Polypropylene colored resin composition and method for producing the same

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]

[0001] The present invention relates to a polypropylene colored resin composition and a method for producing the same. [Background technology]

[0002] Polypropylene (sometimes abbreviated as PP) resin is one of the general-purpose resins. Polypropylene (PP) resin is characterized by its lightness compared to water (specific gravity 0.92), quick-drying properties, heat resistance, chemical resistance, antistatic properties, abrasion resistance, and flexibility, and is used in various fields due to these characteristics. For example, textile products such as nonwoven fabrics are inexpensive, have relatively good mechanical properties and spinnability, and are easy to process. On the other hand, dyeability or color affinity is required, but industrially, the main methods for coloring polypropylene have been manufacturing methods that involve adding organic or inorganic pigments during the spinning process and dyeing them, or directly kneading organic pigments into the resin. However, these methods still have many challenges, such as lack of vividness, variety of colors, difficulty in printing, thicker yarn, and a rough texture. For this reason, its use has hardly progressed in the fields of apparel and sportswear. In recent years, a dyeing method using anthraquinone dyes has been reported as a method for dyeing polypropylene resin (fiber) (see Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 18 / 123811 [Patent Document 2] International Publication No. 19 / 146174 [Overview of the project] [Problems that the invention aims to solve]

[0004] The anthranocine dyes described in the aforementioned literature had problems with high cohesiveness, insufficient color vibrancy, and poor wash resistance. Furthermore, during sea transport, the dyes sublimated due to rising temperatures on board, causing color transfer to adjacent lighter colors. In recent years, concerns have also been raised regarding stable supply due to the availability of raw materials. Therefore, there is a strong demand for the development of dyes and polypropylene colored resin compositions that can dye polypropylene resins with high color vibrancy, excellent wash resistance and sublimation resistance, and stable supply, particularly in the apparel and sportswear sectors where design and functionality are required. [Means for solving the problem]

[0005] The present invention relates to a polypropylene colored resin composition comprising a polypropylene resin and a colorant, characterized in that the colorant comprises at least one compound represented by the following general formulas (1) to (4).

[0006] [ka] [In general formula (1), R1 and R2 each independently represent an alkyl group having 1 to 12 carbon atoms. R3 represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group. R4 represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group. R5 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; if it is a carbon atom, one hydrogen atom is bonded to it.

[0007] [ka] [In general formula (2), R6 and R7 each independently represent 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. R8 represents a linear alkyl group having 1 to 4 carbon atoms or a 3 branched alkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, or an unsubstituted phenyl group. R9 represents a linear alkyl group having 1 to 12 carbon atoms or a 3 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 etc. R 11 and R 12 each independently represent a hydrogen atom, an unsubstituted alkyl group, an alkyl group having a substituent, an unsubstituted aryl group, an aryl group having a substituent, an unsubstituted acyl group, or an acyl group having a substituent. R 11 and R 12 represent a ring formed by bonding to each other.]

[0008]

Chemical formula

[0009] [ka] [In general formula (4), R 19 and R 20 Each of these 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 This represents a linear alkyl group having 1 to 4 carbon atoms. R 22 This is a linear alkyl group having 1 to 12 carbon atoms or a C1 3 Represents ~12 branched alkyl groups, R 23 and R 24 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 substituted acyl group, R 23 and R 24 This represents a ring formed by the bonding of elements. Furthermore, the present invention relates to a method for producing a polypropylene colored resin composition having the above configuration, The present invention relates to a method for producing a polypropylene colored resin composition, characterized by using supercritical carbon dioxide as a medium and coloring a polypropylene resin with a coloring agent in the medium. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a polypropylene colored resin composition that is excellent in terms of high color development, washability, and sublimation resistance, and can be supplied stably. Furthermore, according to the present invention, it is possible to provide a method for producing a polypropylene colored resin composition that is characterized by high color development, excellent washability and sublimation resistance, and stable supply, in which a colorant is highly dispersed in a polypropylene resin using supercritical carbon dioxide as a medium. [Modes for carrying out the invention]

[0011] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments. In the present invention, unless otherwise specified, the notation "○○~××" which represents a numerical range such as the number of carbon atoms means a numerical range that includes the lower and upper limits which are the endpoints.

