JP2002003640A - Polyolefin series resin coloring composition and polyolefin series colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly transparent molding capable of coloring polyolefin series resin vividly and giving excellent nonbleeding characteristics of a colored molding. SOLUTION: This resin coloring composition is provided with rosin acid and/or the metallic salts of 1 to 1,000 pts.wt. to phthalocyanine series dye of 1 pt.wt. represented by formula 1 [wherein, CuPc represents Cu phthalocyanine residue; R1 to R6 represent each independently H, alkyl group, aralkyl group or aryl group; (o), (p) and (q) represent each independently integer of 0 to 4, and (o+p+q) is 1 to 4.]. Polyolefin series resin of 100 pts.wt. and the polyolefin series resin coloring composition of 0.0005 to 15 pts.wt. are contained in the colored resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin coloring composition used for coloring a polyolefin resin and a polyolefin coloring resin composition containing the polyolefin resin coloring composition.

[0002]

2. Description of the Related Art Polyolefin resins are used in various fields such as industrial parts, films and sheets because of their excellent mechanical properties, electrical properties and workability. I have. Polyolefin-based resins used in these fields are often colored for decoration to enhance commercial value and for imparting functionality such as concealment and discrimination. In addition, the fields of application that require transparency of materials, such as automotive exterior parts (headlamps, tail lamps, etc.), building materials (transparent shutters, terraces, etc.), medical equipment, tableware for microwave ovens, etc., are increasing.
There is an increasing demand for polyolefin resins as materials for colored moldings having transparency.

[0003] As a colorant for polyolefin resin,
Although pigments and dyes are used, pigments are overwhelmingly large in quantity and type. This is because various properties such as heat resistance and solvent resistance of the pigment are superior to those of the dye. However, pigments are difficult to disperse finely and uniformly in a resin such as a polyolefin resin, and have opacity, so that they are not suitable for use in a field requiring a high degree of transparency.

On the other hand, when a dye is used for coloring a polyolefin-based resin, since the compatibility between the dye and the resin is good, transparent and vivid coloring can be performed. However, since the dye has high solubility in water and organic solvents and high solubility in the polyolefin resin, when the dye comes into contact with the solvent, the dye migrates to the solvent or migrates to another contacted polyolefin resin. (Hereinafter, referred to as “bleeding property”). This is an important issue particularly when a polyolefin resin is used for a food packaging material.

The present invention has been made in view of the above-mentioned problems in the prior art, and an object of the present invention is to enable a polyolefin resin to be clearly colored with a dye and to be colored. A polyolefin-based resin coloring composition capable of effectively realizing the non-bleeding property of a molded article and capable of obtaining a highly transparent molded article, and a molded article which is sharply colored with a dye. The object of the present invention is to provide a polyolefin-based colored resin composition which effectively realizes the non-bleeding property and can obtain a molded article having high transparency.

[0006]

The polyolefin resin coloring composition of the present invention for achieving the above object comprises a phthalocyanine dye and rosin acid and / or a metal salt thereof.

This polyolefin resin coloring composition is substantially composed of a phthalocyanine dye and rosin acid and / or
Alternatively, it can be composed of a metal salt thereof.

The polyolefin-based colored resin composition of the present invention comprises a polyolefin-based resin and the above-described composition for coloring a polyolefin-based resin.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The phthalocyanine dye used in the present invention is a robust dye having a phthalocyanine skeleton and may have various substituents. Preferred substituents include a carboxy group or a group having a carboxy group, a sulfone group or a group having a sulfone group, a sulfonyl group having a substituent (eg, an alkyl group and an aryl group), a sulfonamide group, and a substituent (for example, , An alkyl group, an aryl group, etc.). The phthalocyanine dye used in the present invention may or may not have a central metal. Examples of the central metal include Cu, Co, Fe, and Al. Preferably it is Cu.

As such phthalocyanine dyes, there can be mentioned, for example, the following ones described in a color index.

As the acid dye, CI Acid blue 119,
185, 197, 228, 242, 243, 254, 255,
Blue dyes such as 275 and 279, and CI Acid green 97
And the like.

As the direct dye, CI Direct blue 8
6, 86: 1, 87, 189, 199, blue dyes such as Direct dye (74350), and green dyes such as CI Direct green 75.

As the oil-soluble dye, CI Solvent blue
24, 25, 38, 44, 48, 55, 64, 67, 7
Blue dyes such as 0, 89, 117, and 129.

