Composition, composition for resin coloring, polymer

Abstract

A first problem of the present invention is to provide a composition having excellent sweat resistance. A second problem of the present invention is to provide a composition for resin coloring and a polymer which have excellent sweat resistance. These compositions of the present invention each comprise a polymer comprising repeating units represented by general formula (1) and repeating units represented by general formula (2) and a thermoplastic resin.

Description

[Technical field]

[0001] The present invention relates to a composition, a composition for coloring resins, and a polymer. [Background technology]

[0002] Nowadays, colored resin molded products are used in various fields. The main methods for coloring resin include a method of directly mixing a dye and a resin to obtain a desired color tone, and a method of using a master batch for coloring resin. Specifically, the method of using a master batch for coloring resin is a method of mixing a dye and a resin to obtain a high dye concentration (e.g., in the form of pellets) as a master batch for coloring resin, and mixing the master batch for coloring resin and a diluted resin to obtain a desired color tone.

[0003] Compounds having a coumarin skeleton (hereinafter also referred to as "coumarin compounds") are mainly used as dyes that exhibit fluorescent yellow color. For example, Patent Document 1 discloses the following low molecular weight coumarin compound.

[0004] [ka]

[0005] Moreover, Patent Document 2 discloses the following low molecular weight coumarin compound.

[0006] [ka] [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2020-007383 A [Patent Document 2] JP 2010-168369 A Summary of the Invention [Problem to be solved by the invention]

[0008] Colored resin molded products are used in a wide range of applications, including as decorative items worn on the skin, and are therefore required to have a high resistance to fading due to sweat from the user (excellent sweat resistance).

[0009] The present inventors have prepared and examined compositions in which the coumarin compounds described in Patent Documents 1 and 2 are mixed as pigments with resins, and have found that the sweat resistance of the compositions may not satisfy current demands.

[0010] Therefore, an object of the present invention is to provide a composition having excellent sweat resistance. Another object of the present invention is to provide a resin coloring composition and a polymer that have excellent sweat resistance. [Means for solving the problem]

[0011] As a result of intensive research into the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.

[0012] [1] A polymer including a repeating unit represented by general formula (1) described later and a repeating unit represented by general formula (2) described later; A composition comprising: [2] The composition according to [1], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the general formula (4) described below. [3] In the above general formula (2), R 2 represents a group represented by general formula (R1A) described later, and R 3 represents a hydrogen atom or a methyl group. [4] The composition according to [1] or [2], wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the general formula (5) described below, and the repeating unit represented by the general formula (2) is a repeating unit represented by the general formula (6) described below. [5] In the above general formula (6), R 3 represents a hydrogen atom or a methyl group, R 15 represents an optionally substituted aryl group, a benzyl group, or an alkyl group, or a hydrogen atom. [6] The composition according to any one of [1] to [5], wherein the thermoplastic resin is at least one selected from the group consisting of polyamide resins and polyolefin resins. [7] The polymer is The weight average molecular weight is 1,000 to 100,000, and The composition according to any one of [1] to [6], wherein the content of the repeating unit represented by the above general formula (1) is 0.1 to 50 mass % based on the total repeating units in the polymer. [8] A composition for resin coloring comprising the composition according to any one of [1] to [7]. [9] A polymer comprising a repeating unit represented by the general formula (4) described later and a repeating unit represented by the general formula (2) described later.

[10] The polymer according to [9], wherein the repeating unit represented by the general formula (4) is a repeating unit represented by the general formula (5) described below, and the repeating unit represented by the general formula (2) is a repeating unit represented by the general formula (6) described below.

[11] In the above general formula (6), R 3 represents a hydrogen atom or a methyl group, R 15 represents an optionally substituted aryl group, a benzyl group, or an alkyl group, or a hydrogen atom.

[12] The weight average molecular weight is 1,000 to 100,000, and The polymer according to any one of [9] to

[11] , wherein the content of the repeating unit represented by the above general formula (4) is 0.1 to 50 mass % based on the total repeating units in the polymer. Effect of the Invention

[0013] According to the present invention, a composition having excellent sweat resistance can be provided. Furthermore, according to the present invention, it is possible to provide a resin coloring composition and a polymer having excellent sweat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, for substituents and the like that are not specified as substituted or unsubstituted, the group may be further substituted with a substituent (e.g., the substituent W described below) within the scope that does not impair the intended effect. For example, the expression "alkyl group" means an alkyl group that may be substituted with a substituent (e.g., the substituent W described below). In addition, in this specification, "organic group" refers to a group containing at least one carbon atom. In addition, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower limit and upper limit. The bonding direction of a divalent group represented in this specification is not particularly limited. For example, in the case of -CO-O-, it may be either -CO-O- or -O-CO-. In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight average molecular weight (Mw) and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a polymer are defined as polystyrene-equivalent values ​​measured using a Gel Permeation Chromatography (GPC) apparatus (HLC-8220GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: refractive index detector).