[0012] As a result of diligent research to solve the above problems, the present inventors have found that by using a polypropylene colored resin composition comprising a polypropylene resin and a colorant, wherein the colorant comprises at least one compound represented by the following general formulas (1) to (4), it is possible to provide a polypropylene colored resin composition that is excellent in high color development, washability, and sublimation resistance, and can be supplied stably.

[0013] [ka] [In general formula (1), R1 and R2 each independently represent an alkyl group having 1 to 12 carbon atoms. R3 represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group. R4 represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group. R5 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; if it is a carbon atom, one hydrogen atom is bonded to it.

[0014] [ka] [In general formula (2), R6 and R7 each independently represent 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. R8 represents a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group. R9 represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms. R 10 This includes hydrogen atoms, alkyl groups, aryl groups, benzyl groups, and -NR groups. 11 R 12 This represents, 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 substituted acyl group, R 11 and R 12 This represents a ring formed by the bonding of elements.

[0015] [ka] [In general formula (3), B represents a carbonyl group or a sulfonyl group. R 13 and R 14 Each of these 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 This represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms. R 16 This includes hydrogen atoms, alkyl groups, aryl groups, benzyl groups, and -NR groups. 17 R 18 This represents, R 17 and R 18Each 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 substituted acyl group, R 17 and R 18 This represents a ring formed by the bonding of elements.

[0016] [ka] [In general formula (4), R 19 and R 20 Each of these 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 This represents a linear alkyl group having 1 to 4 carbon atoms. R 22 This 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 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 substituted acyl group, R 23 and R 24 This represents a ring formed by the bonding of elements.

[0017] The polypropylene colored resin composition of the present invention can be manufactured by dissolving the colorant in carbon dioxide under supercritical conditions, thereby uniformly dispersing the colorant in the polypropylene resin.

[0018] The dyeing mechanism at this time is thought to be as follows: A pressure vessel containing carbon dioxide, a colorant, and polypropylene fibers is brought to a supercritical state of carbon dioxide under high temperature and pressure. When it reaches a supercritical state of carbon dioxide, (1) The coloring agent solvates (dissolves) 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 in the amorphous portion of the polypropylene polymer. (4) The coloring agent is adsorbed onto the polymers that make up the fibers. (5) By releasing the pressure and cooling, the gaps in the polymer chains return to their original state, and the colorant is fixed to the fiber. (6) When washing with acetone or similar substances, discoloration will occur if the fibers and the coloring agent are incompatible. The following steps are involved. Here, we believe that the solvation (solubility) of supercritical carbon dioxide and the colorant, and the compatibility of PP fibers and the colorant are key points.

[0019] The compounds represented by general formulas (1) to (4) of the present invention are characterized by their easy solubility in aliphatic hydrocarbon solvents (such as hexane and heptane). The dissolution of the compounds in a supercritical carbon dioxide state is very similar to that of aliphatic hydrocarbon solvents. Therefore, by creating a supercritical carbon dioxide state, the dye can be dissolved in carbon dioxide, and the colorant can be uniformly dispersed in the polypropylene resin. On the other hand, because the compounds represented by general formulas (1) to (4) of the present invention possess alkyl groups, it is anticipated that the compatibility with PP fibers will be high, resulting in a polypropylene colored resin composition that exhibits excellent color development, washability, and sublimation resistance, and can be supplied stably.

[0020] On the other hand, conventionally known anthraquinone compounds are poorly soluble in aliphatic hydrocarbon solvents and, consequently, are also poorly soluble in supercritical carbon dioxide.

[0021] <Compounds represented by general formula (1)> First, let's explain the compound represented by the general formula (1) above.

[0022] In general formula (1), the alkyl groups having 1 to 12 carbon atoms in R1 and R2 are not particularly limited and may be linear, branched, or cyclic alkyl groups. Specifically, examples include 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.

[0023] Among these, branched alkyl groups having 6 to 12 carbon atoms are preferred, and the 2-ethylhexyl group is particularly preferred, due to their excellent color development, washability, sublimation resistance, and stable supply.

