JP2019001933A - Colored resin, resin composition, and method for producing colored resin - Google Patents

Abstract

To provide a colored resin in which a specific resin is covalently linked with a dye stuff, and which can be easily produced and resists decoloring.SOLUTION: A colored resin has a resin (A) containing at least one selected from the group consisting of an amide resin, a vinyl alcoholic resin and polysaccharide, covalently linked with a dye stuff.SELECTED DRAWING: None

Description

  The present invention relates to a novel colored resin, a resin composition containing the colored resin, and a method for producing the colored resin.

  Resins have various physical properties depending on the functional group, molecular weight, and stereoregularity in the molecular structure, and are utilized utilizing the physical properties. Moreover, it is common that resin is processed and used for molded objects, such as a film and a fiber.

  Such a resin and its molded body may be used by coloring depending on the application. As a method for coloring the resin, a method using a dye or a pigment is generally used, and among them, a method using a dye is widely adopted. As dyes, direct dyes, reactive dyes, acid dyes, cationic dyes, vat dyes, naphthol dyes, and disperse dyes are known.

  As a method for coloring a resin using a dye, in addition to a method for adsorbing a dye on a resin, a method for bonding a dye to a resin is also known. Examples of the bond include van der Waals bonds, hydrogen bonds, and ionic bonds. However, in the method in which the dye is bonded to the resin by these bonds, the interaction between the dye and the resin and the strength of the bond are not sufficient, and the phenomenon that the dye is detached from the resin after coloring, that is, bleeding out or color transfer. Etc. may occur.

  As a solution to this problem, a method in which a dye is bonded to a resin by a covalent bond has been reported. For example, a method in which polyolefin, a dye having a polymerizable group, and a polymerization initiator are melt-kneaded and graft polymerized (Patent Document 1), an acrylate monomer or a styrene monomer and a dye having a polymerizable group are dissolved in a solvent. A method (Patent Document 2) of radical polymerization by adding a polymerization initiator has been proposed.

International Publication No. 2016/002842 International Publication No. 2014/126167 JP 2005-146474 A

  However, Patent Documents 1 and 2 describe only coloring methods for some types of resins. In the method described in Patent Document 1, it is difficult to control side reactions such as gelation during the reaction when the polyolefin, the dye having a polymerizable group, and the polymerization initiator are melt-kneaded and graft polymerization is performed. In particular, since many of hydrophilic resins such as polyvinyl alcohol are decomposed when melted or gelled by cross-linking between molecules, the method described in Patent Document 1 is used for coloring hydrophilic resins such as polyvinyl alcohol. Cannot be adopted.

In addition, hydrophilic resins such as vinyl alcohol resins have poor dyeability, and there are problems in terms of hue sharpness, darkness, and dyeing fastness. As a solution to this problem, a method of blending a specific polyvinyl alcohol-based resin with a specific resin having good dyeability has been proposed (Patent Document 3). However, in the method described in Patent Document 3, since the resin as the main component and other resins are blended, the properties (for example, hydrophilicity and strength) of the resin as the main component are impaired, and dye bleeding is also caused. The problem of out and color transfer could not be solved.
Therefore, at present, no colored resin having high hydrophilicity and difficult to decolorize has been reported.

The present invention has been made in order to solve the above-mentioned problems. The object of the present invention is to provide a coloring resin having a dye covalently bonded to a specific resin (A), which is easy to manufacture and difficult to decolorize, and a resin composition containing such a coloring resin. And providing a method for producing a colored resin.
Another object of the present invention is to provide a colored resin having a high hydrophilicity, easily produced, difficult to decolorize, and having a dye covalently bonded to the specific resin (A).
Another object of the present invention is to provide a colored resin in which a dye is covalently bonded to a specific resin (A), which is easy to produce, difficult to decolorize, and maintains the properties (for example, water solubility) of the resin (A). There is also.

Such an object is achieved by the present inventions (1) to (14) below.
(1) A colored resin in which a dye is covalently bonded to a resin (A) containing at least one selected from the group consisting of amide resins, vinyl alcohol resins and polysaccharides;
(2) The colored resin according to (1), wherein the resin (A) is the vinyl alcohol resin and / or the polysaccharide;
(3) The colored resin according to (1) or (2), wherein the resin (A) is the vinyl alcohol resin;
(4) The colored resin according to any one of (1) to (3), wherein the dye has a maximum absorption peak in a wavelength range of 500 to 700 nm in the visible light absorption spectrum;
(5) The colored resin according to any one of (1) to (4), wherein the pigment is a dye;
(6) The colored resin according to any one of (1) to (5) above, wherein the yellow index (YI) measured according to ASTM D1925 is 0 or less;
(7) The colored resin according to any one of (1) to (6), which is a graft copolymer;
(8) The colored resin according to any one of (1) to (7), including 0.01 to 20 parts by mass of the pigment with respect to 100 parts by mass of the resin (A);
(9) A resin composition comprising the colored resin according to any one of (1) to (8) above;
(10) The resin composition according to (9), further including a hydrophilic resin;
(11) The resin composition according to (10), wherein the hydrophilic resin is a vinyl alcohol resin;
(12) By radically polymerizing a resin (A) containing at least one selected from the group consisting of an amide resin, a vinyl alcohol resin and a polysaccharide, and a dye having a polymerizable group in a liquid medium. A method for producing a colored resin, comprising a step of obtaining a colored resin obtained by covalently bonding the dye to the resin (A);
(13) The method for producing a colored resin according to (12), wherein the radical polymerization is performed by irradiating the resin (A) with active energy rays.
(14) After the radical polymerization irradiates the resin (A) with active energy rays, the resin (A) irradiated with the active energy rays is placed in the liquid medium containing the dye having the polymerizable group. The method for producing a colored resin according to (12) or (13), which is carried out by adding.