[0015] [Composition] The composition of the present invention contains a polymer (hereinafter also referred to as a "specific polymer") containing a repeating unit represented by general formula (1) described later and a repeating unit represented by general formula (2) described later, and a thermoplastic resin. Due to the above constitution, the composition of the present invention exhibits excellent sweat resistance. A feature of the present invention compared to the prior art is the use of a specific polymer containing a coumarin dye as a repeating unit. Although the mechanism of action of the present invention is unclear, it is presumed that the specific polymer containing the coumarin dye in its structure forms a network with the thermoplastic resin, which makes it difficult for the coumarin dye to be desorbed by sweat, and as a result, it is difficult for fading to occur. In addition, the present inventors' recent studies have revealed that the above composition can stably color resins even when the specific polymer is blended at a relatively high concentration, and can be suitably used as a resin coloring composition (resin coloring master batch). It has also been revealed that by appropriately selecting the repeating unit represented by general formula (2) in the specific polymer, the composition has excellent light resistance. Hereinafter, a composition having superior sweat resistance and / or light resistance is also referred to as having "superior effects of the present invention."

[0016] The composition of the present invention will now be described. The composition of the present invention contains a specific polymer and a thermoplastic resin.

[0017] [Specific polymer] The specific polymer will be described below. The specific polymer is a polymer containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). First, the repeating unit represented by formula (1) will be described below.

[0018] [ka]

[0019] In general formula (1), R 1 represents a hydrogen atom or a substituent. R 1 The type of the substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. R 1 In terms of the superior effect of the present invention, preferably represents a hydrogen atom or an alkyl group which may have a substituent, more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, and further preferably represents a hydrogen atom or a methyl group. Examples of the substituent which the above-mentioned alkyl group may have include the groups exemplified as the substituent W described later.

[0020] L represents a divalent linking group. The divalent linking group represented by L is not particularly limited, and examples thereof include -CO-, -O-, -S-, -SO-, -SO2-, -NR A-, an alkylene group (which may be linear, branched, or cyclic; preferably has 1 to 15 carbon atoms, and more preferably has 1 to 6 carbon atoms), an alkenylene group (preferably has 2 to 6 carbon atoms), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, or sulfur atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), a divalent arylene group (preferably a 6- to 10-membered ring, and more preferably a 6-membered ring), a divalent heteroarylene group (preferably a 5- to 10-membered ring having at least one nitrogen atom, oxygen atom, or sulfur atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), and a divalent linking group formed by combining a plurality of these. Above R A is a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The alkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent arylene group, and the divalent heteroarylene group may have a substituent. Examples of the substituent include the groups exemplified as the substituent W described later.

[0021] The divalent linking group represented by L is preferably -CO-O-, an alkylene group, a divalent arylene group, a divalent heteroarylene group, or a divalent linking group formed by combining a plurality of these, more preferably -CO-O-, an alkylene group, a divalent arylene group, or a divalent linking group formed by combining a plurality of these, and even more preferably a divalent linking group formed by combining an alkylene group and a divalent arylene group (for example, *-CH2-Ph-* (Ph represents a phenylene group which may have a substituent, and * represents a bonding position)), in terms of providing better effects for the present invention.

[0022] X 1 represents a residue derived from a compound represented by the following general formula (3).

[0023] [ka]

[0024] In general formula (3), X 2 represents a coumarin ring group which may have a substituent. The coumarin ring group which may have a substituent is intended to mean a group formed by removing one hydrogen atom from a coumarin ring which may have a substituent. The position from which the hydrogen atom is removed is not particularly limited, and may be a hydrogen atom bonded to a carbon atom constituting the coumarin ring (in other words, a carbon atom which is a ring member of the coumarin ring), or may be a hydrogen atom contained in a substituent possessed by the coumarin ring. An example of the coumarin ring group which may have a substituent is a residue derived from a compound represented by the following general formula (3A).

[0025] [ka]

[0026] In general formula (3A), R 9 , R 10 , R 11 , R 12 , R 13 , and R 16 Each independently represents a hydrogen atom or a substituent. 9 , R 10 , R 11 , R 12 , R 13 , and R 16 At least one of the hydrogen atoms represents a hydrogen atom, and by removing one of the hydrogen atoms, a residue derived from the compound represented by general formula (3A) is formed. That is, the position where one of the hydrogen atoms is removed is X as specified in general formula (3). 2 Among them, the effect of the present invention is more excellent in the case where R 16 represents a hydrogen atom, and R 16 It is preferable that the hydrogen atom of is removed to form a residue derived from the compound represented by general formula (3A). R 9 , R 10 , R 11 , R12 , R 13 , and R 16 The substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. In particular, R 9 , R 10 , R 11 , and R 12 At least one of the above preferably has a substituent, and more preferably has a dialkylamine having a total of 2 to 8 carbon atoms as the substituent. Also, R 9 , R 10 , R 11 , R 12 , R 13 , and R 16 Adjacent substituents may be bonded to each other to form a ring.