Preferred as the phthalocyanine dye in the polyolefin resin coloring composition and the polyolefin coloring resin composition of the present invention are compounds represented by the following formula (I) (a mixture of a plurality of types of compounds. May be used.)

[0015]

Embedded image ... (I)

[In the formula (I), CuPc represents a copper phthalocyanine residue, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R
⁶ independently of each other (that is, all or some of R ^{1 to} R ⁶ may be the same or may be different from each other), a hydrogen atom, an alkyl group (for example, alkoxy [for example, carbon 1 to 10] groups and halogens [for example, C
l, Br, etc.], substituted or unsubstituted, branched or unbranched alkyl groups having 1 to 12 carbon atoms), aralkyl groups (eg, benzyl group, α, α-dimethylbenzyl group, phenethyl group) , Naphthylalkyl group or the like) or an aryl group (for example, a substituted or unsubstituted phenyl group or naphthyl group having a substituent such as an alkyl group having 1 to 8 carbon atoms or a hydroxyl group), and o, p and q represent Each represents an integer of 0 to 4, and o + p + q is 1 to 4. ]

Preferred as the compound represented by the formula (I)
Is R¹, R², R³, R⁴, R ⁵, And R⁶But
Independently a hydrogen atom or an alkyl having 1 to 8 carbon atoms
Group (for example, an alkoxy group [for example, having 1 to 10 carbon atoms]
Or a substituent such as halogen [eg, Cl, Br, etc.]
Or unsubstituted, branched or unbranched alkyl
Group).

Further, as the phthalocyanine dye in the polyolefin resin coloring composition and the polyolefin coloring resin composition of the present invention, a compound represented by the following formula (II) (a mixture of plural kinds of compounds is preferable). May be used.).

[0019]

Embedded image ... (II)

In the formula (II), CuPc represents a copper phthalocyanine residue, m represents an integer of 1 to 4, ^{An +} represents a cation of an organic amine, n represents its ionic valence, and k represents
Indicates m / n (quotient of m divided by ionic valence n). ]

Examples of the organic amine include known aromatic amines and aliphatic amines.

Specific examples of the organic amine include butylamine, hexylamine, pentylamine, octylamine, laurylamine, myristylamine, palmitylamine, cetylamine, oleylamine, stearylamine, dibutylamine, 2-ethylhexylamine, and di-ethylamine.
Aliphatic amines such as (2-ethylhexyl) amine, di- (2-ethylhexyl) amine and dodecylamine; alicyclic amines such as cyclohexylamine, di-cyclohexylamine and rosinamine; 3-propoxypropylamine and 2-ethylhexylamine N, alkoxyalkylamines such as di- (3-ethoxypropyl) amine, 3-butoxypropylamine, octoxypropylamine and 3- (2-ethylhexyloxy) propylamine; N
Alkanol-containing amines such as cyclohexylethanolamine, N-dodecylethanolamine, triethanolamine, N-dodecylimino-di-ethanol;
Diamines such as dimethylaminopropylamine and dibutylaminopropylamine; amines of guanidine derivatives such as 1,3-diphenylguanidine, 1-o-tolylguanidine, di-o-tolylguanidine; aniline, benzylamine, naphthylamine and phenylamine And aromatic amines such as phenylenediamine, methylphenylenediamine, xylenediamine (or N-monoalkyl substituent). Preferred examples of the organic amine are an alicyclic amine and a guanidine derivative.

Specific examples of the phthalocyanine dyes represented by the above formulas (I) and (II) are represented by the following basic skeletons (I)
And the basic skeleton (II) and Table 1. Of course,
It goes without saying that the present invention is not limited to these.

[0024]

Embedded image Basic skeleton (I)

[0025]

Embedded image Basic skeleton (II)

[0026]

[Table 1]

The rosin acids in the present invention include, for example, natural rosins such as gum rosin, tall oil rosin and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α, β-ethylenically unsaturated Various modified rosins such as carboxylic acid-modified rosin; purified products of the above-mentioned natural rosin, purified rosins, etc. can be exemplified. The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin includes, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid And methacrylic acid.

Preferred as the rosin acid in the present invention is at least one rosin acid selected from the group consisting of natural rosin, modified rosin, a purified product of natural rosin, and a purified product of modified rosin. More preferably, it is at least one rosin acid selected from dehydroabietic acid, dihydroabietic acid, dihydropimaric acid, and derivatives thereof, and dehydroabietic acid is particularly preferable.