  According to the present invention, it is possible to provide a colored resin that is easy to manufacture and difficult to decolorize, in which a dye is covalently bonded to a specific resin (A). Moreover, in the specific aspect of this invention, high hydrophilicity can be provided to the said colored resin, or the characteristic (for example, water solubility) of resin (A) can be maintained.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
(Colored resin)
In the colored resin of the present invention, a dye is covalently bonded to a resin containing one selected from the group consisting of amide resins, vinyl alcohol resins and polysaccharides (hereinafter sometimes referred to as “resin (A)”). Resin. Since the dye is covalently bonded to the resin (A), the colored resin of the present invention is difficult to decolorize. That is, bleeding out and migration of the dye are prevented, and the colored resin of the present invention can provide stable color development.

  Although it does not specifically limit as amide-type resin, For example, aliphatic polyamide, such as nylon 6, nylon 6,6, nylon 6,10, nylon 6,12, nylon 11, nylon 12, nylon 4,6; aromatic polyamide; Aromatic-aliphatic polyamides. Among these, aliphatic polyamide is preferable as the amide-based resin from the viewpoint of suppressing dye decomposition during processing due to a high melting point. One amide resin may be used alone, or two or more amide resins may be used in combination. In the present specification, the amide resin means a resin having an amide bond.

  Although it does not specifically limit as vinyl alcohol-type resin, For example, polyvinyl alcohol, an ethylene- vinyl alcohol copolymer etc. are mentioned, These 1 type may be used individually or may be used in combination of 2 or more type. In the present specification, the vinyl alcohol resin means that the structural unit derived from vinyl alcohol is 20 mol% or more, preferably 40 mol% or more, more preferably, with respect to all structural units constituting the vinyl alcohol resin. It means a resin containing 50 mol% or more, more preferably 56 mol% or more.

  The content of the structural unit derived from ethylene in the ethylene-vinyl alcohol copolymer is not particularly limited, but is preferably 60 mol% or less, more preferably based on all structural units constituting the ethylene vinyl alcohol copolymer. It is 50 mol% or less, More preferably, it is 44 mol% or less, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more, More preferably, it is 20 mol% or more. When the content of the structural unit derived from ethylene is not more than the above upper limit, the gas barrier property is excellent, and when the content is not less than the above lower limit, the molding processability is excellent.

  The polysaccharide is not particularly limited, and examples thereof include starch, cellulose, chitin, chitosan, hemicellulose, pectin, pullulan, agar, alginic acid, carrageenan, dextran, chitin derivative, chitosan derivative, and the like. It may be used or two or more types may be used in combination. In addition, as the chitin derivative, for example, a deacetylated structure of chitin in which the acetyl group of (1 → 4) -2-acetamido-2-deoxy-β-D-glucan structure is partially or completely removed from the amino group Is mentioned. In addition, as chitosan derivatives, for example, a part of a deacetylated amino group of a chitin deacetylated structure or a part of a hydroxyl group present in the same molecule is converted into an acylation reaction, an etherification reaction, an esterification Structures that have been chemically modified by reaction or other reactions are exemplified.

Among these resins, the resin (A) is a vinyl alcohol resin and / or a polysaccharide because it has excellent crystallinity, high hydrophilicity (water solubility), and is difficult to be colored by a general method. A vinyl alcohol resin (particularly polyvinyl alcohol) is more preferable. When the resin (A) is a vinyl alcohol resin or a polysaccharide, the colored resin of the present invention can maintain hydrophilicity equivalent to that of the vinyl alcohol resin or polysaccharide to which a dye is not covalently bonded.
The vinyl alcohol resin may have at least one other structural unit different from the structural unit derived from vinyl alcohol and the structural unit derived from the vinyl ester monomer as long as the effects of the present invention are obtained. Good. However, the amount of other structural units contained in the vinyl alcohol resin is preferably less than 10 mol% with respect to all the structural units constituting the vinyl alcohol resin.

  Examples of such other structural units include structural units derived from α-olefin monomers such as ethylene, propylene, n-butene, isobutylene and 1-hexene; acrylic acid; methyl acrylate, ethyl acrylate, acrylic acid N -Derived from acrylate monomers such as propyl, i-propyl acrylate, N-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate Structural unit; methacrylic acid; methyl methacrylate, ethyl methacrylate, N-propyl methacrylate, i-propyl methacrylate, N-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, Dodecyl methacrylate, meta Structural units derived from methacrylic acid ester monomers such as octadecyl rilate; such as acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid, acrylamidepropyldimethylamine Structural units derived from acrylamide monomers; structural units derived from methacrylamide monomers such as methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid, methacrylamidepropyldimethylamine; methyl vinyl ether, Ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, Structural units derived from vinyl ether monomers such as t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane; structural units derived from unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile Structural units derived from vinyl halide monomers such as vinyl chloride and vinyl fluoride; structural units derived from vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride; allyl acetate, 2,3-diacetoxy-1- Structural units derived from allylic monomers such as allyloxypropane and allyl chloride; structural units derived from unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, fumaric acid and salts or esters thereof; such as vinyltrimethoxysilane Na Nirushiriru monomer-derived structural units; structural units derived from acetic acid ester monomers such as isopropenyl acetate; and the like.

  The saponification degree of the vinyl alcohol-based resin is not particularly limited, but is preferably 50 mol% or more, more preferably 80 mol% or more, and further preferably 95 mol% or more. A vinyl alcohol resin having a saponification degree within the above range is preferable because it has particularly high hydrophilicity (water solubility). The upper limit of the saponification degree of the vinyl alcohol resin is not particularly limited, but is preferably 99.99 mol%. The degree of saponification can be measured according to JIS K6726.

  Although the number average molecular weight of resin (A) used by this invention is not specifically limited, 4400-440000 are preferable normally, 11000-220,000 are more preferable, and 22000-190000 are further more preferable. In addition, the number average molecular weight in this invention is a value calculated | required by the gel permeation chromatography (GPC) method. For example, in the case of vinyl alcohol resin, it can be measured with a hexafluoroisopropanol (HFIP) column as a conversion value using standard polymethyl methacrylate.