[0027] In the general formula (3), Y is an oxygen atom, a sulfur atom, or NR 8 Represents. As Y, NR is preferable because it has a better effect of the present invention. 8 It is preferred to represent

[0028] In general formula (3), R 4 , R 5 , R 6 , R 7 , and R 8 Each independently represents a hydrogen atom or a substituent. 4 , R 5 , R 6 , R 7 , and R 8 At least one of R represents a hydrogen atom, and by removing one of the hydrogen atoms, a residue derived from the compound represented by general formula (3) is formed. In other words, the position where one of the hydrogen atoms is removed becomes the bonding position with L as shown in general formula (1). 4 , R 5 , R 6 , R 7 , and R 8 Of these, R 8 When only Y represents a hydrogen atom, Y in the above general formula (3) is NR 8 Represents. The effect of the present invention is more excellent when Y in the general formula (3) is NR 8 and R 8 represents a hydrogen atom, and this R 8 is removed to form a residue derived from a compound represented by general formula (3), or R 5 and R 6 At least one of represents a hydrogen atom, and R 5 and R 6 It is preferable that one of the hydrogen atoms of at least one of the formulas is removed to form a residue derived from the compound represented by the general formula (3), and Y in the general formula (3) is NR 8 and R 8 represents a hydrogen atom, and this R 8 It is more preferable that the hydrogen atom of is removed to form a residue derived from the compound represented by general formula (3). R 4 , R 5 , R 6 , R 7 , and R 8 The substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. R 4 , R 5 , R 6 , R 7 , and R 8 Preferably, represents a hydrogen atom.

[0029] As the repeating unit represented by the above general formula (1), a repeating unit represented by the following general formula (4) is preferable, and a repeating unit represented by the following general formula (5) is more preferable.

[0030] [ka]

[0031] In general formula (4), R 4 , R 5 , R 6 , and R 7 is R in the above general formula (3). 4 , R 5, R 6 , and R 7 The same definition and preferred embodiments are also the same. In general formula (4), R 1 and L is R in the above general formula (1). 1 and L, and the preferred embodiments are also the same. In general formula (4), R 9 , R 10 , R 11 , R 12 , and R 13 is R in the above general formula (3A). 9 , R 10 , R 11 , R 12 , and R 13 The same definition and preferred embodiments are also the same.

[0032] [ka]

[0033] The content of the repeating unit represented by formula (1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more, based on the total repeating units in the specific polymer. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. In the specific polymer, the repeating unit represented by formula (1) may be of one type alone or in combination of two or more types.

[0034] Next, the repeating unit represented by formula (2) will be described.

[0035] [ka]

[0036] In general formula (2), R 2 and R 3 each independently represents a hydrogen atom or a substituent. R 2The substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. R 2 Of these, the substituent represented by the following formula (R1A) is preferable. General formula (R1A):*-L 1 -R 14 In general formula (R1A), L 1 represents a single bond or an ester bond (-CO-O-). R 14 represents a hydrogen atom or a substituent. R 14 The substituent represented by is preferably an aryl group, an aralkyl group, an alkyl group, or a heteroaryl group, which may have a substituent, more preferably an aryl group, a benzyl group, or an alkyl group, which may have a substituent, and even more preferably an alkyl group, which may have a substituent. It is preferable that the alkyl group does not have an aryl group as a substituent. In addition, the substituent that the aryl group, the aralkyl group, the alkyl group, and the heteroaryl group may have is not particularly limited, and examples thereof include the groups exemplified by the substituent W described below. * indicates the bond position. In addition, R 14 When represents a hydrogen atom, L 1 Preferably, represents an ester bond. R 14 Among them, preferably represents an aryl group, a benzyl group, or an alkyl group which may have a substituent, or a hydrogen atom, and more preferably represents an alkyl group which may have a substituent.

[0037] In general formula (2), R 3 The type of the substituent represented by the formula (I) is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. R 3In terms of the superior effect of the present invention, preferably represents a hydrogen atom or an alkyl group which may have a substituent, more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, further preferably represents a hydrogen atom or a methyl group, and particularly preferably represents a methyl group. Examples of the substituent which the above-mentioned alkyl group may have include the groups exemplified as the substituent W described later.

[0038] A preferred embodiment of the repeating unit represented by formula (2) is R 2 represents a group represented by the above general formula (R1A), and R 14 represents an aryl group, a benzyl group, an alkyl group, or a hydrogen atom (preferably an alkyl group which may have a substituent); R 3 represents a hydrogen atom or a methyl group (preferably a methyl group). Another preferred embodiment of the repeating unit represented by formula (2) is a repeating unit represented by formula (6).

[0039] [ka]

[0040] In general formula (6), R 3 and R 15 each independently represents a hydrogen atom or a substituent. R in general formula (6) 3 As the group, R in the general formula (2) 3 The same definition and preferred embodiments are also the same.

[0041] R 15 Examples of the substituent represented by the formula (I) include the groups exemplified as the substituent W described below. 15The substituent represented by is preferably an aryl group, an aralkyl group, an alkyl group, or a heteroaryl group, which may have a substituent, more preferably an aryl group, a benzyl group, or an alkyl group, which may have a substituent, and even more preferably an alkyl group, which may have a substituent. Note that the alkyl group preferably does not have an aryl group as a substituent. Furthermore, the substituent that the aryl group, the aralkyl group, the alkyl group, and the heteroaryl group may have is not particularly limited, and examples thereof include the groups exemplified as the substituent W described below. R 15 Among them, preferably represents an aryl group, a benzyl group, or an alkyl group which may have a substituent, or a hydrogen atom, and more preferably represents an alkyl group which may have a substituent.

