JP2022177798A - Polypropylene colored resin composition and method for producing the same - Google Patents

Abstract

To provide a polypropylene colored resin composition that excels in color development, washing resistance, and sublimation resistance and can be stably supplied.SOLUTION: A polypropylene colored resin composition contains a polypropylene resin and a colorant, the colorant including a compound of a predetermined structure.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a polypropylene colored resin composition and a method for producing the same.

One of general-purpose resins is polypropylene (also abbreviated as PP) resin. The characteristics of polypropylene (PP) resin are lighter than water (specific gravity 0.92), quick drying, excellent heat resistance, chemical resistance, antistatic property, abrasion resistance, bending resistance, etc. Used in various fields. For example, textile products such as nonwoven fabrics are inexpensive, have relatively good mechanical properties and spinnability, and are excellent in workability. On the other hand, although dyeability or coloring affinity is required, the industrial coloring of polypropylene can be done by adding organic or inorganic pigments in the spinning process for original dyeing, or by kneading organic pigments directly into resin. was the mainstream manufacturing method. There are still many problems with this method, such as vividness, richness of colors, printing processing, thick threads, and rough texture. Therefore, in the fields of apparel clothing and sports clothing, it has hardly been used. In recent years, a dyeing method using an anthraquinone dye has been reported as a method for dyeing polypropylene resin (fiber) (see Patent Documents 1 and 2).

WO 18/123811 WO 19/146174

The anthranoquine dyes described in the above-mentioned documents have the problem of being highly cohesive and insufficient in vividness of color development and washing resistance. In addition, there is a problem that the dye sublimates due to the temperature rise in the ship during sea transportation, and the dye is transferred to an adjacent pale color. Furthermore, in recent years, concerns have been pointed out in terms of stable supply due to factors such as the availability of raw materials. As a result, polypropylene resin can be dyed with high color development (brightness) in many fields, especially in the apparel and sportswear fields where design and functionality are required. There is a strong need to develop dyes and polypropylene colored resin compositions.

The present invention relates to a polypropylene colored resin composition comprising a polypropylene resin and a coloring agent, wherein the coloring agent contains at least one compound represented by the following general formulas (1) to (4).

［一般式（１）中、
Ｒ₁およびＲ₂は、各々独立して、炭素数１～１２のアルキル基を表し、
Ｒ₃は、炭素数１～４のアルキル基、置換基を有するフェニル基、または無置換のフェニル基を表し、
Ｒ₄は、炭素数１～４のアルキル基または無置換のフェニル基を表し、
Ｒ₅は、炭素数１～１２のアルキル基、無置換のフェニル基、ベンジル基、ジアルキルアミノ基またはジフェニルアミノ基を表し、
Ａは炭素原子または窒素原子を表し、炭素原子である場合には、該炭素原子に水素原子が１つ結合する。］

[In general formula (1),
R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms,
R ₃ represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group;
R ₄ represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group;
R ₅ represents an alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, a benzyl group, a dialkylamino group or a diphenylamino group;
A represents a carbon atom or a nitrogen atom, and when it is a carbon atom, one hydrogen atom is bonded to the carbon atom. ]

［一般式（２）中、
Ｒ₆及びＲ₇は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₈は、炭素数１～４の直鎖状のアルキル基または炭素数１～４の分岐状のアルキル基、置換してもよいフェニル基、無置換のフェニル基を表し、
Ｒ₉は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₁₀は、水素原子、アルキル基、アリール基、ベンジル基、－ＮＲ₁₁Ｒ₁₂を表し、
Ｒ₁₁及びＲ₁₂は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₁₁及びＲ₁₂が互いに結合して形成された環を表す。］

[In general formula (2),
R ₆ and R ₇ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₈ represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, or an unsubstituted phenyl group;
R ₉ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₁ R ₁₂ ,
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₁ and R ₁₂ with each other. ]

［一般式（３）中、
Ｂはカルボニル基またはスルホニル基を表し、
Ｒ₁₃及びＲ₁₄は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₁₅は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₁₆は、水素原子、アルキル基、アリール基、ベンジル基、－ＮＲ₁₇Ｒ₁₈を表し、
Ｒ₁₇及びＲ₁₈は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₁₇及びＲ₁₈が互いに結合して形成された環を表す。］

[In general formula (3),
B represents a carbonyl group or a sulfonyl group,
R ₁₃ and R ₁₄ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₁₅ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₆ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₇ R ₁₈ ,
R ₁₇ and R ₁₈ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₇ and R ₁₈ with each other. ]

［一般式（４）中、
Ｒ₁₉及びＲ₂₀は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₂₁は、炭素数１～４の直鎖状のアルキル基を表す。
Ｒ₂₂は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₂₃及びＲ₂₄は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₂₃及びＲ₂₄が互いに結合して形成された環を表す。］
また、本発明は、上記構成のポリプロピレン着色樹脂組成物の製造方法であって、
媒体として超臨界二酸化炭素を用い、該媒体中でポリプロピレン樹脂を着色剤で着色することを特徴とするポリプロピレン着色樹脂組成物の製造方法に関する。

[In general formula (4),
R ₁₉ and R ₂₀ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₂₁ represents a linear alkyl group having 1 to 4 carbon atoms.
R ₂₂ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₂₃ and R ₂₄ with each other. ]
Further, the present invention is a method for producing a polypropylene colored resin composition having the above configuration,
The present invention relates to a method for producing a colored polypropylene resin composition, which comprises using supercritical carbon dioxide as a medium and coloring a polypropylene resin with a coloring agent in the medium.