The natural rosin includes resin acids such as pimaric acid, sandaracohumic acid, parasudric acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydrobimalic acid, dihydroabietic acid, and tetrahydroabietic acid. , Usually a plurality of types. Dehydroabietic acid can be obtained by disproportionation or dehydrogenation of natural rosin, followed by purification.

The metal forming the rosin acid metal salt in the present invention includes, for example, alkali metals and alkaline earth metals. That is, examples of the metal rosinate in the present invention include alkali metal rosinate and alkaline earth metal rosinate.

Examples of the alkali metal salt of rosin acid include alkali metal salts of the above-mentioned rosin acid such as lithium salt, sodium salt, potassium salt, rubidium salt and cesium salt. As the alkali metal rosinate in the present invention, potassium rosinate and / or sodium rosinate are preferable in that they are excellent in the effect of improving the transparency of the crystalline resin. In particular, potassium rosinate and sodium rosinate are preferred. Are preferably used in combination. When the rosin acid potassium salt and the rosin acid sodium salt are used in combination, the ratio of each is arbitrary, but the rosin acid potassium salt is 1 mol% or more based on the total amount of the rosin acid potassium salt and the rosin acid sodium salt. , Preferably 5 to 95 mol%, and the rosin acid sodium salt is 9
They can be combined in a proportion of 9 mol% or less, preferably 95 to 5 mol%.

Examples of the alkaline earth metal salts of rosin acid include alkaline earth metal salts of the above-mentioned rosin acids such as beryllium salt, magnesium salt, calcium salt, strontium salt and barium salt. Preferred examples of the alkaline earth metal rosinate in the present invention include calcium rosinate and / or magnesium rosinate.

The alkali metal rosinate and the alkaline earth metal rosinate can be used alone, but the alkaline earth metal rosinate is preferably an alkali metal rosinate, particularly potassium rosinate. And / or rosin acid sodium salt has an excellent effect of promoting its function as a crystal nucleating agent.
It is preferable to use rosin acid alkali metal salts and rosin acid alkaline earth metal salts in combination. Particularly preferred in the present invention is a combination of potassium rosinate and calcium rosinate. When the alkali metal rosinate and the alkaline earth metal rosinate are used in combination, the molar ratio of the alkali metal rosinate to the alkaline earth metal rosinate is preferably in the range of 95: 5 to 5:95. It is a target.

The rosin acid metal salt is usually prepared by directly reacting rosin acid with a metal compound (such as an alkali metal compound or an alkaline earth metal compound) in the presence or absence of a solvent (direct method). ) Or a method in which rosin acid and a metal compound are reacted in the presence of water and / or an organic solvent to effect salt exchange (double decomposition method). In this case, the metal compound includes a simple substance of the alkali metal and / or the alkaline earth metal, a double salt of the alkali metal and / or the alkaline earth metal and another metal element, or
The alkali metal and / or alkaline earth metal,
Inorganic metal compounds such as sulfates, nitrates, silicates, carbonates, phosphates, hydroxides, sulfides, and oxides; organic alkali metal compounds and organic alkaline earth metal compounds.

For 1 part by weight of the phthalocyanine dye, rosin acid and / or a metal salt thereof is, for example, 1 to 10 parts.
00 parts by weight.

When the composition for coloring a polyolefin resin of the present invention is used for coloring a polyolefin resin, the compounding amount of rosin acid and / or its metal salt, and rosin acid and / or metal salt in the polyolefin coloring resin composition are used.
Alternatively, the amount of the metal salt is preferably about 0.1 to 5 parts by weight based on 100 parts by weight of the polyolefin resin. Improve the crystallization rate during molding of polyolefin resin and refine the crystals of the molded product,
In order to improve the mechanical properties and the optical properties, it is more preferable that the compounding amount of the rosin acid and / or the metal salt thereof is 0.5 parts by weight or more based on 100 parts by weight of the polyolefin resin. The amount of rosin acid and / or its metal salt is 5 to 100 parts by weight of the polyolefin resin.
Although the amount can be more than the weight part, the effect of improving the transparency corresponding to the compounding amount is hardly expected.