[0024] Regarding cyclic alkyl groups, for example, in the case of "a cyclic alkyl group having 8 carbon atoms," it may be a cyclic structure having 8 carbon atoms, or it may be a structure in which a cyclic structure having 6 carbon atoms is bonded to an alkyl group having 2 carbon atoms.

[0025] In general formula (1), the alkyl group having 1 to 4 carbon atoms in R3 is not particularly limited and may be linear or branched. Specifically, examples include primary alkyl groups such as methyl, ethyl, n-propyl, and n-butyl groups; secondary alkyl groups such as iso-propyl and sec-butyl groups; and tertiary alkyl groups such as tert-butyl groups. Among these, tert-butyl groups are preferred from the viewpoint of high color development, excellent washability and sublimation resistance, and stable supply.

[0026] In general formula (1), when R3 is a substituted phenyl group, it is preferable that the number of carbon atoms, including the substituent, is 6 to 20. Examples of substituents include alkyl groups and alkoxy groups. There may be one or more substituents. Specifically, examples include 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, and 2,4,6-trimethoxyphenyl group. Among these, phenyl groups and 4-methylphenyl groups are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, and stable supply. It is also preferable that R3 is an unsubstituted phenyl group.

[0027] In general formula (1), the alkyl group having 1 to 4 carbon atoms in R4 is not particularly limited and may be linear or branched. Specifically, examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, and tert-butyl group. Among these, methyl group and ethyl group are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply.

[0028] In general formula (1), the alkyl group having 1 to 12 carbon atoms in R5 is not particularly limited and may be linear, branched, or cyclic. Specifically, examples include 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. From the viewpoint of excellent color development, washability, and sublimation resistance, and stable supply, sec-butyl group and neopentyl group are preferred.

[0029] In general formula (1), the dialkylamino group in R5 is not particularly limited, but examples include dimethylamino group, diethylamino group, dipropylamino group, and dibutylamino group. From the viewpoint of excellent color development, washability, and sublimation resistance, and stable supply, dimethylamino group and diethylamino group are preferred.

[0030] Next, the compounds of the present invention can be synthesized by referring to known methods described in the patent document (Japanese Patent Publication No. 08-245896). Specific examples are shown in (1-1) to (1-19) below, but the present invention is not limited to these.

[0031] [ka]

[0032] [ka]

[0033] The compound represented by the above general formula (1) may be used alone, or two or more may be used in combination to adjust the color tone, etc., depending on the application.

[0034] Among these, compounds (1-1), (1-2), (1-3), (1-5), (1-16), and (1-18) are preferred because they yield polypropylene colored resin compositions that exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably.

[0035] <Compounds represented by general formula (2)> Next, we will describe the compound represented by the above general formula (2).

[0036] In general formula (2), the linear alkyl group having 1 to 12 carbon atoms, the branched alkyl group having 3 to 12 carbon atoms, and the cyclic alkyl group having 3 to 12 carbon atoms in R6 and R7 are not particularly limited, but examples include 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.

[0037] Among these, alkyl groups having 8 carbon atoms are preferred because they exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably. Branched alkyl groups such as 2-ethylhexyl groups are particularly preferred.

[0038] In 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 R8 is not particularly limited, but specifically, examples include primary alkyl groups such as methyl, ethyl, n-propyl, and n-butyl groups; secondary alkyl groups such as iso-propyl and sec-butyl groups; and tertiary alkyl groups such as tert-butyl groups. Among these, tert-butyl groups are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply.

[0039] In general formula (2), the substituted phenyl group and the unsubstituted phenyl group at R8 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. When a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. There may be one or more substituents. 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-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-tridimethoxyphenyl group, naphthyl group, and the like. Among these, from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, unsubstituted phenyl groups and 4-methylphenyl groups are preferred, and unsubstituted phenyl groups are more preferred.

[0040] In general formula (2), the linear or branched alkyl group having 1 to 12 carbon atoms in R9 is not particularly limited, but specifically, 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, etc. Among these, from the viewpoint of excellent high color development, washability, and sublimation resistance, and stable supply, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, and 2,3,3-trimethylbutyl group are preferred, and methyl group is particularly preferred.