According to the present invention, it is possible to provide a colored polypropylene resin composition which is excellent in high color development, washing resistance, and sublimation resistance, and which can be stably supplied.
In addition, according to the present invention, a polypropylene resin that has high color development, excellent washing resistance, and excellent sublimation resistance and can be stably supplied is characterized by highly dispersing a coloring agent in a polypropylene resin using supercritical carbon dioxide as a medium. A method for producing a colored resin composition can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to these. In the present invention, the description of "○○ to XX" representing a numerical range such as the number of carbon atoms means a numerical range including the lower limit and the upper limit, which are endpoints, unless otherwise specified.

The present inventors have made intensive studies to solve the above problems, and found that at least one compound containing a polypropylene resin and a colorant, wherein the colorant is represented by the following general formulas (1) to (4): By using a polypropylene colored resin composition characterized by comprising, it is possible to provide a polypropylene colored resin composition that can be stably supplied with excellent color development, washing resistance, and sublimation resistance.

［一般式（１）中、
Ｒ₁およびＲ₂は、各々独立して、炭素数１～１２のアルキル基を表し、
Ｒ₃は、炭素数１～４のアルキル基、置換基を有するフェニル基、または無置換のフェニル基を表し、
Ｒ₄は、炭素数１～４のアルキル基または無置換のフェニル基を表し、
Ｒ₅は、炭素数１～１２のアルキル基、無置換のフェニル基、ベンジル基、ジアルキルアミノ基またはジフェニルアミノ基を表し、
Ａは炭素原子または窒素原子を表し、炭素原子である場合には、該炭素原子に水素原子が１つ結合する。］

[In general formula (1),
R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms,
R ₃ represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group;
R ₄ represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group;
R ₅ represents an alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, a benzyl group, a dialkylamino group or a diphenylamino group;
A represents a carbon atom or a nitrogen atom, and when it is a carbon atom, one hydrogen atom is bonded to the carbon atom. ]

［一般式（２）中、
Ｒ₆及びＲ₇は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₈は、炭素数１～４の直鎖状のアルキル基または炭素数１～４の分岐状のアルキル基、置換してもよいフェニル基、無置換のフェニル基を表し、
Ｒ₉は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₁₀は、水素原子、アルキル基、アリール基、ベンジル基、－ＮＲ₁₁Ｒ₁₂を表し、
Ｒ₁₁及びＲ₁₂は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₁₁及びＲ₁₂が互いに結合して形成された環を表す。］

[In general formula (2),
R ₆ and R ₇ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₈ represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, or an unsubstituted phenyl group;
R ₉ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₁ R ₁₂ ,
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₁ and R ₁₂ with each other. ]

［一般式（３）中、
Ｂはカルボニル基またはスルホニル基を表し、
Ｒ₁₃及びＲ₁₄は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₁₅は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₁₆は、水素原子、アルキル基、アリール基、ベンジル基、－ＮＲ₁₇Ｒ₁₈を表し、
Ｒ₁₇及びＲ₁₈は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₁₇及びＲ₁₈が互いに結合して形成された環を表す。］

[In general formula (3),
B represents a carbonyl group or a sulfonyl group,
R ₁₃ and R ₁₄ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₁₅ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₆ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₇ R ₁₈ ,
R ₁₇ and R ₁₈ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₇ and R ₁₈ with each other. ]

［一般式（４）中、
Ｒ₁₉及びＲ₂₀は、各々独立して、炭素数１～１２の直鎖状のアルキル基、炭素数３～１２の分岐状のアルキル基または炭素数３～１２の環状のアルキル基を表し、
Ｒ₂₁は、炭素数１～４の直鎖状のアルキル基を表す。
Ｒ₂₂は、炭素数１～１２の直鎖状のアルキル基または炭素数１～１２の分岐状のアルキル基を表し、
Ｒ₂₃及びＲ₂₄は、各々独立して水素原子、無置換のアルキル基、置換基を有するアルキル基、無置換のアリール基、置換基を有するアリール基、無置換のアシル基、または置換基を有するアシル基を表し、Ｒ₂₃及びＲ₂₄が互いに結合して形成された環を表す。］

[In general formula (4),
R ₁₉ and R ₂₀ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₂₁ represents a linear alkyl group having 1 to 4 carbon atoms.
R ₂₂ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₂₃ and R ₂₄ with each other. ]

The polypropylene colored resin composition of the present invention can be produced by dissolving the coloring agent in carbon dioxide by bringing it into a supercritical carbon dioxide state and dispersing the coloring agent uniformly in the polypropylene resin.