When a metal rosinate is used in the present invention, rosin acid may be added, if necessary, to assist in the uniform dispersion of the phthalocyanine dye and the metal rosinate in the polyolefin resin and to further improve the optical properties of the resin molded product. Can be used in combination. As the rosin acid in this case, the above-mentioned rosin acid can be used. The rosin acid used is preferably the same as or the same as the rosin acid forming the metal salt of rosin acid used in combination. In this case, the compounding amount of rosin acid can be about 0.1 to 10 parts by weight, preferably about 5 parts by weight, based on 100 parts by weight of the polyolefin resin.

The polyolefin resin in the present invention comprises
There is no particular limitation. Examples thereof include homopolymers of α-olefins such as ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and octene-1, copolymers thereof, and other polymers. Copolymers with copolymerizable unsaturated monomers (as copolymers,
Block copolymers, random copolymers, and graft copolymers can be mentioned. ) And the like.
Specific examples thereof include polyethylene resins such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer; propylene homopolymer And polypropylene-based resins such as propylene-ethylene block copolymer or random copolymer and propylene-ethylene-butene-1 copolymer; and polybutene-1 and poly-4-methylpentene-1. These polyolefin resins may be used alone or in combination of two or more. In the present invention, among these, it is preferable to use a polypropylene resin and / or a polyethylene resin.
Particularly preferred is a polypropylene resin. The polypropylene resin is not particularly limited, and a wide range of molecular weight can be used.

As the polyolefin resin, a resin containing a foaming agent in the resin itself, such as an acid-modified polyolefin modified with an unsaturated carboxylic acid or a derivative thereof or a foamed polypropylene, can also be used. Further, ethylene-α-olefin-based copolymer rubber, ethylene-α-olefin-non-conjugated diene-based compound copolymer (for example, EP
DM), ethylene-aromatic monovinyl compound-conjugated diene compound copolymer rubber, or rubbers such as hydrogenated products thereof may be contained in the polyolefin resin.

When the polyolefin resin coloring composition of the present invention is used for coloring a polyolefin resin, and in the polyolefin coloring resin composition, the phthalocyanine dye and the rosin acid are added to 100 parts by weight of the polyolefin resin. And / or the metal salt thereof (the total amount thereof) may be, for example, 0.0005 to 15% by weight. It is preferably 0.001 to 10% by weight, and more preferably 0.001 to 1% by weight in applications where transparency is emphasized. The amount of the coloring agent used in the case of the master batch can be, for example, 1 to 50% by weight based on the polyolefin resin. Preferably it is 2 to 40% by weight. In applications where importance is placed on transparency, the haze value of the polyolefin-based colored resin composition is preferably 85% or less.

The polyolefin-based colored resin composition of the present invention contains the polyolefin-based resin coloring composition. That is, it contains a polyolefin resin, a phthalocyanine dye, and rosin acid and / or a metal salt thereof. Various methods can be adopted for the preparation of the polyolefin-based colored resin composition.

Various additives can be added to the polyolefin colored resin composition according to the purpose.
Such additives include, for example, color assistants, dispersants, fillers, stabilizers, plasticizers, crystal nucleating agents, modifiers, foaming agents, ultraviolet absorbers, light stabilizers, antioxidants, antibacterial agents, Fungicides,
Examples include an antistatic agent, a flame retardant, an inorganic filler, and an elastomer for improving impact resistance.

Examples of UV absorbers or light stabilizers include
Examples include benzotriazole-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, benzoate-based compounds, oxalate-based compounds, oxalic anilide-based compounds, cyanoacrylate-based compounds, hindered amine-based compounds, and nickel complex salts.

Examples of the antioxidant include phenol compounds, phosphorus compounds, sulfur compounds, thioether compounds and the like.

Further, the polyolefin-based colored resin composition of the present invention may contain various fibrous reinforcing materials in appropriate amounts depending on applications and purposes. Examples of the fibrous reinforcing material include glass fiber, carbon fiber, and various organic fibers. Glass fibers are preferred for applications requiring transparency.

The master batch of the polyolefin colored resin composition of the present invention can be obtained by any method. For example, after mixing a polyolefin resin powder or pellet serving as a base of a master batch with a phthalocyanine dye, rosin acid and / or a metal salt thereof, and other necessary components using a mixer such as a tumbler or a super mixer, an extruder is used. It can be obtained by heating and melting with a batch kneader or a roll kneader to form pellets or coarse particles. Further, for example, after adding a phthalocyanine dye and rosin acid and / or a metal salt thereof to a polyolefin resin for a masterbatch still in a solution state after synthesis, the masterbatch can be obtained by removing the solvent.

