorine, the reaction mixture was poured into a large amount of water, washed with filtered water, dried and pulverized to obtain 58 parts of chlorinated copper phthalocyanine. The obtained chlorinated copper phthalocyanine was added to 300 parts of 98% sulfuric acid and stirred at 40 to 45 ° C. for 4 hours, and then the mixture was added to 2000 parts of water. After stirring at 80 ° C. for 2 hours, filtration, washing with water, drying and pulverization were carried out to obtain 57 parts of chlorinated copper phthalocyanine. The number of halogen substituents of chlorinated copper phthalocyanine was 5 to 11, and the average number of substituents was 8.0.

<Production Example 4>
200 parts of aluminum chloride and 40 parts of sodium chloride were heated to form a molten salt, and 40 parts of crude copper phthalocyanine was added, followed by heating to 180 ° C., and bromine was added dropwise at a rate of 6 parts per hour for a total of 42 parts. After dropwise addition of bromine, 20 parts of chlorine was introduced at a rate of 2 parts per hour for 9 hours. After introducing chlorine, the reaction mixture was poured into a large amount of water, washed with filtered water, dried and pulverized to obtain 92 parts of brominated chlorinated copper phthalocyanine. The resulting brominated chlorinated copper phthalocyanine was added to 600 parts of 98% sulfuric acid and stirred at 40-45 ° C. for 4 hours, and then the mixture was added to 4000 parts of water. After stirring at 80 ° C. for 2 hours, filtration, washing with water, drying and pulverization were carried out to obtain 90 parts of brominated chlorinated copper phthalocyanine. The number of halogen substituents of brominated chlorinated copper phthalocyanine was 12 to 16, and the average number of substituents was 14.5.

<Example 1> 88 parts of phthalocyanine pigment (CIPigment Blue 15; 3, trade name Lionol Blue FG-7351, manufactured by Toyo Ink Manufacturing Co., Ltd.), 10 parts of halogenated phthalocyanine prepared according to Preparation Example 1, Compound A 2 parts of the phthalocyanine derivative shown in the above was mixed with a mixer to obtain a pigment composition. Next, 100 parts of this pigment composition and 100 parts of calcium stearate were mixed with a mixer to obtain a colorant. 2 parts of the resulting colorant was added to a high-density polyethylene resin (product name: Hizex 2100J
After 1000 parts of Sumitomo Mitsui Polyolefin Co., Ltd. and several drops of adhesive were tumbled and mixed well, they were molded into a plate shape with an injection molding machine, and warpage, deformation, and hue were evaluated. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was a plate with good hue and high tinting strength similar to the plate colored with phthalocyanine pigment alone.

Compound A

  <Comparative Example 1> A molded plate was prepared in the same manner as in Example 1 except that the halogenated phthalocyanine and the phthalocyanine derivative were not used. Compared to the natural plate, the shrinkage difference rate was large, and the warpage and deformation were large even visually.

  <Comparative example 2> In Example 1, the molding plate was created by the same method except not using a phthalocyanine derivative. Compared with the natural plate and Example 1, the shrinkage difference rate was large, and warping and deformation were large even visually.

  <Comparative example 3> In Example 1, the shaping | molding plate was created by the same method except not using halogenated phthalocyanine. Compared with the natural plate and Example 1, the shrinkage difference rate was large, and warping and deformation were large even visually.

  <Comparative example 4> In Example 1, 20 parts of phthalocyanine derivatives were used without using a halogenated phthalocyanine, and a molded plate was prepared in the same manner except that. Although the shrinkage difference was small and no warping was observed visually, the hue was poor and the color development was not as good as 95% compared to the comparative object.

  <Comparative Example 5> A molded plate was obtained in the same manner as in Example 1, except that 100 parts of halogenated phthalocyanine produced according to Production Example 1 was used instead of the pigment composition. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. However, the hue was poor, and the color development was not as excellent as 90% compared to the comparative object.

  <Example 2> Molding was performed in the same manner as in Example 1 except that a polypropylene resin (product name: Mitsumi Mitomo PP, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.) was used instead of the high-density polyethylene resin (product name: Hizex2100J, manufactured by Sumitomo Mitsui Polyolefin) A plate was obtained. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was good and the coloring power was equivalent to that of the comparative object.

  <Comparative Example 6> A molded plate was prepared in the same manner as in Example 2 except that the halogenated phthalocyanine and the phthalocyanine derivative were not used. Compared to the natural plate, the shrinkage difference rate was large, and the warpage and deformation were large even visually.

  <Comparative example 7> In Example 2, the molding plate was created by the same method except not using a phthalocyanine derivative. Compared with the natural plate and Example 1, the shrinkage difference rate was large, and warping and deformation were large even visually.

  <Comparative example 8> In Example 2, the shaping | molding plate was created by the same method except not using halogenated phthalocyanine. Compared with the natural plate and Example 1, the shrinkage difference rate was large, and warping and deformation were large even visually.

  <Example 3> A molded plate was produced in the same manner as in Example 1, except that the halogenated phthalocyanine was replaced with the halogenated phthalocyanine produced according to Production Example 2. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was good and the coloring power was equivalent to that of the comparative object.