[0042] The content of the repeating unit represented by formula (2) is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total repeating units in the specific polymer, and the upper limit is preferably 99.9% by mass or less, more preferably 99% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass or less. In the specific polymer, the repeating unit represented by formula (2) may be of one type alone or in combination of two or more types.

[0043] The specific polymer may contain repeating units other than the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) described above, as long as the effects of the present invention are not impaired.

[0044] The specific polymer can be synthesized according to a conventional method (for example, radical polymerization). The weight average molecular weight of the specific polymer, as calculated as polystyrene by the GPC method, is preferably from 1,000 to 100,000, more preferably from 1,000 to 20,000, further preferably from 1,500 to 15,000, and particularly preferably from 1,500 to 10,000. The dispersity (molecular weight distribution) of the specific polymer is preferably 1-3, more preferably 1.2-3, and even more preferably 1.2-2.

[0045] In the composition, the lower limit of the content of the specific polymer is preferably 0.001% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more, based on the total solid content of the composition. The upper limit of the content of the specific polymer is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 25% by mass or less, particularly preferably 20% by mass or less, and most preferably 15% by mass or less, based on the total solid content of the composition. In this specification, the "solid content" of a composition means all components excluding the solvent. In addition, any component other than the solvent that is in a liquid state is also considered to be a solid content. The specific polymer may be used alone or in combination of two or more.

[0046] (substituent W) The substituent W in this specification will be described. Examples of the substituent W include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group (which may also be called a heterocyclic group), a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group (including an anilino group), an ammonio group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonyl Examples of the substituent include an amino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl or arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkyl or arylsulfinyl group, an alkyl or arylsulfonyl group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a phosphono group, a silyl group, a hydrazino group, a ureido group, a boronic acid group (-B(OH)2), and other known substituents. The substituent W may be further substituted with a substituent W. For example, the alkyl group may be substituted with a halogen atom. Details of the substituent W are described in paragraph

[0023] of JP-A-2007-234651.

[0047] (Aryl group, alkyl group, and heteroaryl group that may be contained in a specific polymer) Examples of the aryl group, alkyl group, aralkyl group, and heteroaryl group that the specific polymer may have are shown below.

[0048] Unless otherwise specified, the number of carbon atoms in the aryl group of the specific polymer is preferably 6 to 30, more preferably 6 to 18, and even more preferably 6. The aryl group may be a monocyclic structure or a condensed ring structure (condensed ring structure) in which two or more rings are condensed. In addition, the aryl group may be substituted with a substituent (for example, the substituent W). The aryl group is, for example, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

[0049] Unless otherwise specified, the number of carbon atoms in the alkyl group of the specific polymer is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. The alkyl group may be substituted with a substituent (for example, the substituent W). Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a 2-ethylhexyl group, and a cyclohexyl group.

[0050] The aralkyl group of the specific polymer is a group in which one hydrogen atom of an alkyl group is replaced with an aryl group.The alkyl group part of the aralkyl group of the specific polymer is the same as the preferred embodiment of the alkyl group of the specific polymer described above.In addition, the aryl group part of the aralkyl group of the specific polymer is the same as the preferred embodiment of the aryl group of the specific polymer described above. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0051] Unless otherwise specified, the number of carbon atoms in the heteroaryl group (monovalent aromatic heterocyclic group) contained in the specific polymer is preferably 3 to 30, and more preferably 3 to 18. The heteroaryl group may be substituted with a substituent (for example, the substituent W). The heteroaryl group has a heteroatom other than carbon and hydrogen atoms, such as a sulfur atom, an oxygen atom, a nitrogen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and is preferably a sulfur atom, an oxygen atom, or a nitrogen atom. Unless otherwise specified, the number of heteroatoms in the heteroaryl group is usually about 1 to 10, preferably 1 to 4, and more preferably 1 or 2. Unless otherwise specified, the number of ring members of the heteroaryl group is preferably 3 to 8, more preferably 5 to 7, and further preferably 5 to 6. The heteroaryl group may have a monocyclic structure or a condensed ring structure in which two or more rings are condensed. In the case of a condensed ring structure, an aromatic hydrocarbon ring (e.g., a benzene ring) having no heteroatom may be included.

[0052] A specific example of the specific polymer is shown below. In the following, repeating unit (A), repeating unit (B), and repeating unit (C) refer to repeating units derived from the monomers shown in the columns for repeating unit (A), repeating unit (B), and repeating unit (C), respectively. In addition, "Me" in the polymer represents a methyl group, and "Et" represents an ethyl group.

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [Thermoplastic resin] The composition includes a thermoplastic resin. The thermoplastic resin is a resin different from the specific polymer described above. The thermoplastic resin is not particularly limited, and examples thereof include polyamide resins, polyolefin resins, polyester resins, polyurethane resins, polyether ketone resins, polyether resins, polyimide resins, polyarylene sulfide resins, polyarylene ether resins, and polycarbonate resins.

[0060] As the thermoplastic resin, it is preferable that the resin is at least one selected from the group consisting of polyamide resins and polyolefin resins, and it is more preferable that the resin is a polyamide resin.