Examples of the form of the resin (A) include powder, particles, granules, scales, pellets, and the like, and powder or particles are preferable. When the resin (A) is in the form of powder or particles, the specific surface area can be sufficiently increased, and the target amount of the dye can be more covalently bonded to the resin (A). From the viewpoint of ease of handling, the resin (A)
It is also a preferable aspect that the form of is a pellet form.

  When the resin (A) is in the form of powder, particles or pellets, the average particle diameter is not particularly limited, but is preferably 4000 μm or less, more preferably 3500 μm or less, and more preferably 3000 μm or less. More preferably, it is particularly preferably 2000 μm or less, and most preferably 1000 μm or less. When the average particle diameter is within the above range, the specific surface area of the resin particles is further increased, so that the dye can be efficiently covalently bonded to the resin (A). Although the lower limit of the average particle diameter of the resin particles is not particularly limited, it is usually 10 μm. In addition, the said average particle diameter means a volume average particle diameter, and can measure it in the state which disperse | distributed resin (A) in methanol using the laser diffraction apparatus "LA-950V2" by Horiba, Ltd.

In the colored resin of the present invention, the dye is covalently bonded to the resin (A). As this pigment, various dyes and various pigments can be used.
Examples of the dye include a direct reactive dye, an azo dye, a xanthene dye, a carotenoid dye, a flavonoid dye, a quinone dye, a polyphenol dye, an indole dye, a rhodamine dye, a triarylmethane dye, and a cyanine. And dyes such as aluminum dyes and aluminum lake dyes.
Examples of the pigment include organic pigments such as azo pigments and polycyclic pigments (eg, anthraquinone pigments, quinophthalone pigments, isoindoline pigments); chromate pigments, sulfide pigments, oxide pigments, silica pigments, and the like. Examples thereof include inorganic pigments such as acid salt pigments and phosphate pigments.
Among these, as the pigment, a dye is preferable. A colored resin in which a dye is covalently bonded to the resin (A) is preferable because it has a clear color and high light transmittance. Moreover, it is preferable that a pigment | dye is a pigment | dye which has a polymeric group from a viewpoint which can manufacture easily the colored resin of this invention which the pigment | dye covalently bonded to resin (A).

  The absorption wavelength of the dye is not particularly limited, and can be appropriately selected according to the target hue of the colored resin. For example, the dye preferably has a maximum absorption peak in the range of about 500 to 700 nm (preferably in the range of about 550 to 650 nm) in the visible light absorption spectrum. The colored resin in which such a dye is covalently bonded to the resin (A) has a blue color or a hue close to blue. By mixing such a colored resin with another resin, it is possible to reduce (improve) the degree of yellowing caused by the deterioration (for example, thermal deterioration) of the other resin.

  The colored resin of the present invention preferably has a yellow index (YI) measured according to ASTM D1925 of 0 or less, more preferably −20 or less, and further preferably −50 or less. When the YI of the colored resin is controlled in such a range, when the colored resin of the present invention is mixed with another resin, the degree of yellowing due to deterioration of the other resin can be more reliably reduced.

In the colored resin of the present invention, the dye may be covalently bonded to the resin (A), and the bonding mode of the dye to the resin (A) is not particularly limited. Accordingly, the colored resin of the present invention includes, for example, a graft copolymer including a structural unit in which the main chain includes the resin (A) and the side chain (graft chain) is derived from the pigment, and a block and a pigment including the resin (A). And a block copolymer having a block containing a structural unit derived from the above, a random copolymer of a monomer and a dye constituting the resin (A), and the like. Among these, the colored resin of the present invention is preferably a graft copolymer, more preferably a graft copolymer in which the main chain includes the resin (A) and the side chain includes a structural unit derived from a pigment. More preferably, it is a graft copolymer in which the main chain is composed of the resin (A) and the side chain includes a structural unit derived from a pigment. When the colored resin of the present invention is a graft copolymer, the characteristics (for example, crystallinity and solubility) of the resin (A) can be more reliably maintained, and the production tends to be easy. In the present invention, the graft copolymer may be one in which the side chain (graft chain) is composed of only one molecule of the dye, may be a polymer of a plurality of dyes, and other than the dye and the dye. It may be a polymerized monomer.

  The bonding mode of the dye to the resin (A) is not particularly limited, but it is preferable that the dye is directly covalently bonded to the carbon atom of the resin (A). When the coupling | bonding mode with respect to resin (A) of a pigment | dye is the said aspect, the colored resin of this invention is excellent in chemical stability. In particular, when the resin (A) is a vinyl alcohol-based resin, a saponification step may be included in the production of the colored resin of the present invention. When the binding mode of the dye to the resin (A) is the above embodiment, In the saponification step, the dye is hardly detached from the resin (A). The colored resin in which the binding mode of the dye to the resin (A) is the above-described embodiment can be produced by a production method described later in (Colored resin production method), for example.

  The amount of the dye covalently bonded to the resin (A) is appropriately set according to the target hue of the colored resin and is not particularly limited, but is 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin (A). It is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass. When the amount of the dye is controlled within the above range, the colored resin of the present invention can favorably maintain the physical properties (for example, crystallinity and solubility) of the resin (A) in which the dye is not covalently bonded.

  When the colored resin of the present invention is a graft copolymer, the graft ratio is not particularly limited, but is preferably 0.001 to 30%, and more preferably 0.01 to 20%. In the present invention, the graft ratio means a value calculated by the method described in the examples.

(Method for producing colored resin)
Although the manufacturing method in particular of the colored resin of this invention is not restrict | limited, For example, the following method is preferable. That is, by radically polymerizing a resin (A) containing at least one selected from the group consisting of an amide resin, a vinyl alcohol resin and a polysaccharide, and a dye having a polymerizable group in a liquid medium, A step of obtaining a colored resin obtained by covalently bonding a dye to the resin (A).