[0041] In general formula (2), R 10The alkyl group in this context is not particularly limited, but examples include linear alkyl groups having 1 to 12 carbon atoms or branched alkyl groups having 1 to 12 carbon atoms. Specifically, 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, etc. Among these, linear alkyl groups having 1 to 4 carbon atoms or branched alkyl groups having 1 to 4 carbon atoms are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and linear alkyl groups such as methyl group, ethyl group, propyl group, and n-butyl group are particularly preferred.

[0042] In general formula (2), R 10 ga-NR 11 R 12 When showing R 11 and R 12 This represents an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituted acyl group.

[0043] R 11 and R 12 The alkyl group is not particularly limited, but examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. If a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. Specific examples of unsubstituted alkyl groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, octyl, dodecyl, nonadecyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, and 2-ethylhexyl. Examples of substituents in substituted alkyl groups include cyclohexenyl groups. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups are particularly preferred.

[0044] R 11 and R 12The aryl group in this formula is not particularly limited, but examples include substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. Examples of substituents include alkyl groups and alkoxy groups. When substituents are present, the carbon number refers to the number of carbon atoms including those of the substituent. There may be one or more substituents. From the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, phenyl groups, 4-methylphenyl groups, 4-methoxyphenyl groups, etc., are particularly preferred as substituted or unsubstituted aryl groups having 6 to 10 carbon atoms.

[0045] R 11 and R 12 The acyl group in this formula is not particularly limited, but examples include substituted or unsubstituted acyl groups having 1 to 30 carbon atoms. If a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. Specifically, examples include formyl group; substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms such as acetyl group, propionyl group, and pivaloyl group; substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms such as benzoyl group and naphthoyl group; and heterocyclic carbonyl groups such as 2-pyridylcarbonyl group and 2-furylcarbonyl group. Among these, acetyl group, pivaloyl group, or benzoyl group is preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and acetyl group or benzoyl group is more preferred.

[0046] R 11 and R 12 The rings formed by the bonding of these elements are not particularly limited, but include pyridine rings, piperazine rings, morpholine rings, and phthalimide rings.

[0047] Next, a method for producing the compound represented by general formula (2) according to the present invention will be described. The compound of the present invention can be synthesized by referring to the known method described in WO2014 / 034094.

[0048] Compounds represented by general formula (2) have cis-trans isomers, both of which are within the scope of the present invention, and the compound represented by general formula (2) may be a mixture thereof.

[0049] Examples of preferred 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 to these.

[0050] [ka]

[0051] The compound represented by the above general formula (2) may be used alone, or two or more may be used in combination to adjust the color tone, etc., depending on the application.

[0052] Among these, compounds (2-1), (2-2), (2-3), (2-4), (2-7), and (2-10) are preferred because they yield polypropylene colored resin compositions that exhibit high color development, excellent washability, and sublimation resistance, and can be supplied stably.

[0053] <Compounds represented by general formula (3)> Next, we will describe the compound represented by the above general formula (3).

[0054] In general formula (3), R 13 and R 14 The linear alkyl groups having 1 to 12 carbon atoms, the branched alkyl groups having 3 to 12 carbon atoms, and the cyclic alkyl groups having 3 to 12 carbon atoms are not particularly limited, but examples include 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.

[0055] Among these, alkyl groups having 8 carbon atoms are preferred because they exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably. Branched alkyl groups such as 2-ethylhexyl groups are particularly preferred.

[0056] In general formula (3), R 15 The linear alkyl group having 1 to 12 carbon atoms or the branched alkyl group having 1 to 12 carbon atoms in the above is not particularly limited, but specifically, 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, etc. Among these, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, and 2,3,3-trimethylbutyl group are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and methyl group is particularly preferred.

[0057] In general formula (3), R 16 The alkyl group in this context is not particularly limited, but examples include linear alkyl groups having 1 to 12 carbon atoms or branched alkyl groups having 1 to 12 carbon atoms. Specifically, 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, etc. Among these, linear alkyl groups having 1 to 4 carbon atoms or branched alkyl groups having 1 to 4 carbon atoms are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and linear alkyl groups such as methyl group, ethyl group, propyl group, and n-butyl group are particularly preferred.

[0058] In general formula (3), R 16 ga-NR 17 R 18 When showing R 17 and R 18 This represents an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aryl group, a substituted aryl group, an unsubstituted acyl group, or a substituted acyl group.