The molding of the polyolefin-based colored resin composition of the present invention can be carried out by various procedures usually performed. For example, using a colored pellet, an extruder, an injection molding machine, a molding machine such as a roll meal, etc., can also be molded, and a polyolefin-based resin pellet or powder, a pulverized phthalocyanine-based dye, rosin acid and / or The metal salt and, if necessary, various additives are mixed in a suitable mixer, and the mixture can be formed using a processing machine.

According to the polyolefin-based colored resin composition of the present invention, a colored resin molded article having excellent transparency can be obtained. It can be used as a material.

The polyolefin-based colored resin composition of the present invention is mainly colored blue or green, but is mixed with another colorant capable of coloring the resin with good transparency to form a multicolored colorant. And can be used as For example, the polyolefin-based colored resin composition of the present invention using a blue phthalocyanine dye, a green-colored resin molded product is obtained by mixing with a yellow colorant, and a purple-colored resin molded product by mixing with a red colorant. Is obtained.

[0050]

According to the composition for coloring a polyolefin-based resin of the present invention, the polyolefin-based resin can be vividly colored with a dye and the bleeding of the colored molded product such as solvent transferability and resin transferability. Properties can be effectively prevented, and a molded article having high transparency can be obtained.

Further, according to the polyolefin-based colored resin composition of the present invention, it is possible to obtain a molded article having a high transparency by vividly coloring with a dye, effectively realizing the non-bleeding property of the molded article. It is possible.

[0052]

Next, the present invention will be described in detail with reference to examples, but it is needless to say that the present invention is not limited to these examples. In the following description, “parts by weight” is replaced by “parts”.
Abbreviated.

Production Example 1 Production of blue colorant (coloring composition) Phthalocyanine dye 4 (Compound Example 4) 50 g Metal salt of rosin acid (trade name: Pine Crystal KM-1300, manufactured by Arakawa Chemical Industries, Ltd.) 500 g

The above composition was placed in a stainless steel tumbler and mixed with stirring for 1 hour. 300 g of ethanol was added to the mixture and stirred for 1 hour with a stirrer. Next, the mixed liquid was put into a three-roll mill and kneaded at 100 ° C. for 30 minutes.
g of blue colorant were obtained.

Production Example 2 Production of Blue Colorant (Composition for Coloring) 500 g of metal rosinate (trade name: Pine Crystal KM-1300, manufactured by Arakawa Chemical Industry Co., Ltd.) was placed in 800 g of tetrahydrofuran (solvent) for 1 hour. It was dissolved by stirring. Then, the phthalocyanine dye 5
(Compound Example 5) 480 g of a blue colorant was obtained by spray-drying the dissolved solution of the rosinate in the spray-drying device while 150 g of the solution was blown up in the spray-drying device.

Production Example 3 Production of Master Batch (M / B) Phthalocyanine Dye 1 (Compound Example 1) 50 g Metal salt of rosin acid (trade name: Pine Crystal KM-1300, manufactured by Arakawa Chemical Industry Co., Ltd.) 500 g Polypropylene resin (Takafuku Chemical name: Tokuyama Polypro PN510T) 500g

The above composition was placed in a stainless steel tumbler and mixed with stirring for 1 hour. The mixture was subjected to a 22-screw extruder (trade name: PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) for 22 minutes.
Blue pellets were obtained by melt-kneading at 0 ° C.
The pellets were dried under reduced pressure at 120 ° C. for 24 hours to obtain a master batch having a coloring concentration of 4.8% by weight.

Production Example 4 Production of Masterbatch (M / B) Phthalocyanine Dye 6 (Compound Example 6) 50 g Metal salt of rosin acid (trade name: Pine Crystal KM-1300 manufactured by Arakawa Chemical Industries, Ltd.) 500 g Polyethylene resin (Nippon Polyolefin) Product name:
Jerex JM906A) 500g

The above composition was placed in a stainless steel tumbler and mixed with stirring for 1 hour. The mixture was added to a twin-screw extruder (trade name: PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) for 15 minutes.
Blue pellets were obtained by melt-kneading at 0 ° C.
The pellets were dried under reduced pressure at 120 ° C. for 24 hours to obtain a master batch having a coloring concentration of 4.8% by weight.