  Examples of the dye having a polymerizable group include a dye having a polymerizable group and a pigment having a polymerizable group. Here, the polymerizable group is not particularly limited as long as a radical polymerization reaction is possible, but is preferably an ethylenic polymerizable group. From the viewpoint of high reactivity, a (meth) acryloyl group, a vinyl group is preferable. It is more preferable that

As the dye having a polymerizable group, for example, a monomer having a structure of sulfatoethylsulfonic acid which is a reactive dye can be used. Moreover, you may synthesize | combine the dye which has a polymeric group by introduce | transducing a polymeric group into the dye mentioned above.
The pigment having a polymerizable group is, for example, a method of coating the surface of the above-described pigment particle (hereinafter also referred to as “pigment particle”) with a resin having a polymerizable group by coacervation, the surface of the pigment particle, and the like. Can be produced by a method of treating with a coupling agent having a polymerizable group (such as a silane coupling agent or a titanium coupling agent).

  A commercial item can also be used as a pigment | dye which has a polymeric group. For example, RDW series B01 (absorption wavelength: 624 nm) manufactured by Wako Pure Chemical Industries, Ltd., which is a direct reactive dye having a methacryloyl group, and Kiwa Chemical Industry Co., Ltd., which is a direct reactive dye having a sulfatoethylsulfonic acid structure. KP-ZOL series T.M. Blue G 150 (absorption wavelength 625 nm), Blue RN 150 (absorption wavelength 590 nm), Brill. And Blue BB 133 (absorption wavelength 609 nm).

By radically polymerizing the resin (A) and the dye having a polymerizable group in a liquid medium,
A colored resin (colored resin of the present invention) obtained by covalently bonding a dye to the resin (A) is obtained. That is, in the present invention, radical polymerization is performed in a liquid medium without melting and kneading the resin as in Patent Document 1 described above. For this reason, thermal decomposition and intense gelation of the resin (A) can be prevented. As a result, a colored resin that suitably maintains the characteristics of the resin (A) can be obtained.

  At this time, the method of radical polymerization is not particularly limited, and examples thereof include a method of adding a polymerization initiator and a method of irradiating the resin (A) with active energy rays. Among these, from the viewpoint of industrial convenience and suppression of homopolymerization of a dye having a polymerizable group, a method of irradiating the resin (A) with active energy rays is preferable. Examples of active energy rays include ionizing radiations such as α rays, β rays, γ rays, accelerating electron rays, and ultraviolet rays; X rays, g rays, i rays, excimer lasers, etc. Among them, ionizing radiation is preferable and practical. Is more preferably an accelerating electron beam or γ-ray, and more preferably an accelerating electron beam having a high processing speed and simple equipment.

  The radical polymerization is performed by adding resin (A) irradiated with active energy rays to a liquid medium containing a dye having the polymerizable group after I: resin (A) is irradiated with active energy rays. Alternatively, II may be carried out by irradiating the mixture containing the resin (A), the dye having a polymerizable group and the liquid medium with active energy rays, but the method I is more preferable. According to the method I, since active energy rays are irradiated to the resin (A) in advance, when the resin (A) and the dye having a polymerizable group are radically polymerized, homopolymerization of the dye having the polymerizable group is performed. Side reactions such as these hardly occur, and gelation due to intermolecular crosslinking between the resins (A) can also be suppressed.

  The radical polymerization is preferably performed by heating the liquid medium, and more preferably by heating and refluxing the liquid medium at a temperature slightly higher than the boiling point of the liquid medium. Further, it is preferable to replace the inside of the reaction system with an inert gas such as argon gas. If the inside of the reaction system is replaced with an inert gas, the disappearance of radicals generated in the resin (A) can be prevented or suppressed.

  The resin (A) before irradiation with active energy rays preferably has a moisture content of 15% by mass or less. When the moisture content of the resin (A) is 15% by mass or less, radicals generated in the resin (A) by irradiation with active energy rays are difficult to disappear, and the resin (A) for the dye having a polymerizable group Sufficient reactivity can be ensured.

  The irradiation dose of the active energy ray is not particularly limited, but is preferably about 5 to 200 kGy, more preferably about 10 to 150 kGy, further preferably about 20 to 100 kGy, and about 30 to 90 kGy. It is particularly preferred. When the irradiation dose of the active energy ray is within the above range, the target amount of the dye can be covalently bonded (radical polymerization) to the resin while suitably preventing an increase in the production cost of the colored resin and the deterioration of the resin.

  The resin (A) irradiated with active energy rays is added to a liquid medium containing a dye having a polymerizable group, and at this time, the resin (A) irradiated with active energy rays does not dissolve in the liquid medium. A dispersed state is preferable. That is, the liquid medium is preferably one that does not dissolve the resin (A) irradiated with active energy rays. If the liquid medium does not dissolve the resin (A), the progress of radical polymerization and the deactivation of radicals generated in the resin (A) do not proceed at the same time, so the amount of dye to be covalently bonded to the resin is controlled. Easy to do. In addition, although the pigment | dye which has a polymeric group does not need to melt | dissolve in a liquid medium, it is preferable to melt | dissolve. When the dye having a polymerizable group is dissolved in the liquid medium, radical polymerization with the resin is performed more rapidly. From such a viewpoint, the dye having a polymerizable group is preferably a dye having a polymerizable group.

Examples of the liquid medium include lower alcohols such as methanol, ethanol and isopropanol; ethers such as tetrahydrofuran, dioxane and diethyl ether; ketones such as acetone and methyl ethyl ketone; amides such as dimethylformamide and dimethylacetamide. Aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane, and the like. These may be used alone or in combination of two or more. When these liquid media are used, the resin (A) can be swollen, so that it is easy to radically polymerize a dye having a polymerizable group uniformly and in a large amount on the resin. Therefore, it is preferable to select the liquid medium to be used in consideration of the affinity with the resin (A).

  The usage-amount of the pigment | dye which has a polymeric group is suitably adjusted according to the reactivity with respect to resin (A). For example, when the particulate resin (A) is used as a raw material, the reactivity changes depending on the ease of penetration of the dye having a polymerizable group into the resin (A). Therefore, although the usage-amount of the pigment | dye which has a polymeric group is adjusted according to the kind and quantity of a liquid medium to be used, it is 0.1-200 mass parts with respect to 100 mass parts of resin (A), for example. It is preferably 0.5 to 100 parts by mass, and more preferably 1 to 50 parts by mass. When the amount of the dye having a polymerizable group is within the above range, a colored resin in which the amount of the dye covalently bonded to the resin (A) is within the above range can be obtained in high yield.