The staining mechanism at this time is considered as follows. A pressure vessel containing carbon dioxide, a colorant, and polypropylene fibers is brought to a supercritical carbon dioxide state at high temperature and high pressure. In the supercritical carbon dioxide state,
(1) The coloring agent is solvated (dissolved) with supercritical carbon dioxide.
(2) Heating increases the free volume of the polypropylene polymer.
(3) The colorant solvated with supercritical carbon dioxide diffuses into the gaps between the amorphous portions of the polypropylene polymer.
(4) The coloring agent is adsorbed to the polymer that constitutes the fiber.
(5) By cooling and releasing the pressure, the gaps between the polymer chains are restored and the colorant is fixed to the fibers.
(6) When washed with acetone or the like, if the fibers and the coloring agent are not compatible, the fibers will be decolored.
steps. Here, we believe that the solvation (solubility) of the supercritical carbon dioxide and the colorant and the compatibility of the PP fiber and the colorant are key points.

The compounds represented by the general formulas (1) to (4) of the present invention are characterized by being readily soluble in aliphatic hydrocarbon solvents (hexane, heptane, etc.). Dissolution of compounds in supercritical carbon dioxide is very similar to aliphatic hydrocarbon solvents. Therefore, the supercritical carbon dioxide state allows the dye to dissolve in the carbon dioxide and the coloring agent to be uniformly dispersed in the polypropylene resin. On the other hand, since the compounds represented by the general formulas (1) to (4) of the present invention have alkyl groups, the compatibility with PP fibers is high, resulting in high color development, washing resistance, and sublimation resistance. It is presumed that it will be a polypropylene colored resin composition that can be supplied stably.

On the other hand, conventionally known anthraquinone-based compounds are a group of compounds that are difficult to dissolve in aliphatic hydrocarbon-based solvents and therefore difficult to dissolve in supercritical carbon dioxide.

<Compound Represented by Formula (1)>
First, the compound represented by the general formula (1) will be described.

In general formula (1), the alkyl group having 1 to 12 carbon atoms in R ₁ and R ₂ is not particularly limited, and may be any of linear, branched and cyclic alkyl groups. good. Specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-heptyl group, n-octyl group , n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2-ethylhexyl group and cyclohexyl group.

Among these, a branched alkyl group having 6 to 12 carbon atoms is preferred, and a 2-ethylhexyl group is particularly preferred, from the viewpoint of excellent color development, washing resistance, and sublimation resistance and stable supply.

Regarding the cyclic alkyl group, for example, in the case of "a cyclic alkyl group having 8 carbon atoms", a cyclic structure having 8 carbon atoms may be used, and an alkyl group having 2 carbon atoms may be added to a cyclic structure having 6 carbon atoms. may be a structure in which is bound.

In general formula (1), the alkyl group having 1 to 4 carbon atoms in R ₃ is not particularly limited, and may be linear or branched. Specifically, primary alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group; secondary alkyl groups such as iso-propyl group and sec-butyl group; higher alkyl groups. Among these, a tert-butyl group is preferred from the viewpoint of high color development, washing resistance, and sublimation resistance and stable supply.

In general formula (1), when R ₃ is a phenyl group having a substituent, it preferably has 6 to 20 carbon atoms including the substituent. Examples of substituents include alkyl groups and alkoxy groups. Also, the number of substituents may be one or plural. Specifically, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, pentamethylphenyl group, 4 -methoxyphenyl group, 2,6-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group and the like. Among these, a phenyl group and a 4-methylphenyl group are preferable from the viewpoint of excellent color development, washing resistance, and sublimation resistance and stable supply. It is also preferred that R ₃ is an unsubstituted phenyl group.

In general formula (1), the alkyl group having 1 to 4 carbon atoms in R ₄ is not particularly limited, and may be linear or branched. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group and tert-butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of excellent high color development, washing resistance, and sublimation resistance and stable supply.

In general formula (1), the alkyl group having 1 to 12 carbon atoms in R ₅ is not particularly limited, and may be linear, branched or cyclic. Specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group , cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, 2-ethylpropyl group and 2-ethylhexyl group. A sec-butyl group and a neopentyl group are preferable from the viewpoint of excellent color development, washing resistance, and sublimation resistance, and stable supply.

In general formula (1), the dialkylamino group for R ₅ is not particularly limited, but examples thereof include dimethylamino, diethylamino, dipropylamino and dibutylamino groups. A dimethylamino group and a diethylamino group are preferable from the viewpoint of excellent color development, washing resistance, and sublimation resistance and stable supply.

Next, the compound of the present invention can be synthesized by referring to the known method described in the patent document (JP-A-08-245896). Specific examples are shown in (1-1) to (1-19) below, but the present invention is not limited to these.