[0059] R 17 and R 18 The alkyl group is not particularly limited, but examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. If a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. Specific examples of unsubstituted alkyl groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, octyl, dodecyl, nonadecyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, and 2-ethylhexyl. Examples of substituents in substituted alkyl groups include cyclohexenyl groups. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups are particularly preferred.

[0060] R 17 and R 18 The aryl group in this formula is not particularly limited, but examples include substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. Examples of substituents include alkyl groups and alkoxy groups. When substituents are present, the carbon number refers to the number of carbon atoms including those of the substituent. There may be one or more substituents. From the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, phenyl groups, 4-methylphenyl groups, 4-methoxyphenyl groups, etc., are particularly preferred as substituted or unsubstituted aryl groups having 6 to 10 carbon atoms.

[0061] R 17 and R 18The acyl group in this formula is not particularly limited, but examples include substituted or unsubstituted acyl groups having 1 to 30 carbon atoms. If a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. Specifically, examples include formyl group; substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms such as acetyl group, propionyl group, and pivaloyl group; substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms such as benzoyl group and naphthoyl group; and heterocyclic carbonyl groups such as 2-pyridylcarbonyl group and 2-furylcarbonyl group. Among these, acetyl group, pivaloyl group, or benzoyl group is preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and acetyl group or benzoyl group is more preferred.

[0062] R 17 and R 18 The rings formed by the bonding of these elements are not particularly limited, but include pyridine rings, piperazine rings, morpholine rings, and phthalimide rings.

[0063] The compound represented by general formula (3) according to the present invention can be synthesized by referring to the known method described in publication WO08 / 114886. Azo-hydrazo tautomers of this compound exist, all of which are within the scope of the present invention, and mixtures thereof may also be used. Examples of preferred compounds are shown below in (3-1) to (3-15) using the azo isomer notation, but the present invention is not limited to these.

[0064] [ka]

[0065] [ka]

[0066] The compound represented by the above general formula (3) may be used alone, or two or more may be used in combination to adjust the color tone, etc., depending on the application.

[0067] Among these, compounds (3-1), (3-2), (3-5), (3-6), (3-10), and (3-14) are preferred because they yield polypropylene colored resin compositions that exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably.

[0068] <Compounds represented by general formula (4)> Next, we will describe the compound represented by the above general formula (4).

[0069] In general formula (4), R 19 and R 20 The linear alkyl group having 1 to 12 carbon atoms, the branched alkyl group having 3 to 12 carbon atoms, or the cyclic alkyl group having 3 to 12 carbon atoms are not particularly limited, but examples include 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.

[0070] Among these, alkyl groups with 4 or fewer carbon atoms are preferred because they exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably. Methyl, ethyl, n-propyl, and n-butyl groups are more preferred.

[0071] In general formula (4), R 21 The linear alkyl group having 1 to 4 carbon atoms in this compound is not particularly limited, but examples include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, and tert-butyl groups. Among these, the methyl group is preferred.

[0072] In general formula (4), R 22The linear alkyl group having 1 to 12 carbon atoms or the branched alkyl group having 1 to 12 carbon atoms in the above is not particularly limited, but specifically, 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, etc. Among these, methyl group, ethyl group, propyl group, n-butyl group, 2-methylbutyl group, and 2,3,3-trimethylbutyl group are preferred from the viewpoint of excellent color development, washability, and sublimation resistance, as well as stable supply, and methyl group is particularly preferred.

[0073] In general formula (4), R 23 and R 24 The alkyl group in is not particularly limited, but examples include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. If a substituent is present, the carbon number refers to the number of carbon atoms including the substituent. Specific examples of unsubstituted alkyl groups include linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, octyl, dodecyl, nonadecyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, and 2-ethylhexyl. Examples of substituents in substituted alkyl groups include cyclohexenyl groups. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and methyl groups are particularly preferred.

[0074] R 23 and R 24The aryl group in [compound] is not particularly limited, and examples thereof include substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. Examples of the substituent include an alkyl group and an alkoxy group. When having a substituent, the above carbon number represents the number including the carbon number of the substituent. The substituent may be one or more. From the viewpoints of excellent high color development, washing resistance, and sublimation resistance and stable supply, specific examples of the substituted or unsubstituted aryl group having 6 to 10 carbon atoms include a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, etc., which are preferable.