  Although the usage-amount of a liquid medium is not specifically limited, Usually, it is preferable that it is 100-4,000 mass parts with respect to 100 mass parts of resin (A), and it is more preferable that it is 200-2,000 mass parts, More preferably, it is 300-1500 mass parts.

  Note that the glass transition temperature of the polyolefin is not limited even when an attempt is made to covalently bond the dye to the resin other than the amide resin, vinyl alcohol resin and polysaccharide (for example, polyolefin) by applying the method for producing the colored resin of the present invention. Due to the low, the radicals generated in the polyolefin are very unstable. For this reason, the polyolefin in which radicals are generated can be handled only at extremely low temperatures so that the radicals do not disappear. Therefore, it is industrially difficult to apply a method for producing a colored resin that performs radical polymerization by irradiating the resin (A) with active energy rays to a resin having a low glass transition temperature such as polyolefin.

  The resin composition of the present invention includes the above colored resin. Thereby, according to the hue of colored resin, the resin composition can also be colored in the same hue as colored resin. In addition, although the resin composition of this invention may be comprised only with colored resin and may also contain other resin, when containing other resin, the resin of this invention is utilized especially effectively. For example, in general, many resins are colored yellow (yellowing) due to deterioration (for example, thermal deterioration), but a resin composition in which a colored resin having a hue close to blue or blue is mixed is yellowed. Is reduced.

  The other resin is not particularly limited, but is preferably a hydrophilic resin. Since the colored resin of the present invention also has hydrophilicity, when the other resin is a hydrophilic resin, the colored resin of the present invention and the other resin can be mixed more uniformly. Many hydrophilic resins have the property of easily yellowing, but the degree of yellowing can be reliably reduced by mixing a colored resin having a blue color or a hue close to blue.

Examples of the hydrophilic resin include amide resins, vinyl alcohol resins, polysaccharides, etc. Among them, vinyl alcohol resins are preferable. Since the vinyl alcohol-based resin is a resin that is particularly easily yellowed by forming a polyene structure by dehydration, it is extremely useful to mix the colored resin of the present invention.
Moreover, when mixing colored resin and other resin, the mixing amount of colored resin is not specifically limited, However, It is preferable that it is 0.01-100 mass parts with respect to 100 mass parts of other resin, 0.1. More preferably, it is 10 mass parts.

  The resin composition of the present invention may further include a solvent, an organic or inorganic filler, a coupling agent, a leveling agent, a photosensitive agent, an antifoaming agent, depending on the use of a molded article produced using the resin composition. You may contain various additives like a ultraviolet absorber, a foaming agent, antioxidant, and a flame retardant.

  As mentioned above, although the colored resin of this invention, the resin composition, and the manufacturing method of colored resin were demonstrated, this invention is not limited to these. For example, the colored resin and the resin composition of the present invention may contain other arbitrary components, respectively, or may be replaced with arbitrary components that exhibit the same function. Moreover, the manufacturing method of the colored resin of this invention may include the other process of the arbitrary objectives.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples.

[Calculation of graft ratio]
The difference in which the dry weight (Wg) of the resins obtained in Examples and Comparative Examples changed (increased) relative to the dry weight (W0) of the raw material resin was determined, and the graft ratio was calculated according to the following formula.
Graft ratio (%) = [(Wg−W0) / W0] × 100

[Measurement of Hue (Yellow Index; YI)]
YI (ASTM D1925) of the resin obtained in Examples and Comparative Examples was measured using a spectrocolorimeter (“CM-8500d” manufactured by Konica Minolta, Inc.). D65 was used as a light source, CM-A120 was used as a white calibration plate, and CM-A126 was used as a petri dish set. Further, YI was measured under conditions of SCE (regular reflection light removal) and measurement diameter φ30 mm. In this YI measurement, 5 g of the resin obtained in Examples and Comparative Examples was added to the petri dish, and the side of the petri dish was tapped and shaken so as not to suppress the resin (powder). It was spread evenly in the petri dish. In this state, YI was measured 10 times in total, and the average value was taken as YI of the resins obtained in the examples and comparative examples. Before the second and subsequent YI measurements, the petri dish was shaken again, and then the next YI measurement was performed.

[Evaluation of water solubility]
The raw material resin and the resins obtained in Examples and Comparative Examples were added to ion-exchanged water so as to have a concentration of 5% by mass and stirred at 100 ° C. to dissolve. Based on the dissolution rate and whether the dissolution state can be maintained, water solubility was evaluated according to the following criteria.
A: When it was stirred at 100 ° C. for 30 minutes, it was completely dissolved, and even after the internal temperature was lowered to 25 ° C., the completely dissolved state was maintained.
B: Although dissolution of a part of the resin was visually confirmed at the time of stirring at 100 ° C. for 30 minutes, and the residue of the gel-like insoluble matter was visually observed, or it was completely dissolved within 30 minutes after the temperature increase. When the internal temperature was lowered to 25 ° C. after complete dissolution, precipitation of a part of the resin was visually observed.
C: Even if it stirred for 30 minutes at 100 degreeC, the change of the state of resin was not confirmed visually.