The compounds represented by the general formula (1) may be used singly or in combination of two or more in order to adjust the color tone and the like depending on the application.

Among these, compounds (1-1), (1-2), (1-3), (1-5), (1-16), and (1-18) exhibit high color development, wash resistance, And excellent in sublimation resistance, because it is possible to obtain a polypropylene colored resin composition that can be stably supplied, it is preferable.

<Compound Represented by Formula (2)>
Next, the compound represented by the general formula (2) will be described.

In general formula (2), for R ₆ and R ₇ , as a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a cyclic alkyl group having 3 to 12 carbon atoms, is not particularly limited, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2-ethylhexyl group and cyclohexyl group.

Among these, an alkyl group having 8 carbon atoms is preferable because it is excellent in high color development, washing resistance, and sublimation resistance and can be stably supplied, and particularly a branched alkyl group such as 2-ethylhexyl group. is more preferable.

In the general formula (2), the linear alkyl group having 1 to 4 carbon atoms or the branched alkyl group having 1 to 4 carbon atoms in R ₈ is not particularly limited, but specifically , methyl group, ethyl group, n-propyl group, primary alkyl group such as n-butyl group; iso-propyl group, secondary alkyl group such as sec-butyl group; tertiary alkyl group such as tert-butyl group mentioned. Among these, a tert-butyl group is preferred from the viewpoint of high color development, washing resistance, and sublimation resistance and stable supply.

In general formula (2), the substituted phenyl group and unsubstituted phenyl group for R ₈ are not particularly limited, but include substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms. . Examples of substituents include alkyl groups and alkoxy groups. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Also, the number of substituents may be one or plural. Specific examples of substituted or unsubstituted phenyl groups having 6 to 20 carbon atoms include phenyl group, 4-methylphenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethyl phenyl group, 2,4,6-trimethylphenyl group, pentamethylphenyl group, 4-methoxyphenyl group, 2,6-dimethoxyphenyl group, 2,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 2, 4,6-tridimethoxyphenyl group, naphthyl group and the like. Among these, unsubstituted phenyl group and 4-methylphenyl group are preferable, and unsubstituted phenyl group is preferable from the viewpoint of excellent color development, washing resistance, and sublimation resistance and stable supply. is more preferable.

In general formula (2), the linear or branched alkyl group having 1 to 12 carbon atoms in R ₉ is not particularly limited, but specific examples include methyl group, ethyl group, n- propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-methylbutyl group, 2,3,3-trimethylbutyl group, octyl group and the like. Among these, from the viewpoint of excellent high color development, washing resistance, and sublimation resistance and stable supply, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, 2,3,3 A -trimethylbutyl group is preferred, and a methyl group is particularly preferred.

In general formula (2), the alkyl group for R ₁₀ is not particularly limited, but examples thereof include a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 1 to 12 carbon atoms. be done. Specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-methylbutyl group, 2,3,3-trimethylbutyl group, octyl group and the like. mentioned. Among these, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms is considered to be excellent in high color development, washing resistance, and sublimation resistance and to be stably supplied. are preferred, and straight-chain alkyl groups such as methyl, ethyl, propyl and n-butyl are particularly preferred.

In general formula (2), when R ₁₀ represents —NR ₁₁ R ₁₂ , R ₁₁ and R ₁₂ are an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, or a substituted aryl group, an unsubstituted acyl group, or an acyl group having a substituent.

The alkyl groups for R ₁₁ and R ₁₂ are not particularly limited, but include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specific examples of unsubstituted alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, dodecyl group and nonadecyl. cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, 2-ethylhexyl, linear, branched or cyclic alkyl groups. Further, examples of the substituent in the substituted alkyl group include a cyclohexenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.

The aryl group for R ₁₁ and R ₁₂ is not particularly limited, but includes a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Substituents include alkyl groups and alkoxy groups. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Also, the number of substituents may be one or plural. The substituted or unsubstituted aryl group having 6 to 10 carbon atoms is specifically a phenyl group and a 4-methylphenyl group from the viewpoint of high color development, excellent washing resistance, and excellent sublimation resistance and stable supply. , 4-methoxyphenyl group and the like are preferred.

The acyl groups for R ₁₁ and R ₁₂ are not particularly limited, but include substituted or unsubstituted acyl groups having 1 to 30 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specifically, formyl group; substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms such as acetyl group, propionyl group and pivaloyl group; substituted or unsubstituted alkylcarbonyl group having 7 to 30 carbon atoms such as benzoyl group and naphthoyl group. arylcarbonyl group; 2-pyridylcarbonyl group, heterocyclic carbonyl group such as 2-furylcarbonyl group, and the like. Among these, the acetyl group, the pivaloyl group or the benzoyl group is preferable, and the acetyl group or the benzoyl group is more preferable, from the viewpoint of excellent high color development, washing resistance and sublimation resistance and stable supply. preferable.