[0075] R 23 and R 24 The acyl group in [compound] is not particularly limited, and examples thereof include substituted or unsubstituted acyl groups having 1 to 30 carbon atoms. When having a substituent, the above carbon number represents the number including the carbon number of the substituent. Specifically, a formyl group; substituted or unsubstituted alkylcarbonyl groups having 2 to 30 carbon atoms such as an acetyl group, a propionyl group, a pivaloyl group; substituted or unsubstituted arylcarbonyl groups having 7 to 30 carbon atoms such as a benzoyl group, a naphthoyl group; heterocyclic carbonyl groups such as a 2-pyridylcarbonyl group, a 2-furylcarbonyl group, etc. Among these, from the viewpoints of excellent high color development, washing resistance, and sublimation resistance and stable supply, it is preferably an acetyl group, a pivaloyl group or a benzoyl group, and more preferably an acetyl group or a benzoyl group.

[0076] R 23 and R 24 The ring formed by R and R bonding to each other is not particularly limited, and examples thereof include a pyridine ring, a piperazine ring, a morpholine ring, and a phthalimide ring.

[0077] Preferred examples include compounds (4-1) to (4-7) shown below, but are not limited to the following compounds.

[0078]

Chemical formula

[0079] The compound represented by the above general formula (4) may be used alone, or two or more may be used in combination to adjust the color tone, etc., depending on the application.

[0080] Among these, compounds (4-1), (4-2), and (4-3) are preferred because they yield polypropylene colored resin compositions that exhibit excellent color development, washability, and sublimation resistance, and can be supplied stably.

[0081] <Polypropylene resin> Next, the polypropylene resin according to the present invention will be described.

[0082] The polypropylene resin used in the present invention is not particularly limited, and any known polypropylene resin may be used.

[0083] The shape of the polypropylene resin of the present invention is not particularly limited, but fibrous, fine particle, or thread-like forms are particularly preferred.

[0084] Furthermore, the material may be in the form of a processed product. For example, fabric-like fibers (woven fabrics, knitted fabrics, nonwoven fabrics, felt, tufts, etc.), yarn-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. Furthermore, polypropylene fibers can be suitably used when blended with other fibers such as polyester and / or as a blended fiber.

[0085] Specifically, examples include woven fabrics, knitted fabrics, nonwoven fabrics, clothing, underwear, socks, gloves, zippers, hats, sportswear, seat covers, vehicle packaging materials, shoes, curtains, carpets, mats, sofas, wall coverings, and other building materials.

[0086] <Method for producing colored polypropylene resin composition> The present invention provides a method for producing a polypropylene colored resin composition in which a polypropylene resin is colored with a colorant containing at least one compound represented by general formulas (1) to (4) in a medium, wherein carbon dioxide is used as the medium and the colorant is uniformly dispersed in the polypropylene resin by creating a supercritical carbon dioxide state.

[0087] In the polypropylene colored resin composition of the present invention, components other than the polypropylene resin and at least one compound represented by general formulas (1) to (4) may be appropriately mixed with additives, etc., to the extent that they do not impair the properties in the form of use.

[0088] In the present invention, carbon dioxide is essential as the medium, but a second medium, such as a ketone solvent like acetone, or a lower alcohol solvent like methanol or ethanol, may be added as needed (generally known as the entrainer effect). The amount of the second medium is in the range of 0.1% to 5% by volume relative to the internal volume of the container, preferably in the range of 0.3% to 3% by volume, and more preferably in the range of 0.5% to 2% by volume.

[0089] <Supercritical carbon dioxide treatment> The processing conditions using supercritical carbon dioxide can be set to any conditions that suit the purpose of supercritical processing.

[0090] In this invention, supercritical carbon dioxide refers to a non-condensable, high-density fluid obtained by applying a pressure of 7.38 MPa or higher and a temperature of 31.1°C or higher to carbon dioxide.