[Example 1]
First, the electron beam (30 kGy) was irradiated to the polyvinyl alcohol particle (Kuraray Co., Ltd. product, "Elvanol 71-30"). The particle diameter of the polyvinyl alcohol particles was 0.3 to 300 μm. Moreover, the moisture content of the polyvinyl alcohol particles was 10% by mass.
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.) and methanol 19 A methanol solution in which a pigment having a polymerizable group was dissolved was obtained. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of polyvinyl alcohol particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) of polyvinyl alcohol and a dye having a polymerizable group. Thereafter, the polyvinyl alcohol particles colored from the methanol solution (hereinafter sometimes referred to as colored polyvinyl alcohol particles) were collected by filtration.
Next, in order to remove the pigment | dye which has an unreacted polymeric group, the coloring polyvinyl alcohol particle | grains was moved to the beaker, 200 mass parts of methanol was added, and it wash | cleaned, and collect | recovered after that. Subsequently, the collected colored polyvinyl alcohol particles were transferred to a beaker, and 45 parts by mass of ion-exchanged water was added to the beaker. Thereafter, the ion exchange water was heated to 100 ° C., and the colored polyvinyl alcohol particles were dissolved in the ion exchange water to obtain an aqueous solution. Next, this aqueous solution was added to 500 mL of methanol to precipitate colored polyvinyl alcohol (hereinafter sometimes referred to as colored polyvinyl alcohol). The above dissolution and precipitation operations were repeated 5 times, and it was confirmed that there was no elution of the dye having a polymerizable group, and then the colored polyvinyl alcohol was dried to obtain the desired graft copolymer colored polyvinyl alcohol. Obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored polyvinyl alcohol. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Example 2]
First, the electron beam (30 kGy) was irradiated to the polyvinyl alcohol particle (Kuraray Co., Ltd. product, "Elvanol 71-30").
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 0.1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.) 19 parts by mass of methanol was charged to obtain a methanol solution in which a dye having a polymerizable group was dissolved. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of polyvinyl alcohol particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) of polyvinyl alcohol and a dye having a polymerizable group. Washing, precipitation and drying after this operation were performed in the same manner as in Example 1. As described above, a colored polyvinyl alcohol which is a target graft copolymer was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored polyvinyl alcohol. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Example 3]
First, the electron beam (30 kGy) was irradiated to the polyvinyl alcohol particle (Kuraray Co., Ltd. product, "Elvanol 71-30").
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, a dye having a polymerizable group (“KP ZOL T. Blue G 150” manufactured by Kiwa Chemical Industry Co., Ltd.) 2.5 The methanol solution in which the pigment | dye which has a polymeric group melt | dissolved was prepared by charging a mass part, 47.5 mass parts of methanol, and 1.45 mass parts of 14 mass% sodium hydroxide methanol solution. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of polyvinyl alcohol particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) of polyvinyl alcohol and a dye having a polymerizable group. Washing, precipitation and drying after this operation were performed in the same manner as in Example 1. As described above, a colored polyvinyl alcohol which is a target graft copolymer was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored polyvinyl alcohol. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Example 4]
First, the electron beam (30 kGy) was irradiated to the polyvinyl alcohol particle (Kuraray Co., Ltd. product, "Elvanol 71-30").
Next, a dye having a polymerizable group (“KP ZOL T. Blue G 150”) 1.2 having a polymerizable group is added to a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port. The methanol solution in which the pigment | dye which has a polymeric group melt | dissolved was prepared by charging a mass part, 48.8 mass parts of methanol, and 0.73 mass part of 14 mass% sodium hydroxide methanol solution. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes. Thereby, the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of polyvinyl alcohol particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) of polyvinyl alcohol and a dye having a polymerizable group. Washing, precipitation and drying after this operation were performed in the same manner as in Example 1. As described above, a colored polyvinyl alcohol which is a target graft copolymer was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored polyvinyl alcohol. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Example 5]
First, an electron beam (30 kGy) was irradiated to ethylene-vinyl alcohol copolymer particles (manufactured by Kuraray Co., Ltd., “EVAL-F101”). The average particle size of the ethylene-vinyl alcohol copolymer particles was 102 μm.
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.) and methanol 19 A methanol solution in which a pigment having a polymerizable group was dissolved was obtained. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of ethylene-vinyl alcohol copolymer particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to carry out radical polymerization (graft polymerization) between the ethylene-vinyl alcohol copolymer and the dye having a polymerizable group. Thereafter, the colored ethylene-vinyl alcohol copolymer particles (hereinafter sometimes referred to as colored ethylene-vinyl alcohol copolymer particles) were recovered from the methanol solution by filtration.
Next, in order to remove the pigment | dye which has an unreacted polymeric group, the colored ethylene-vinyl alcohol copolymer particle | grains was moved to the beaker, 200 mass parts of methanol was added, and it wash | cleaned by stirring, and collect | recovered after that. Subsequently, the collected colored ethylene-vinyl alcohol copolymer particles were transferred to a beaker and added to 45 parts by mass of ion-exchanged water in the beaker. Thereafter, the ion exchange water was heated to 100 ° C., and the colored ethylene-vinyl alcohol copolymer particles were dissolved in the ion exchange water to obtain an aqueous solution. Next, this aqueous solution was added to 500 mL of methanol to precipitate a colored ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as a colored ethylene-vinyl alcohol copolymer). The above dissolution and precipitation operations were repeated 5 times, and after confirming that there was no elution of the dye having a polymerizable group, the colored ethylene-vinyl alcohol copolymer was dried. As described above, a colored ethylene-vinyl alcohol copolymer, which is a target graft copolymer, was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored ethylene-vinyl alcohol copolymer. Table 1 also shows the results of evaluating the water solubility of the starting ethylene-vinyl alcohol copolymer.

[Example 6]
First, corn-derived starch particles (Wako Pure Chemical Industries, Ltd.) were irradiated with an electron beam (30 kGy). The average particle size of the starch particles was 10 μm.
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.) and methanol 19 A methanol solution in which a pigment having a polymerizable group was dissolved was obtained. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of starch particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) between starch and a dye having a polymerizable group. Thereafter, the starch particles colored from the methanol solution (hereinafter sometimes referred to as colored starch particles) were collected by filtration.
Next, in order to remove the pigment | dye which has an unreacted polymeric group, the colored starch particle was moved to the beaker, 200 mass parts of methanol was added, it wash | cleaned by stirring, and it collect | recovered after that. Next, the collected colored starch particles were transferred to a beaker, and 45 parts by mass of ion-exchanged water was added to the beaker. Thereafter, the ion exchange water was heated to 100 ° C., and the colored starch particles were dissolved in the ion exchange water to obtain an aqueous solution. Next, this aqueous solution was added to 500 mL of methanol to precipitate colored starch. The above dissolution and precipitation operations were repeated 5 times, and after confirming that there was no elution of the dye having a polymerizable group, the colored starch (hereinafter sometimes referred to as colored starch) was dried. As described above, a colored starch which was the target graft copolymer was obtained. The evaluation results of various physical properties of the obtained colored starch are shown in Table 1. Table 1 also shows the results of evaluating the water solubility of the raw material starch.