The ring formed by combining R ₁₁ and R ₁₂ is not particularly limited, but represents pyridine ring, piperazine ring, morpholine ring and phthalimide ring.

Next, a method for producing the compound represented by formula (2) according to the present invention will be described. The compound of the present invention can be synthesized with reference to the known method described in WO2014/034094.

The compound represented by the general formula (2) has cis-trans isomers, but both are within the scope of the present invention, and the compound represented by the general formula (2) is a mixture thereof. good too.

Preferred examples of compounds of the present invention represented by general formula (2) are shown in (2-1) to (2-14) below, but the present invention is not limited thereto.

The compounds represented by the general formula (2) may be used singly or in combination of two or more in order to adjust the color tone and the like depending on the application.

Among these, compounds (2-1), (2-2), (2-3), (2-4), (2-7), and (2-10) exhibit high color development, wash resistance, And excellent in sublimation resistance, because it is possible to obtain a polypropylene colored resin composition that can be stably supplied, it is preferable.

<Compound Represented by Formula (3)>
Next, the compound represented by the general formula (3) will be described.

In general formula (3), as R ₁₃ and R ₁₄ , linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 3 to 12 carbon atoms, is not particularly limited, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2-ethylhexyl group and cyclohexyl group.

Among these, an alkyl group having 8 carbon atoms is preferable because it is excellent in high color development, washing resistance, and sublimation resistance and can be stably supplied, and particularly a branched alkyl group such as 2-ethylhexyl group. is more preferable.

In general formula (3), the linear alkyl group having 1 to 12 carbon atoms or the branched alkyl group having 1 to 12 carbon atoms in R ₁₅ is not particularly limited, but specifically , methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-methylbutyl group, 2,3,3-trimethylbutyl group, octyl group and the like. Among these, from the viewpoint of excellent high color development, washing resistance, and sublimation resistance and stable supply, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, 2,3,3 A -trimethylbutyl group is preferred, and a methyl group is particularly preferred.

In the general formula (3), the alkyl group for R ₁₆ is not particularly limited, but examples thereof include a linear alkyl group having 1 to 12 carbon atoms and a branched alkyl group having 1 to 12 carbon atoms. be done. Specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-methylbutyl group, 2,3,3-trimethylbutyl group, octyl group and the like. mentioned. Among these, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms is considered to be excellent in high color development, washing resistance, and sublimation resistance and to be stably supplied. are preferred, and straight-chain alkyl groups such as methyl, ethyl, propyl and n-butyl are particularly preferred.

In general formula (3), when R ₁₆ represents —NR ₁₇ R ₁₈ , R ₁₇ and R ₁₈ are an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, or a substituted aryl group, an unsubstituted acyl group, or an acyl group having a substituent.

The alkyl groups for R ₁₇ and R ₁₈ are not particularly limited, but include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specific examples of unsubstituted alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, dodecyl group and nonadecyl. cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, 2-ethylhexyl, linear, branched or cyclic alkyl groups. Further, examples of the substituent in the substituted alkyl group include a cyclohexenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.

The aryl group for R ₁₇ and R ₁₈ is not particularly limited, but includes a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Substituents include alkyl groups and alkoxy groups. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Also, the number of substituents may be one or plural. The substituted or unsubstituted aryl group having 6 to 10 carbon atoms is specifically a phenyl group and a 4-methylphenyl group from the viewpoint of high color development, excellent washing resistance, and excellent sublimation resistance and stable supply. , 4-methoxyphenyl group and the like are preferred.

The acyl group for R ₁₇ and R ₁₈ is not particularly limited, but includes a substituted or unsubstituted acyl group having 1 to 30 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specifically, formyl group; substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms such as acetyl group, propionyl group and pivaloyl group; substituted or unsubstituted alkylcarbonyl group having 7 to 30 carbon atoms such as benzoyl group and naphthoyl group. arylcarbonyl group; 2-pyridylcarbonyl group, heterocyclic carbonyl group such as 2-furylcarbonyl group, and the like. Among these, the acetyl group, the pivaloyl group or the benzoyl group is preferable, and the acetyl group or the benzoyl group is more preferable, from the viewpoint of excellent high color development, washing resistance and sublimation resistance and stable supply. preferable.

The ring formed by combining R ₁₇ and R ₁₈ is not particularly limited, but represents pyridine ring, piperazine ring, morpholine ring and phthalimide ring.

The compound represented by general formula (3) according to the present invention can be synthesized with reference to the known method described in WO08/114886. This compound has azo-hydrazo tautomers, and all of them are within the scope of the present invention, and mixtures thereof may also be used. Examples of preferred compounds are shown in the following (3-1) to (3-15) in terms of azo forms, but the present invention is not limited to these.

The compounds represented by the general formula (3) may be used singly or in combination of two or more in order to adjust the color tone and the like depending on the application.