Comparative Production Example 1 Production of Masterbatch (M / B) Phthalocyanine Dye 1 (Compound Example 1) 50 g Polypropylene resin (trade name: Tokuyama Polypro PN510T, manufactured by Takafuku Chemical Co., Ltd.) 500 g

The above composition was placed in a stainless steel tumbler and mixed with stirring for 1 hour. The mixture was subjected to a 22-screw extruder (trade name: PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) for 22 minutes.
Blue pellets were obtained by melt-kneading at 0 ° C.
The pellets were dried under reduced pressure at 120 ° C. for 24 hours to obtain a master batch having a color density of 9.1% by weight.

Comparative Production Example 2 Production of Masterbatch (M / B) 50 g of phthalocyanine pigment (trade name: KET BLUE111, manufactured by Dainippon Ink and Chemicals, Inc.) Metal salt of rosin acid (trade name: Pine Crystal KM-, manufactured by Arakawa Chemical Co., Ltd.) 1300) 500 g 500 g of polypropylene resin (trade name: TOKUYAMA POLYPRO PN510T manufactured by Takafuku Chemical Co., Ltd.)

The above composition was placed in a stainless steel tumbler and mixed with stirring for 1 hour. The mixture was heated at 220 ° C. using a twin-screw extruder (trade name: PCM-30, manufactured by Ikegai Iron Works).
To obtain blue pellets. The pellets were dried under reduced pressure at 120 ° C. for 24 hours to obtain a master batch having a coloring concentration of 4.8% by weight.

Examples 1 to 5 and Comparative Examples 1 and 2
The present invention relates to a polyolefin-based colored resin composition.

[0065]Example 1  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
(Polypropylene PN510T) 500 g and blue coloration of Production Example 1
Add 10g of the agent to a stainless steel tumbler for 1 hour
Stirred well.

This mixture was melt-mixed at 220 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo) to produce colored pellets by a conventional method, and the pellets were vacuumed at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 240 to 260 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.). A blue molded plate [48 × 86 × 3 (mm)] was obtained.

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0068]Example 2  Polyethylene resin (manufactured by Nippon Polyolefin Co., Ltd.)
JELEX JM906A) 500 g and blue color of Production Example 2
Put 10g of coloring agent in stainless steel tumbler,
Stirred well.

This mixture was melted and mixed at 150 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.), and colored pellets were prepared by a conventional method. These pellets were vacuumed at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 170 to 180 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.). A blue molded plate [48 × 86 × 3 (mm)] was obtained.

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0071]Example 3  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
Polypropylene PN510T) 1000 g and the blue color of Production Example 3
8g of Star Batch (M / B) and stainless steel tumbler
And stirred well for 1 hour.

The mixture was melted and mixed at 220 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.) to form colored pellets by a conventional method, and the pellets were vacuumed at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 240 to 260 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.). A blue molded plate [48 × 86 × 3 (mm)] was obtained.

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0074]Example 4  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
Polypropylene PN510T) 1000g and polyethylene resin
(Mitsui Chemicals product name: HI-WAX420P) 8g
And 3.5 g of the blue masterbatch (M / B) of Production Example 4
Into a stainless steel tumbler and stir well for one hour.
Was.

This mixture was melted and mixed at 220 ° C. using a vent type extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.), and colored pellets were prepared by a conventional method. The pellets were vacuumed at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 240 to 260 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.). A blue molded plate [48 × 86 × 3 (mm)] was obtained.

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0077]Example 5  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
Polypropylene PN510T) 1000 g Polyethylene resin (trade name: HI-WA, manufactured by Mitsui Chemicals, Inc.)
X420P) 8 g Phthalocyanine Dye 1 (Compound Example 1) 0.5 g Rosinate (Arakawa Chemical Industries, Ltd., trade name: Pine Criss)
Tal KM-1300) 5g

The above composition was placed in a stainless steel tumbler and stirred well for 1 hour. Then, using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.), 240 to 2
When a test plate was prepared at 60 ° C. by a normal method,
A blue molded plate [48 × 86 × 3 (mm)] with good compatibility between the resin and the dye and excellent transparency was obtained.

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0080]Comparative Example 1  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
Polypropylene PN510T) 1000 g and blue of Comparative Production Example 1
8g of color master batch (M / B) with stainless steel
It was put in a blur and stirred well for 1 hour.