[Example 7]
First, nylon 6 (manufactured by Ube Industries, Ltd., “SF1018A”) was pulverized to obtain nylon 6 particles having an average particle diameter of 200 μm, and then the nylon 6 particles were irradiated with an electron beam (30 kGy).
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.), 19 parts by mass of methanol The methanol solution in which the dye having a polymerizable group was dissolved was obtained. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of nylon 6 particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to carry out radical polymerization (graft polymerization) between nylon 6 and a dye having a polymerizable group. Thereafter, colored nylon 6 particles (hereinafter sometimes referred to as colored nylon 6 particles) were recovered from the methanol solution by filtration.
Next, in order to remove the dye having an unreacted polymerizable group, the colored nylon 6 particles were transferred to a beaker, washed by adding 200 parts by mass of methanol, and then collected. Next, the colored nylon 6 particles collected once were transferred to a beaker, and 45 parts by mass of ion-exchanged water was added to the beaker. Thereafter, the ion exchange water was heated to 100 ° C., and the colored nylon 6 particles were dissolved in the ion exchange water to obtain an aqueous solution. Next, this aqueous solution was added to 500 mL of methanol to precipitate colored nylon 6 (hereinafter sometimes referred to as colored nylon 6). The above dissolution and precipitation operations were repeated 5 times, and after confirming that there was no elution of the dye having a polymerizable group, the colored nylon 6 was dried. As described above, colored nylon 6 which is a target graft copolymer was obtained. The evaluation results of various physical properties of the obtained colored nylon 6 are shown in Table 1. Table 1 also shows the water solubility evaluation results of the raw material nylon 6.

[Example 8]
First, an electron beam (30 kGy) was irradiated to cellulose particles (manufactured by Asahi Kasei Chemicals Corporation, “Selfia (registered trademark) 203”). In addition, the average particle diameter of the cellulose particle was 150-300 micrometers.
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, 1 part by mass of a dye having a polymerizable group (“RDW B01” manufactured by Wako Pure Chemical Industries, Ltd.) and methanol 19 A methanol solution in which a pigment having a polymerizable group was dissolved was obtained. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of cellulose particles irradiated with an electron beam from the sample addition port were added to the methanol solution, and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes to perform radical polymerization (graft polymerization) between cellulose and a dye having a polymerizable group. Thereafter, the colored cellulose particles (hereinafter sometimes referred to as colored cellulose particles) were recovered from the methanol solution by filtration.
Next, in order to remove the pigment | dye which has an unreacted polymeric group, the colored cellulose particle was moved to the beaker, 200 mass parts of methanol was added, and it wash | cleaned by stirring, and collect | recovered after that. Next, the collected colored cellulose particles were transferred to a beaker, and 45 parts by mass of ion-exchanged water was added to the beaker. Thereafter, the ion exchange water was heated at 100 ° C. to dissolve the colored cellulose particles in the ion exchange water to obtain an aqueous solution. Next, this aqueous solution was added to 500 mL of methanol to precipitate colored cellulose (hereinafter sometimes referred to as colored cellulose). The above dissolution and precipitation operations were repeated 5 times to confirm that there was no elution of the dye having a polymerizable group, and then the colored cellulose was dried. As described above, a colored cellulose as the target graft copolymer was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored cellulose. Table 1 also shows the evaluation results of the water solubility of the raw material cellulose.

[Example 9]
To an aluminum zip produced by Nippon Shokuhin Co., Ltd., 5 parts by mass of polyvinyl alcohol particles (manufactured by Kuraray Co., Ltd., “Elvanol 71-30”) and a dye having a polymerizable group (manufactured by Wako Pure Chemical Industries, Ltd., “RDW B01”) “) 1 part by mass and 19 parts by mass of methanol were charged and mixed. Subsequently, after replacing the inside of an aluminum zip with argon, the electron beam (30 kGy) was irradiated. In this way, a colored polyvinyl alcohol which is the target graft copolymer was obtained.
Next, in order to remove the pigment | dye which has an unreacted polymeric group, the coloring polyvinyl alcohol particle | grains was moved to the beaker, 200 mass parts of methanol was added, and it wash | cleaned, and collect | recovered after that. Subsequently, the collected colored polyvinyl alcohol particles were transferred to a beaker, and 45 parts by mass of ion-exchanged water was added to the beaker. Thereafter, the ion-exchanged water was heated to 100 ° C. to dissolve the colored polyvinyl alcohol particles in the ion-exchanged water. Although there were undissolved portions, the subsequent operation was continued, and washing, precipitation and drying were performed in the same manner as in Example 1. As described above, a colored polyvinyl alcohol which is a target graft copolymer was obtained. Table 1 shows the evaluation results of various physical properties of the obtained colored polyvinyl alcohol. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Example 10]
Instead of 5 parts by mass of polyvinyl alcohol particles, 2.5 parts by mass of polyvinyl alcohol particles (manufactured by Kuraray Co., Ltd., “Elvanol 71-30”) and starch particles derived from corn (manufactured by Wako Pure Chemical Industries, Ltd.) 2.5 Except having used the mixture with a mass part, it carried out similarly to the said Example 1, and obtained the coloring mixture of the coloring polyvinyl alcohol which is the target graft copolymer, and coloring starch. Table 1 shows the evaluation results of various physical properties of the obtained colored mixture. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Comparative Example 1]
The polyvinyl alcohol particles were dried without irradiating the polyvinyl alcohol particles (“Elvanol 71-30” manufactured by Kuraray Co., Ltd.) with an electron beam. Table 1 shows the evaluation results of various physical properties of the polyvinyl alcohol particles. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Comparative Example 2]
First, the polyvinyl alcohol particles were dried without irradiating the polyvinyl alcohol particles (Kuraray Co., Ltd., “Elvanol 71-30”) with an electron beam.
Next, in a reactor equipped with a stirrer, a reflux condenser, an argon inlet, and a sample addition port, a dye having a polymerizable group (“KP ZOL T. Blue G 150” manufactured by Kiwa Chemical Industry Co., Ltd.) 2.5 The methanol solution in which the pigment | dye which has a polymeric group melt | dissolved was prepared by charging a mass part, 47.5 mass parts of methanol, and 1.45 mass parts of 14 mass% sodium hydroxide methanol solution. Thereafter, argon was introduced into the methanol solution from an argon inlet tube and bubbled for 30 minutes, whereby the inside of the reactor (inside the system) was replaced with argon.
Next, 5 parts by mass of polyvinyl alcohol particles were added to the methanol solution from the sample addition port and dispersed in the methanol solution by stirring. In this state, the methanol solution was heated to reflux for 300 minutes and stirred. Washing, precipitation and drying after this operation were performed in the same manner as in Example 1. Polyvinyl alcohol was obtained as described above. The evaluation results of various physical properties of the obtained polyvinyl alcohol are shown in Table 1. Table 1 also shows the results of evaluating the water solubility of the raw material polyvinyl alcohol.