Among these, compounds (3-1), (3-2), (3-5), (3-6), (3-10), and (3-14) exhibit high color development, wash resistance, And excellent in sublimation resistance, because it is possible to obtain a polypropylene colored resin composition that can be stably supplied, it is preferable.

<Compound Represented by Formula (4)>
Next, the compound represented by the general formula (4) will be described.

In general formula (4), linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms or cyclic alkyl groups having 3 to 12 carbon atoms in R ₁₉ and R ₂₀ are , but not limited to, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, n- Examples include heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 2-ethylhexyl group and cyclohexyl group.

Among these, an alkyl group having 4 or less carbon atoms is preferable because it has high color development, excellent washing resistance, and excellent sublimation resistance and can be stably supplied, and is methyl, ethyl, n-propyl, and n-butyl. more preferably a group.

In the general formula (4), the straight-chain alkyl group having 1 to 4 carbon atoms in R ₂₁ is not particularly limited, but a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group and the like. Among these, a methyl group is preferred.

In general formula (4), the straight-chain alkyl group having 1 to 12 carbon atoms or the branched alkyl group having 1 to 12 carbon atoms in R ₂₂ is not particularly limited, but specifically , methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, 2-methylbutyl group, 2,3,3-trimethylbutyl group, octyl group and the like. Among these, from the viewpoint of excellent high color development, washing resistance, and sublimation resistance and stable supply, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, 2,3,3 A -trimethylbutyl group is preferred, and a methyl group is particularly preferred.

In general formula (4), the alkyl group for R ₂₃ and R ₂₄ is not particularly limited, but includes a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specific examples of unsubstituted alkyl groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, octyl group, dodecyl group and nonadecyl. cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, 2-ethylhexyl, linear, branched or cyclic alkyl groups. Further, examples of the substituent in the substituted alkyl group include a cyclohexenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.

Aryl groups for R ₂₃ and R ₂₄ are not particularly limited, but include substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. Substituents include alkyl groups and alkoxy groups. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Also, the number of substituents may be one or plural. The substituted or unsubstituted aryl group having 6 to 10 carbon atoms is specifically a phenyl group and a 4-methylphenyl group from the viewpoint of high color development, excellent washing resistance, and excellent sublimation resistance and stable supply. , 4-methoxyphenyl group and the like are preferred.

The acyl group for R ₂₃ and R ₂₄ is not particularly limited, but includes a substituted or unsubstituted acyl group having 1 to 30 carbon atoms. In addition, when it has a substituent, the said carbon number represents the number including the carbon number of this substituent. Specifically, formyl group; substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms such as acetyl group, propionyl group and pivaloyl group; substituted or unsubstituted alkylcarbonyl group having 7 to 30 carbon atoms such as benzoyl group and naphthoyl group. arylcarbonyl group; 2-pyridylcarbonyl group, heterocyclic carbonyl group such as 2-furylcarbonyl group, and the like. Among these, the acetyl group, the pivaloyl group or the benzoyl group is preferable, and the acetyl group or the benzoyl group is more preferable, from the viewpoint of excellent high color development, washing resistance and sublimation resistance and stable supply. preferable.

The ring formed by combining R ₂₃ and R ₂₄ is not particularly limited, but represents pyridine ring, piperazine ring, morpholine ring and phthalimide ring.

Compounds (4-1) to (4-7) are shown below as preferred examples, but are not limited to the following compounds.

The compounds represented by the general formula (4) may be used singly or in combination of two or more in order to adjust the color tone and the like according to the application.

Among these, compounds (4-1), (4-2), and (4-3) are excellent in high color development, washing resistance, and sublimation resistance, and obtain a polypropylene colored resin composition that can be stably supplied. preferred because

<Polypropylene resin>
Next, the polypropylene resin according to the present invention will be described.

The polypropylene resin used in the present invention is not particularly limited, and any type of known polypropylene resin may be used.

The shape of the polypropylene resin of the present invention is not particularly limited, and is preferably fibrous, particulate, filamentous, or the like.

It may also be in the form of a processed product. For example, cloth-like fibers (woven fabrics, knitted fabrics, non-woven fabrics, felt, tufts, etc.), thread-like fibers (filament yarns, spun yarns, slit yarns, split yarns, etc.), cotton-like fibers, string-like fibers, etc. are suitable. . In addition, commercially available polypropylene fibers can also be used. In addition, the polypropylene fiber can be suitably used by blending and/or blending other fibers such as polyester.

Specifically, construction materials such as woven fabrics, knitted fabrics, non-woven fabrics, clothing, underwear, socks, gloves, zippers, hats, sports clothing, seat sheets, vehicle interior materials, shoes, curtains, carpets, mats, sofas, and wall coverings. etc. can be given.

<Method for producing polypropylene colored resin composition>
The present invention is a method for producing a polypropylene colored resin composition in which a polypropylene resin is colored with a coloring agent containing at least one compound represented by general formulas (1) to (4) in a medium, wherein Provided is a method for producing a colored polypropylene resin composition in which a coloring agent is uniformly dispersed in a polypropylene resin by using carbon dioxide to create a supercritical carbon dioxide state.