[0061] Polyamide resins are polymers that have an acid amide bond (-CONH-) in the main chain. Examples of such polyamide resins include nylon 6 (also known as poly(caprolactam)), nylon 11 (also known as poly(11-aminoundecanoic acid)), nylon 12 (also known as poly(lauryllactam) or poly(12-aminododecanoic acid)), nylon 6.6 (also known as poly(hexamethylene adipamide)), nylon 6.9 (also known as poly(hexamethylene azelamide) or poly(hexamethylene nonanediamide)), nylon 6.10 (also known as poly(hexamethylene sebacamide) or Examples include poly(hexamethylene decanediamide)), nylon 6.12 (also known as poly(hexamethylene dodecanodiamide)), nylon 4 (also known as poly(delta-butyrolactam)), nylon 7 (also known as poly(7-aminoheptanoic acid) or poly(7-aminocaprylic acid)), nylon 8 (also known as poly(8-aminocaprylic acid) or poly(8-aminooctanoic acid)), nylon 10,6 (also known as poly(decamethylene adipamide)), and partially aromatic nylons (PARNS). Commercially available products include, for example, "Nylon 6" manufactured by Sigma-Aldrich and "Daiamide" manufactured by Daicel-Evonik.

[0062] Examples of polyolefin resins include crystalline or amorphous polypropylene, polybutene-1, poly-4-methylpentene, low-density or high-density polyethylene, random, block, or graft copolymers of ethylene-propylene, copolymers of α-olefins and ethylene or propylene, ethylene-alkyl (meth)acrylate copolymers, ethylene-(meth)acrylic acid copolymers, poly(meth)acrylates, resins made of metal ion-neutralized binary copolymers of olefins and α,β-unsaturated carboxylic acids, and resins made of metal ion-neutralized ternary copolymers of olefins, α,β-unsaturated carboxylic acids, and α,β-unsaturated carboxylic esters. In addition, in a resin composed of a metal ion-neutralized binary copolymer of an olefin and an α,β-unsaturated carboxylic acid, and a resin composed of a metal ion-neutralized ternary copolymer of an olefin, an α,β-unsaturated carboxylic acid, and an α,β-unsaturated carboxylic acid ester, the type and valence of the metal ion that neutralizes at least a portion of the carboxy groups are not particularly limited, and examples include monovalent metal ions such as sodium, potassium, and lithium; divalent metal ions such as magnesium, calcium, zinc, barium, and cadmium; trivalent metal ions such as aluminum; and other ions such as tin and zirconium.

[0063] In the composition, the lower limit of the content of the thermoplastic resin is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 30% by mass or more, and particularly preferably 60% by mass or more, based on the total solid content of the composition. The upper limit of the content of the thermoplastic resin is preferably 99.999% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99% by mass or less, based on the total solid content of the composition. The thermoplastic resin may be used alone or in combination.

[0064] The combination of the specific polymer and the thermoplastic resin is preferably selected from the viewpoint of compatibility between the repeating unit represented by general formula (2) contained in the specific polymer and the thermoplastic resin. The combination of the repeating unit represented by general formula (2) contained in the specific polymer and the thermoplastic resin is preferably in the following form in terms of excellent compatibility between the two (and thus in terms of ease of obtaining a uniformly colored resin molded product). Suitable embodiments of the thermoplastic resin in which the repeating unit represented by formula (2) is a repeating unit derived from a (meth)acrylate include polyolefin resins, polyamide resins, polyurethane resins, and polyester resins. Preferred embodiments of the thermoplastic resin in which the repeating unit represented by formula (2) is a repeating unit derived from (meth)acrylic acid include polyolefin resins and polyamide resins. A preferred embodiment of the thermoplastic resin in which the repeating unit represented by formula (2) is a repeating unit derived from styrene is a polyolefin resin.

[0065] [Other additives] The composition may contain additives other than the specific polymer and thermoplastic resin. The additives can be appropriately selected depending on the application, and are not particularly limited. Examples of the additives include flame retardants, antioxidants, weather resistance agents, release agents, lubricants, plasticizers, fillers, and reinforcing materials.

[0066] [Manufacturing method] The method for producing the composition is not particularly limited, but may be, for example, a method of premixing the specific polymer, thermoplastic resin, and any additives as raw material components as necessary, and then melt-kneading. The melt-kneading is preferably performed by heating to a temperature equal to or higher than the melting point of the thermoplastic resin. After melt-kneading, it is preferable to extrude the mixture into a strand shape, cut it, and mold it into granules such as pellets and chips. As the melt kneader, for example, a Banbury mixer, a mixing roll, a single-screw or twin-screw extruder, or a melt kneader equipped with a heating mechanism, such as a kneader, can be used.

[0067] [Application] The composition can be processed into a resin molded product having a desired shape by various melt moldings such as injection molding, compression molding, extrusion molding such as composites, sheets, and pipes, pultrusion molding, blow molding, and transfer molding. The shape of the resin molded product is not particularly limited, but examples thereof include fibers, sheets, and films. The obtained resin molded product also has excellent sweat resistance.