  <Comparative Examples 9 to 10> In Example 3, the halogenated phthalocyanine was produced in accordance with Production Example 3 in the case of Comparative Example 9, and the production in accordance with Production Example 4 in the case of Comparative Example 10. A molded plate was obtained in the same manner except that the halogenated phthalocyanine was used. Each of them had a large shrinkage difference rate, and warping and deformation were also large visually. The hue was also poor.

実施例５：
化合物C

実施例６：
化合物D

実施例７：
化合物E

実施例８：
化合物F

実施例９：
化合物G

実施例１０：
化合物H

実施例１１：
化合物I

<Examples 4 to 11> Molded plates were prepared in the same manner except that the phthalocyanine derivatives used in Example 1 were replaced with the following chemical phthalocyanine derivatives. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was good and the coloring power was equivalent to that of the comparative object.
Example 4:
Compound B

Example 5:
Compound C

Example 6:
Compound D

Example 7:
Compound E

Example 8:
Compound F

Example 9:
Compound G

Example 10:
Compound H

Example 11:
Compound I

<Example 12> Phthalocyanine pigment (CIPigment Blue
15; 3, product name Lionol Blue FG-7351, manufactured by Toyo Ink Manufacturing Co., Ltd.) 88 parts, halogenated phthalocyanine 10 parts produced according to Production Example 1, 2 parts phthalocyanine derivative shown in Compound A To obtain a pigment composition. 100 parts of the pigment composition and polyethylene wax (trade name: High Wax NL-500, manufactured by Mitsui Chemicals) were sufficiently mixed, melt-kneaded with three rolls and pulverized to obtain a processed pigment. 4 parts of this processed pigment and 100 parts of high-density polyethylene were mixed and then melt-kneaded with a twin-screw extruder to obtain a pellet master batch. Next, after mixing 5 parts of this master batch and 100 parts of high-density polyethylene resin (product name Hizex 2100J, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.), it was injection-molded in the same manner as in Example 1 with an injection molding machine and evaluated in the same manner. . Compared with the natural plate and Example 1, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually.
Compound A

  <Example 13> In the same manner as in Example 1, except that the pigment used was replaced with a phthalocyanine pigment (CIPigment Blue 15: 1, trade name Lionol Blue 7110-V, manufactured by Toyo Ink Manufacturing Co., Ltd.). A molded plate was obtained. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was a plate with good hue and high tinting strength similar to the plate colored with phthalocyanine pigment alone.

<Example 14> Phthalocyanine pigment (CIPigment Blue
15; 3, product name Lionol Blue FG-7351, manufactured by Toyo Ink Manufacturing Co., Ltd.) 88 parts, halogenated phthalocyanine 10 parts produced according to Production Example 1, 2 parts phthalocyanine derivative shown in Compound A To obtain a pigment composition. 1 part of the obtained pigment composition, 1 part of magnesium stearate and 1000 parts of polyethylene terephthalate resin (trade name VylopetEMC-307, manufactured by Toyobo Co., Ltd.) are mixed, and the injection conditions are set to a molding temperature of 275 ° C. and a mold temperature of 85 ° C. The molded plate was obtained by molding with the injection molding machine. Compared with the natural plate, the shrinkage difference rate showed a close value, and the warpage and deformation were the same level visually. Also, the hue was a plate with good hue and high tinting strength similar to the plate colored with phthalocyanine pigment alone.
Compound A

  <Comparative Example 11> A molded plate was obtained in the same manner as in Example 9 except that halogenated phthalocyanine and a phthalocyanine derivative were not used. Compared to the natural plate, the shrinkage difference rate was large, and the warpage and deformation were large even visually.

The results of Examples 1 to 14 and Comparative Examples 1 to 11 are shown in Table 1.

Claims (6)

50 to 95% by weight of phthalocyanine, 1 to 45% by weight of halogenated phthalocyanine having 1 to 9 halogen atoms and an average number of substituents of 2.0 to 4.0, and the following general formula (1) or general formula (2 The pigment composition which consists of 0.1-10 weight% of copper phthalocyanine derivatives shown by this.
General formula (1)
P- (X) m
(In the formula, P represents a copper phthalocyanine skeleton, X represents an alkyl group having 12 to 18 carbon atoms, an alkoxy group having 12 to 18 carbon atoms, —SO ₂ NHR, —SO ₂ NR ₂ , —NR ₂ , —CONR _2. , -CONHR, -SR (R represents an alkyl group or alkenyl group having 12 to 18 carbon atoms), and m represents an integer of 1 to 4.)
General formula (2)

(However, P in the formula represents a copper phthalocyanine skeleton, Y represents hydrogen also properly represents a C androgenic atoms, n is an integer of 1-4.) A plastic colorant comprising the pigment composition according to claim 1. A powdery colorant comprising the pigment composition according to claim 1 and an aliphatic carboxylic acid metal salt or an aromatic carboxylic acid metal salt. The coloring agent obtained by mix | blending 0.1-300 weight part of pigment compositions of Claim 1 with 100 weight part of plastics . The colorant according to claim 4, wherein the plastic is polyolefin. A molded product obtained by blending the colorant according to any one of claims 2 to 5 with a plastic.