In the polypropylene colored resin composition of the present invention, the components other than the polypropylene resin and at least one compound represented by the general formulas (1) to (4) are added to the extent that the properties in the usage form are not impaired. You may add an agent etc. suitably.

Carbon dioxide is essential as the medium in the present invention, but if necessary, a second medium such as a ketone solvent such as acetone, or a lower alcohol solvent such as methanol or ethanol may be added (generally, entrainer effect is said). The second medium is in the range of 0.1% to 5% by volume, preferably 0.3% to 3% by volume, more preferably 0.5% to 2% by volume, relative to the internal volume of the container. is in the range of

<Supercritical carbon dioxide treatment>
The processing conditions using supercritical carbon dioxide can be any conditions suitable for the purpose of supercritical processing.

The term "supercritical carbon dioxide" as used in the present invention refers to a non-condensable high-density fluid obtained by subjecting carbon dioxide to a pressure of 7.38 MPa or higher and a temperature of 31.1° C. or higher.

The dyeing method of the present invention will be described. When supercritical carbon dioxide is used as a medium, the dyeing temperature may be 5° C. or more higher than the critical temperature of carbon dioxide. It is preferably in the range of 50 to 150°C, more preferably in the range of 70 to 120°C. A dyeing temperature higher than 150° C. is also possible, but it is not preferable because it may cause problems such as melting of polypropylene fibers and an increase in production cost. On the other hand, when the temperature is lower than the critical temperature of carbon dioxide, the injection into the polypropylene fiber does not proceed sufficiently, which is not preferable.

The dyeing pressure may be 7.38 MPa or higher, which is the critical pressure of carbon dioxide, preferably 12 to 35 MPa, more preferably 15 to 25 MPa. If the pressure is higher than 25 MPa, equipment with even higher pressure resistance is required, which is economically undesirable.

Although the supercritical treatment time is not particularly limited, it is usually more preferably in the range of about 15 minutes to 3 hours.

The coloring agent of the present invention may be used alone or in combination of two or more. In addition, other colorants such as known dyes may be used in combination as long as the solubility or dispersibility in the carbon dioxide medium is not impaired.

The content of the colorant is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the polypropylene resin. is. Within the above range, sufficient coloring power is obtained, and the coloring agent has good diffusibility in the polypropylene resin, and the coloring agent is dispersed in the resin by releasing pressure and cooling. Settle in.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Identification of the obtained compound, 1H nuclear magnetic resonance spectroscopy (1H-NMR) device (ECA-400, manufactured by JEOL Ltd.), and LC / TOF MS device (LC / MSD TOF, manufactured by Agilent Technologies ) was used.

<Production of polypropylene colored resin composition>
A colored polypropylene resin composition of the present invention and a colored polypropylene resin composition for comparison were produced by the method described below.

[Example 1: Production of colored polypropylene resin composition (1) (supercritical treatment method)]
Polypropylene cloth of 10 cm×10 cm (0.45 g) was sewn together with polyethylene thread to form a cylinder having an inner diameter of 1 cm. Next, 0.01 g of compound (1-1) wrapped in polypropylene cloth and one sheet of Kimwipe (weight of cloth x 0.66% by mass) was placed in a 500 mL supercritical fluid extraction and separation apparatus (manufactured by AKICO Co., Ltd.). put in and sealed. The inner temperature was raised to 140° C., the layer pressure was adjusted to 25 MPa with carbon dioxide, and the layer was treated in a supercritical state for 60 minutes. After the treatment, carbon dioxide was discharged and the tank was depressurized. The colored polypropylene cloth was removed from the layer, washed with acetone at 35° C. for 20 minutes, and dried to obtain a colored polypropylene resin composition (1).

[Examples 2 to 15: Polypropylene colored resin compositions (2) to (15), Comparative Examples 1 to 3: Production of comparative polypropylene colored resin compositions (1) to (3)]
In Example 1, in the same manner as in Example 1, except that the compound represented by the general formula (1-1) and the production conditions (pressure, temperature, retention time, medium 2) were changed to those shown in Table 1. , polypropylene colored resin compositions (2) to (15), and comparative polypropylene colored resin compositions (1) to (3) were obtained. The following comparative compounds were used.

The following evaluations were performed on each of the obtained colored polypropylene resin compositions, and the results are shown in Table 2.