[0068] The composition can also be used as a resin coloring composition (resin coloring masterbatch). Specifically, the composition can be mixed with a diluent resin, which is a thermoplastic resin, to form a resin molded product with a desired color. The obtained resin molded product also has excellent sweat resistance. When the above composition is used as a resin coloring composition (resin coloring masterbatch), it is preferable to set the content of the specific polymer in the composition to a relatively high concentration in order to broaden the color selection range. When used as a resin coloring masterbatch, the content of the specific polymer in the composition is preferably 10 to 70 mass% based on the total solid content of the composition. When the above composition is used as a resin coloring composition (resin coloring master batch), the blending ratio of the resin coloring composition (resin coloring master batch) to the diluting resin (thermoplastic resin) is not particularly limited. In one embodiment, the blending amount of the resin coloring composition is preferably 1 to 50 parts by mass, more preferably 3 to 10 parts by mass, per 100 parts by mass of the diluting resin (thermoplastic resin).

[0069] The diluent resin is a thermoplastic resin as described above, and examples thereof include the same resins as the thermoplastic resin contained in the above-mentioned composition. Among them, a polyamide resin or a polyolefin resin is preferable, and a polyamide resin is more preferable. The diluent resin to which the resin coloring composition is applied is preferably selected from the viewpoint of compatibility between the thermoplastic resin and the diluent resin contained in the resin coloring composition. The combination of the thermoplastic resin and the diluent resin contained in the resin coloring composition is preferably the following in terms of excellent compatibility between the two (and thus in terms of the ease of obtaining a uniformly colored resin molding). In the case where the thermoplastic resin contained in the resin coloring composition is a polyamide resin, a suitable embodiment of the diluent resin includes a polyamide resin, a polyurethane resin, and a polyolefin resin (preferably a poly(meth)acrylate), etc. Among them, a polyamide resin is preferable. When the thermoplastic resin contained in the resin coloring composition is a polyolefin resin, a suitable embodiment of the diluent resin is a polyolefin resin.

[0070] As a method for mixing the resin coloring composition with the diluted resin, a manufacturing method can be mentioned in which the resin coloring composition (resin coloring master batch), the thermoplastic resin as the diluted resin, and any additive components are premixed as necessary, and then melt-kneaded. It is preferable to heat the resin coloring composition to a temperature higher than the melting point of the thermoplastic resin and the diluted resin as the thermoplastic resin. After melt-kneading, it is preferable to extrude the resin into a strand shape, cut it, and mold it into granules such as pellets and chips. The melt kneader that can be used can be the melt kneader described above.

[0071] The colored resin composition obtained by mixing the resin coloring composition with the diluted resin can be processed into a resin molded product having a desired shape by various melt moldings such as injection molding, compression molding, extrusion molding such as composites, sheets, and pipes, pultrusion molding, blow molding, and transfer molding. The shape of the obtained resin molded product is not particularly limited, and examples thereof include fibers, sheets, and films.

[0072] [Polymer (polymer for resin coloring)] The present invention also relates to a polymer. The polymer of the present invention is a polymer containing a repeating unit represented by the above general formula (4) and a repeating unit represented by the above general formula (2). The polymer of the present invention corresponds to one embodiment of the specific polymer described above, and the preferred embodiments thereof are the same as those of the specific polymer described above. The polymer of the present invention can stably function as a colorant for a resin even when used in a high concentration. EXAMPLES

[0073] The present invention will be described in more detail below based on examples. The materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0074] [Synthesis example] [Examples of synthesis of specific polymers] <Synthesis Example 1 (Synthesis of Monomer M-1)> The monomer M-1 shown below was synthesized with reference to JP-A-11-130817. The specific procedure is as follows. Coumarin 7 (20 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in N,N-dimethylacetamide (300 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution, to which tert-butoxypotassium (7.14 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 30 minutes under a nitrogen stream. Next, nitrobenzene (0.3 mL, Fujifilm Wako Pure Chemical Industries, Ltd.), sodium iodide (13.5 g, Fujifilm Wako Pure Chemical Industries, Ltd.), and 4-chloromethylstyrene (11.9 g, Tokyo Chemical Industry Co., Ltd.) were further added to the stirred solution, and the solution was stirred at 50° C. for 2 hours. After the stirring, the solution was returned to room temperature, diluted with ethyl acetate, and water was added to separate the solution. After the separation, the organic phase was concentrated to precipitate a yellow solid, which was filtered and dried to obtain monomer M-1.

[0075] [ka]

[0076] <Synthesis Example 2 (Synthesis of Monomer M-2)> Monomer M-2 shown below was synthesized by the same procedure as for the synthesis of monomer M-1, except that allyl bromide (9.43 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of 4-chloromethylstyrene.

[0077] [ka]

[0078] <Synthesis of polymer P-1> The synthesized monomer M-1 (0.5 g) and methyl methacrylate (4.5 g, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in DMAc ((dimethylacetamide) 20 g, Fujifilm Wako Pure Chemical Industries, Ltd.), and stirred at 85 ° C. for 3 hours under a nitrogen stream. Next, V-601 (0.74 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the stirred liquid, and the mixture was further stirred for 1 hour. Then, V-601 (0.32 g, Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the mixture was further stirred for 2 hours. After the stirring, the mixture was returned to room temperature, water (900 mL) was added to perform reprecipitation, and the precipitate was filtered and dried to obtain polymer P-1. It was confirmed that the weight average molecular weight of polymer P-1 was 4000 by GPC measurement.