[Reference Example 1]
5 parts by mass of polyvinyl alcohol particles (manufactured by Kuraray Co., Ltd., “Elvanol 71-30”) and 1 part by mass of a dye having a polymerizable group (manufactured by Wako Pure Chemical Industries, Ltd., “RDW B01”) were kneaded in advance. Thereafter, 0.05 part by mass of benzoyl peroxide (radical polymerization initiator) was added and melt kneaded to produce a colored resin, but polyvinyl alcohol was thermally decomposed and the desired colored resin could not be obtained. .

[Reference Example 2]
Instead of 5 parts by mass of the polyvinyl alcohol particles, an attempt was made to produce a colored resin in the same manner as in Reference Example 1, using 5 parts by mass of cellulose particles (Asahi Kasei Chemicals Corporation, “Selfia (registered trademark) 203”). However, the cellulose was thermally decomposed and the desired colored resin could not be obtained.

[Reference Example 3]
In place of 5 parts by mass of polyvinyl alcohol particles, an attempt was made to produce a colored resin in the same manner as in Reference Example 1 by using 5 parts by mass of nylon 6 (manufactured by Ube Industries, Ltd., “SF1018A”). The gelation of nylon 6 accompanying the reaction was intense, and the desired colored resin could not be obtained.

As shown in Table 1, in the colored resin of Comparative Example 2 obtained by simply blending a resin and a dye having a polymerizable group, the YI value is a positive value, and the dye is fixed to the resin. It can be seen that the dye is eluted in the washing and precipitation steps.
On the other hand, the colored resins obtained in Examples 1 to 10 have a negative YI value even after washing, indicating that the pigment is securely fixed to the resin.
In addition, in the colored resin of Example 9 obtained by irradiating an electron beam with respect to the mixture containing resin and the pigment | dye which has a polymeric group, water solubility is higher than the colored resin obtained in Examples 1-8. Declined. This is considered to be a result based on gelation in the radical polymerization reaction.
The colored resin thus obtained can be used as a resin composition alone or mixed with other resins. Thereby, a desired hue can be simply provided to the resin composition.

In addition, the same result is obtained even if it manufactures colored resin like the said Examples 1-9 using alpha rays, beta rays, gamma rays, and an ultraviolet ray instead of an electron beam.
Moreover, it replaces with the pigment | dye which has a polymeric group, and the same result is obtained even if it manufactures colored resin like the said Examples 1-9 using the pigment which has a polymeric group.
Further, even when a colored resin is produced in the same manner as in Examples 1 to 9 using a mixture of two or more of the resin particles described above as the resin, the same result can be obtained.
Furthermore, a colored resin that is a block copolymer or a random copolymer can be produced by appropriately setting the resin structure and conditions for radical polymerization.

Claims (14)

  A colored resin in which a dye is covalently bonded to a resin (A) containing at least one selected from the group consisting of amide resins, vinyl alcohol resins and polysaccharides.   The colored resin according to claim 1, wherein the resin (A) is a vinyl alcohol resin and / or a polysaccharide.   The colored resin according to claim 1 or 2, wherein the resin (A) is a vinyl alcohol resin.   The colored resin according to any one of claims 1 to 3, wherein the dye has a maximum absorption peak in a wavelength range of 500 to 700 nm in an absorption spectrum of visible light.   The colored resin according to claim 1, wherein the pigment is a dye.   The colored resin according to any one of claims 1 to 5, wherein a yellow index (YI) measured according to ASTM D1925 is 0 or less.   The colored resin according to any one of claims 1 to 6, which is a graft copolymer.   The colored resin according to any one of claims 1 to 7, comprising 0.01 to 20 parts by mass of the dye with respect to 100 parts by mass of the resin (A).   The resin composition containing the colored resin of any one of Claim 1 thru | or 8.   Furthermore, the resin composition of Claim 9 containing hydrophilic resin.   The resin composition according to claim 10, wherein the hydrophilic resin is a vinyl alcohol resin.   A resin (A) containing at least one selected from the group consisting of an amide resin, a vinyl alcohol resin and a polysaccharide, and a dye having a polymerizable group are radically polymerized in a liquid medium, whereby the resin The manufacturing method of colored resin provided with the process of obtaining the colored resin formed by covalently bonding the said pigment | dye to (A).   The method for producing a colored resin according to claim 12, wherein the radical polymerization is performed by irradiating the resin (A) with active energy rays.   The radical polymerization is performed by irradiating the resin (A) with active energy rays and then adding the resin (A) irradiated with the active energy rays into a liquid medium containing the dye having the polymerizable group. The manufacturing method of the colored resin of Claim 12 or 13.