[Saturation evaluation]
A standard white plate is placed under the polypropylene colored resin composition obtained above, and the values of L ^* , a ^* , and b ^* are measured using a spectral densitometer (fluorescence spectral densitometer FD-7, manufactured by Konica Minolta). It was measured. From the values of L ^* , a ^* , and b ^* thus obtained, chroma (C ^* ) was determined based on the following formula and evaluated.
C ^* = ((a ^* ) ² + (b ^* ) ² ) ^1/2

As the chroma C ^* increases, the chroma spreads better and can be said to have high chroma.
AA: C ^* is 70 or more A: C ^* is 50 or more and less than 70 B: C ^* is 30 or more and less than 50 C: C ^* is less than 30

[Washing fastness evaluation]
The color fastness to washing of the polypropylene colored resin composition obtained above (staining resistance and discoloration/fading) was evaluated according to the washing fastness test JIS L0844 A-2 method. Specifically, the polypropylene colored resin composition obtained above is coated with a white multi-fiber mixed woven fabric (mixed weave No. 1: compliant with JIS L0803, woven with cotton, nylon, acetate, wool, rayon, acrylic, silk and polyester. It was washed with a washing tester and dried after washing. The staining property was evaluated based on the staining gray scale for the most stained portion of the dried multi-fiber woven fabric. In addition, in this test, evaluation is carried out in nine grades of grade 5, grade 4-5, grade 4, grade 3-4, grade 3, grade 2-3, grade 2, grade 1-2, and grade 1. The closer to grade 5, the whiter, indicating that no contamination occurred.
A: Grade 4 or higher B: Grade 2-3 or higher and lower than Grade 4 C: Grade 2 or lower

[Sublimation fastness evaluation]
Evaluation of fastness to sublimation (staining property among staining property and discoloration/fading) of the colored polypropylene resin composition obtained above was carried out in accordance with JIS L0854. Nylon (single fiber cloth (I) No. 7: JIS L0803:2005) was used for the attached white cloth, and evaluation was made based on the gray scale for staining. In addition, in this test, evaluation is carried out in nine grades of grade 5, grade 4-5, grade 4, grade 3-4, grade 3, grade 2-3, grade 2, grade 1-2, and grade 1. The closer to grade 5, the whiter, indicating that no contamination occurred.
A: 4th grade to 5th grade B: 2-3rd grade to 3-4th grade C: 1st grade to 2nd grade

As shown in Table 2, it is clear that the polypropylene colored resin compositions of Examples are superior to the comparative colored resin compositions in all of high color development, washing resistance, and sublimation resistance.

INDUSTRIAL APPLICABILITY The polypropylene colored resin composition of the present invention is excellent in high color development, washing resistance and sublimation resistance, and can be stably supplied. By using the polypropylene colored resin composition, woven fabrics, knitted fabrics, non-woven fabrics, clothes, underwear, socks, gloves, zippers, hats, sports clothes, seat sheets, vehicle interior materials, shoes, curtains, carpets, ropes, tents, It can be suitably used for building materials such as mats, sofas and wall cloths.

Claims (5)

A colored polypropylene resin composition comprising a polypropylene resin and a coloring agent, wherein the coloring agent contains at least one compound represented by the following general formulas (1) to (4).

[In general formula (1),
R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms,
R ₃ represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group;
R ₄ represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group;
R ₅ represents an alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, a benzyl group, a dialkylamino group or a diphenylamino group;
A represents a carbon atom or a nitrogen atom, and when it is a carbon atom, one hydrogen atom is bonded to the carbon atom. ]

[In general formula (2),
R ₆ and R ₇ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₈ represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms, a phenyl group having a substituent, or an unsubstituted phenyl group;
R ₉ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₁ R ₁₂ ,
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₁ and R ₁₂ with each other. ]

[In general formula (3),
B represents a carbonyl group or a sulfonyl group,
R ₁₃ and R ₁₄ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms,
R ₁₅ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₁₆ represents a hydrogen atom, an alkyl group, an aryl group, a benzyl group, -NR ₁₇ R ₁₈ ,
R ₁₇ and R ₁₈ each independently represents a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₁₇ and R ₁₈ with each other. ]

[In general formula (4),
R ₁₉ and R ₂₀ each independently represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms, R ₂₁ represents a linear alkyl group having 1 to 4 carbon atoms.
R ₂₂ represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms,
R ₂₃ and R ₂₄ each independently represent a hydrogen atom, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituent; and represents a ring formed by combining R ₂₃ and R ₂₄ with each other. ] 2. The colored polypropylene resin composition according to claim 1, wherein the shape of the polypropylene resin is fibrous, particulate or filamentous. R 1 and R ₂ of the compound represented by the general formula ( ₁ ), R ₆ and R ₇ of the compound represented by the general formula (2), and R ₁₃ of the compound represented by the general formula (3) and R ₁₄ is a 2-ethylhexyl group, the colored polypropylene resin composition according to claim 1 or 2. A method for producing a polypropylene colored resin composition according to any one of claims 1 to 3,
Polypropylene coloring characterized by using supercritical carbon dioxide as a medium and coloring the polypropylene resin in the medium with a coloring agent containing at least one compound represented by the general formulas (1) to (4). A method for producing a resin composition. 5. The method for producing a colored polypropylene resin composition according to claim 4, wherein a lower alcohol or ketone is added to the medium.