[0079] <Synthesis of polymers P-2 to P-7> Polymers P-2 to P-7 were synthesized in accordance with the synthesis method for polymer P-1, except that the monomer types were changed as shown in Table 1. In Table 1, "MMA" means methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), "MAA" means methacrylic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and "BzMA" means benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The compositions of polymers P-1 to P-7 are shown in Table 1. In Table 1, the "mass %" shown in the "raw material monomer 1" to "raw material monomer 3" columns indicates the content of each repeating unit derived from "raw material monomer 1" to "raw material monomer 3" relative to the total repeating units in each polymer.

[0080] [Table 1]

[0081] [Preparation and evaluation of compositions of examples and comparative examples] [Preparation of compositions of examples and comparative examples] <Example 1> Polymer P-1 and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of polymer P-1 was 1 mass% relative to the content of polyamide resin, and kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0082] <Example 2> Colored pellets of Example 2 were prepared in the same manner as in Example 1, except that polymer P-2 was used instead of polymer P-1.

[0083] <Example 3> Colored pellets of Example 3 were prepared in the same manner as in Example 1, except that polymer P-3 was used instead of polymer P-1.

[0084] <Example 4> Colored pellets of Example 4 were prepared in the same manner as in Example 1, except that polymer P-4 was used instead of polymer P-1.

[0085] <Example 5> Polymer P-5 and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of polymer P-5 was 0.5 mass% relative to the total amount of polyamide resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0086] <Example 6> Polymer P-6 and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of polymer P-6 was 0.2 mass% relative to the content of polyamide resin, and kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0087] <Example 7> Colored pellets of Example 7 were prepared in the same manner as in Example 1, except that polymer P-7 was used instead of polymer P-1.

[0088] <Example 8> Polymer P-6 and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of polymer P-6 was 50 mass% relative to the content of polyamide resin, and kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0089] <Example 9> Polymer P-1 and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of polymer P-1 was 1 mass% relative to the content of polyethylene resin, and kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0090] <Example 10> Colored pellets of Example 10 were prepared in the same manner as in Example 9, except that polymer P-2 was used instead of polymer P-1.

[0091] <Example 11> Colored pellets of Example 11 were prepared in the same manner as in Example 9, except that polymer P-3 was used instead of polymer P-1.

[0092] <Example 12> Colored pellets of Example 12 were prepared in the same manner as in Example 9, except that polymer P-4 was used instead of polymer P-1.

[0093] <Example 13> Polymer P-5 and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of polymer P-5 was 0.5 mass% relative to the content of polyethylene resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0094] <Example 14> Polymer P-6 and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of polymer P-6 was 0.2 mass% relative to the content of polyethylene resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0095] <Example 15> Colored pellets of Example 15 were prepared in the same manner as in Example 9, except that polymer P-7 was used instead of polymer P-1.

[0096] <Example 16> Polymer P-6 and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of polymer P-6 was 50 mass% relative to the content of polyethylene resin, and kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0097] <Example 17> Polymer P-1 and polyester resin (product name "Polyethylene terephthalate", manufactured by Unitika Ltd.) were mixed so that the content of polymer P-1 was 1 mass% relative to the content of polyester resin, and the mixture was kneaded in a twin-screw extruder set at a cylinder temperature of 280°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0098] <Example 18> Colored pellets of Example 18 were prepared in the same manner as in Example 17, except that polymer P-2 was used instead of polymer P-1.

[0099] <Example 19> Colored pellets of Example 19 were prepared in the same manner as in Example 17, except that polymer P-3 was used instead of polymer P-1.

[0100] <Example 20> Colored pellets of Example 20 were prepared in the same manner as in Example 17, except that polymer P-4 was used instead of polymer P-1.

[0101] <Example 21> Polymer P-5 and polyester resin (product name "Polyethylene terephthalate", manufactured by Unitika Ltd.) were mixed so that the content of polymer P-5 was 0.5 mass% relative to the content of polyester resin, and the mixture was kneaded in a twin-screw extruder set at a cylinder temperature of 280°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0102] <Example 22> Polymer P-6 and polyester resin (product name "Polyethylene terephthalate", manufactured by Unitika) were mixed so that the content of polymer P-6 was 0.2 mass% relative to the content of polyester resin, and the mixture was kneaded in a twin-screw extruder set at a cylinder temperature of 280°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0103] <Example 23> Colored pellets of Example 23 were prepared in the same manner as in Example 17, except that polymer P-7 was used instead of polymer P-1.