[0091] The dyeing method of the present invention will now be described. When using supercritical carbon dioxide as the medium, the dyeing temperature should be at least 5°C higher than the critical temperature of carbon dioxide. Preferably, it is in the range of 50 to 150°C, and more preferably 70 to 120°C. Although it is possible to dye at a temperature higher than 150°C, this is undesirable because it may lead to problems such as melting of polypropylene fibers and an increase in manufacturing costs. On the other hand, if the temperature is lower than the critical temperature of carbon dioxide, it is undesirable because the injection into the polypropylene fibers does not proceed sufficiently.

[0092] The dyeing pressure should be at least 7.38 MPa, which is the critical pressure of carbon dioxide, preferably 12 to 35 MPa, and more preferably 15 to 25 MPa. If the pressure is higher than 25 MPa, equipment with even higher pressure resistance is required, which presents economically undesirable problems.

[0093] While there are no specific restrictions on the supercritical processing time, it is generally preferable that it be in the range of 15 minutes to 3 hours.

[0094] The colorants of the present invention may be used individually or in combination of two or more. Furthermore, other colorants, such as known dyes, may be used in combination, provided that they do not impair solubility or dispersibility in the carbon dioxide medium.

[0095] The coloring agent content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 3 parts by mass, per 100 parts by mass of polypropylene resin. Within this range, sufficient coloring power can be obtained, and the coloring agent will have good diffusion properties into the polypropylene resin. Upon release of pressure and cooling, the coloring agent will be fixed in a dispersed state within the resin. [Examples]

[0096] 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. The obtained compounds were identified using a 1H nuclear magnetic resonance (1H-NMR) spectrometer (ECA-400, manufactured by JEOL Ltd.) and an LC / TOF MS spectrometer (LC / MSD TOF, manufactured by Agilent Technologies).

[0097] <Manufacturing of colored polypropylene resin composition> The polypropylene colored resin composition of the present invention and a comparative polypropylene colored resin composition were produced by the method described below.

[0098] [Example 1: Production of polypropylene colored resin composition (1) (supercritical fluid treatment method)] A 10cm x 10cm (0.45g) piece of polypropylene cloth was sewn together with polyethylene thread to form a tube with an inner diameter of 1cm. Next, 0.01g (0.66% of the cloth's weight) of compound (1-1), wrapped in the polypropylene cloth and one Kimwipe, was placed in a 500mL supercritical fluid extraction and separation apparatus (manufactured by AKICO Co., Ltd.) and sealed. The internal temperature was raised to 140°C, the internal pressure was adjusted to 25MPa with carbon dioxide, and the apparatus was treated in a supercritical state for 60 minutes. After treatment, carbon dioxide was discharged to release the pressure inside the chamber. The colored polypropylene cloth was removed from the chamber, washed with acetone at 35°C for 20 minutes, and dried to obtain the colored polypropylene resin composition (1).

[0099] [Examples 2-15: Production of polypropylene colored resin compositions (2)-(15), Comparative Examples 1-3: Production of comparative polypropylene colored resin compositions (1)-(3)] Polypropylene colored resin compositions (2) to (15) and comparative polypropylene colored resin compositions (1) to (3) were obtained in the same manner as in Example 1, except that the compound represented by general formula (1-1) and the manufacturing conditions (pressure, temperature, holding time, medium 2) were changed to those shown in Table 1. The comparative compounds used were as follows.

[0100] [ka]

[0101] For each of the obtained polypropylene colored resin compositions, the following evaluations were carried out, and the results are shown in Table 2.

[0102] [Chroma evaluation] A standard white plate was placed under the polypropylene colored resin composition obtained above, and using a spectrophotometer (fluorescence spectrophotometer FD-7, manufactured by Konica Minolta), L * , a * , b * values were measured. From the obtained L * , a * , b * values, chroma (C * ) was determined based on the following formula and evaluated. C * =((a * ) 2 +(b * ) 2 ) 1 / 2

[0103] The larger the chroma C * , the better the elongation of the chroma, and it can be said that the chroma is high. 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