This mixture was melted and mixed at 220 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo) to prepare colored pellets by a conventional method, and these pellets were vacuum-dried at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 240 to 260 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.). A blue molded plate with good dispersibility of resin and dye [ 48 × 86 × 3 (mm)].

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0083]Comparative Example 2  Polypropylene resin (manufactured by Takafuku Chemical Co., Ltd .: Tokuyama
Polypropylene PN510T) 500 g and blue of Comparative Production Example 2
10g of master batch (M / B) and stainless steel tank
It was put in a blur and stirred well for 1 hour.

This mixture was melted and mixed at 220 ° C. using a vented extruder (trade name: E30SV, manufactured by Enpla Sangyo Co., Ltd.), and colored pellets were prepared by a conventional method. These pellets were vacuumed at 120 ° C. for 6 hours. Let dry. After drying, a test plate was prepared by an ordinary method at 240 to 260 ° C. using an injection molding machine (trade name: KM50-C, manufactured by Kawaguchi Iron & Steel Co., Ltd.).
6 × 3 (mm)].

Table 2 shows the results of measurement and evaluation of the physical properties of the test piece.

[0086]Physical property tests and methods of measurement and evaluation  (1) Transparency JIS K using test pieces obtained by an injection molding machine
The transparency (haze value) according to 6714 was measured. F
If the noise value is 85% or less, it is determined that the transparency is high. Transparent
The lightness evaluation is as follows. ◎: Excellent ○: Good ×: Poor

(2) Bleedability A test piece obtained by an injection molding machine was superimposed on a predetermined test piece, and about 200 g (1.96 g) in the direction of superposition.
After applying a pressure of N) / cm ² and leaving at 80 ° C. for 48 hours, the degree of coloring of a predetermined test piece was observed. The evaluation is as follows. ○: No bleed ×: With bleed

The predetermined test pieces are polypropylene resin (PP), low density polyethylene resin (LDPE),
High-density polyethylene resin (HDPE) and polyethylene terephthalate resin (PET) are each colored with 0.1% titanium oxide.

(3) Dispersibility In the test piece obtained by the injection molding machine, it was visually confirmed whether the colorant was uniformly dispersed. The evaluation is as follows. ○: dispersed ×: not dispersed

[0090]

[Table 2]

Claims (11)

[Claims] 1. A polyolefin resin coloring composition comprising a phthalocyanine dye and rosin acid and / or a metal salt thereof. 2. The composition for coloring a polyolefin resin according to claim 1, which substantially comprises a phthalocyanine dye and rosin acid and / or a metal salt thereof. 3. The composition for coloring a polyolefin resin according to claim 1, wherein the phthalocyanine dye is a compound represented by the following formula (I). Embedded image ... (I) [In the formula (I), CuPc represents a copper phthalocyanine residue, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, Represents an alkyl group, an aralkyl group, or an aryl group, o, p, and q each represent an integer of 0 to 4, and o + p + q represents 1 to 4; ] 4. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶
The polyolefin resin coloring composition according to claim 3, wherein each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 5. The composition for coloring a polyolefin resin according to claim 1, wherein the phthalocyanine dye is a compound represented by the following formula (II). Embedded image ... (II) [In formula (II), CuPc represents a copper phthalocyanine residue, m represents an integer of 1 to 4, ^{An +} represents a cation of an organic amine, n represents its ionic valence, and k represents Indicates m / n. ] 6. The composition for coloring a polyolefin resin according to claim 5, wherein the organic amine is an alicyclic amine or a guanidine derivative. 7. The composition for coloring a polyolefin resin according to claim 1, wherein rosin acid and / or a metal salt thereof is used in an amount of 1 to 1000 parts by weight based on 1 part by weight of the phthalocyanine dye. 8. A polyolefin resin, and a polyolefin resin.
A polyolefin-based colored resin composition comprising the polyolefin-based resin coloring composition according to any one of the above. 9. The polyolefin-based colored resin composition according to claim 8, wherein the polyolefin-based resin is a polypropylene resin and / or a polyethylene resin. 10. The polyolefin-based colored resin according to claim 8, wherein the total amount of the phthalocyanine-based dye and rosin acid and / or its metal salt is 0.0005 to 15 parts by weight based on 100 parts by weight of the polyolefin-based resin. Composition. 11. The method according to claim 8, wherein the haze value is 85% or less.
11. The polyolefin-based colored resin composition according to 9 or 10.