[0104] <Comparative Example 1> Comparative compound C-1 described below and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of comparative compound C-1 was 0.1 mass% relative to the content of the polyamide resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0105] <Comparative Example 2> Comparative compound C-2 described later and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of comparative compound C-2 was 0.1 mass% relative to the content of the polyamide resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0106] <Comparative Example 3> Comparative compound C-2 described later and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of comparative compound C-2 was 25 mass% relative to the content of the polyamide resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0107] <Comparative Example 4> Comparative compound C-1 described below and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of comparative compound C-1 was 0.1 mass% relative to the content of polyethylene resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0108] <Comparative Example 5> Comparative compound C-2 described below and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of comparative compound C-2 was 0.1 mass% relative to the content of polyethylene resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0109] <Comparative Example 6> Comparative compound C-2 described below and polyethylene resin (product name "Sumikasen", manufactured by Sumitomo Chemical Co., Ltd.) were mixed so that the content of comparative compound C-2 was 25 mass% relative to the content of polyethylene resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm to produce colored pellets.

[0110] [ka]

[0111] [Evaluation of the compositions of the examples and comparative examples] The compositions of the Examples and Comparative Examples were evaluated as follows (evaluation of light resistance and sweat resistance). In the evaluation, each composition (colored pellet) of the Examples and Comparative Examples was heated and molded to prepare a resin film having a thickness of 2 mm, which was used as an evaluation sample. <Light resistance evaluation> A light resistance test was carried out on each resin film of the examples and comparative examples. Specifically, the resin film was exposed to light for 45 hours using a xenon lamp (product name "BXDN-500N", manufactured by Nowdata), and the degree of fading was visually observed and evaluated based on the following evaluation criteria. (Lightfastness evaluation: Evaluation criteria) "A": Less fading "B": Moderate degree of fading "C": High degree of fading The results are shown in Table 2.

[0112] <Sweat resistance evaluation> A sweat resistance test was carried out on each resin film of the Examples and Comparative Examples. Specifically, a cloth soaked in artificial sweat (Kishida Chemical) for 30 minutes was placed on the resin film and pressure was applied at 40°C for 4 hours, and the degree of fading was visually observed and evaluated based on the following evaluation criteria. (Sweat resistance evaluation: Evaluation criteria) "A": Less fading "B": High degree of fading The results are shown in Table 2.

[0113] [Table 2]

[0114] As shown in Table 2, it is clear that the compositions of the examples are excellent in light fastness and sweat fastness. Furthermore, from the results of Examples 1 to 23, it was confirmed that when the repeating unit represented by general formula (1) in the specific polymer is a repeating unit represented by general formula (5), the light resistance is superior (results of Examples 7, 15, 23, etc.). Furthermore, from the results of Examples 1 to 23, it was confirmed that when the repeating unit represented by general formula (2) in the specific polymer satisfies the following condition 1 or condition 2 (preferably satisfies condition 2), the light resistance tends to be more excellent (results of Examples 10, 11, 18 to 20, etc.). Condition 1: In the repeating unit represented by the general formula (2) in the specific polymer, R 2 represents a group represented by the above general formula (R1A), and R 14 represents an alkyl group which may have a substituent; R 3 represents a hydrogen atom or a methyl group. Condition 2: The content of the repeating units satisfying condition 1 is 50% by mass or more based on the total repeating units in the specific polymer. On the other hand, the comparative compositions did not meet the desired requirements.

[0115] [Example 24: Performance evaluation as a resin coloring composition] The colored pellets produced in Example 8 and polyamide resin (nylon 6, manufactured by Sigma-Aldrich) were mixed so that the content of the colored pellets produced in Example 8 was 4% by mass relative to the content of the polyamide resin, and the mixture was kneaded using a twin-screw extruder set at a cylinder temperature of 270°C and a screw rotation speed of 100 rpm to produce colored pellets. The obtained colored pellets were then heated and formed to produce a resin film with a thickness of 2 mm. When the produced resin film was visually observed, it was confirmed that the polyamide resin was uniformly colored. In addition, the above-mentioned light resistance evaluation and sweat resistance evaluation were performed on the produced resin film, and it was confirmed that the degree of fading was small in both cases (evaluated as "A").

Claims

1. A polymer including a repeating unit represented by the following general formula (5) and a repeating unit represented by the following general formula (6), A composition comprising: 【Chemistry 1】 In formula (6), R 3 represents a hydrogen atom or a methyl group, and R 15 represents an aryl group, a benzyl group, or an alkyl group which may have a substituent, or a hydrogen atom.

2. The composition according to claim 1, wherein the thermoplastic resin is at least one selected from the group consisting of polyamide resins and polyolefin resins.

3. The polymer is The weight average molecular weight is 1,000 to 100,000, and 3. The composition according to claim 1, wherein the content of the repeating unit represented by the general formula (5) is 0.1 to 50 mass % based on all repeating units in the polymer.

4. A composition for resin coloring comprising the composition according to any one of claims 1 to 3.

5. A polymer comprising a repeating unit represented by the following general formula (5) and a repeating unit represented by the following general formula (6): 【Chemistry 2】 In formula (6), R 3 represents a hydrogen atom or a methyl group, and R 15 represents an aryl group, a benzyl group, or an alkyl group which may have a substituent, or a hydrogen atom.

6. The weight average molecular weight is 1,000 to 100,000, and The polymer according to claim 5, wherein the content of the repeating unit represented by the general formula (5) is 0.1 to 50 mass % based on all repeating units in the polymer.

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