[0104] [Washing fastness evaluation] The wash fastness (stain resistance, specifically stain resistance among discoloration) of the polypropylene colored resin compositions obtained above was evaluated in accordance with the wash fastness test method JIS L0844 A-2. Specifically, a white multi-fiber woven fabric (mixed fabric No. 1: in accordance with JIS L0803, a fabric woven from cotton, nylon, acetate, wool, rayon, acrylic, silk, and polyester) was sewn onto the polypropylene colored resin compositions obtained above, and the fabric was washed in a washing machine and dried after washing. Stain resistance was evaluated on the most stained part of the dried multi-fiber woven fabric, using a gray scale for stain resistance as a reference. In this test, evaluation is performed on a 9-level scale: 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 the fabric, indicating that no staining occurred. A: Level 4 or higher B: Grades 2-3 and above, but less than Grade 4 C: Level 2 or below

[0105] [Sublimation fastness evaluation] The sublimation fastness (stain resistance, specifically stain resistance among discoloration) of the polypropylene colored resin compositions obtained above was evaluated in accordance with JIS L0854. Nylon (single fiber cloth (I) No. 7: JIS L0803:2005) was used as the attached white cloth, and the evaluation was based on a gray scale for stain resistance. In this test, evaluation is performed on a nine-level scale: 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 the color, indicating that no staining occurred. A: 4th grade ~ 5th grade B: 2-3 grade ~ 3-4 grade C: 1st grade ~ 2nd grade

[0106] [Table 1]

[0107] [Table 2]

[0108] As shown in Table 2, the polypropylene colored resin compositions of the examples are clearly superior to the comparative colored resin compositions in terms of high color development, washability, and sublimation resistance. [Industrial applicability]

[0109] The polypropylene colored resin composition of the present invention exhibits excellent high color development, washability, and sublimation resistance, and can be supplied stably. By using this polypropylene colored resin composition, it can be suitably used in woven fabrics, knitted fabrics, nonwoven fabrics, clothing, underwear, socks, gloves, zippers, hats, sportswear, seat covers, vehicle packaging materials, shoes, curtains, carpets, ropes, tents, mats, sofas, wall coverings, and other building materials.

Claims

1. A polypropylene colored resin composition comprising a polypropylene resin and a colorant, wherein the colorant comprises at least one compound represented by the following general formulas (1) to (4). 【Chemistry 1】 [In general formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 12 carbon atoms. R 3 This represents an alkyl group having 1 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group. R 4 This represents an alkyl group having 1 to 4 carbon atoms or an unsubstituted phenyl group. R 5 This 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. If it is a carbon atom, one hydrogen atom is bonded to it. 【Chemistry 2】 [In general formula (2), R 6 and R 7 Each of these 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 This represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, a substituted phenyl group, or an unsubstituted phenyl group. R 9 represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms, R 10 is a hydrogen atom, alkyl group, aryl group, benzyl group, -NR 11 R 12 This represents, 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 substituted acyl group, R 11 and R 12 This represents a ring formed by the bonding of elements. 【Transformation 3】 [In general formula (3), B represents a carbonyl group or a sulfonyl group. R 13 and R 14 Each of these 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 This represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. R 16 is a hydrogen atom, alkyl group, aryl group, benzyl group, -NR 17 R 18 This represents, 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 substituted acyl group, R 17 and R 18 This represents a ring formed by the bonding of elements. 【Chemistry 4】 [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 This represents a linear alkyl group having 1 to 4 carbon atoms. R 22 This represents a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. R 23 and R 24 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 substituted acyl group, R 23 and R 24 This represents a ring formed by the bonding of elements.

2. The polypropylene colored resin composition according to claim 1, wherein the shape of the polypropylene resin is fibrous, fine particles, or thread-like.

3. R of the compound represented by the general formula (1) 1 and R 2 , the R of the compound represented by the general formula (2) 6 and R 7 , the R of the compound represented by the general formula (3) 13 and R 14 The polypropylene colored resin composition according to claim 1 or 2, wherein the group is a 2-ethylhexyl group.

4. A method for producing a polypropylene colored resin composition according to any one of claims 1 to 3, A method for producing a colored polypropylene resin composition, characterized by using supercritical carbon dioxide as a medium and coloring a polypropylene resin in the medium with a coloring agent containing at least one compound represented by the general formulas (1) to (4).

5. A method for producing a polypropylene colored resin composition according to claim 4, wherein a lower alcohol or ketone is added to the above medium.

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