JP2020033533A - Resin composition for molding and molded body - Google Patents

Abstract

To provide a resin composition for molding that can be molded into a molded body capable of suppressing migration of a dye and to provide a molded body.SOLUTION: The resin composition for molding includes a thermoplastic resin (A) and a salt-forming compound (B) being a reaction product of an ionic resin and an ionic dye (provided that the thermoplastic resin (A) excludes polyolefin and the salt-forming compound (B) excludes a combination with a monoazo dye). The salt-forming compound (B) is preferably a reaction product (B1) of a resin having a cationic group in the side chain and an anionic dye or a reaction product (B2) of a resin having an anionic group in the side chain and a cationic dye.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for molding capable of producing molded articles and the like.

  Conventionally, pigments and dyes have been used as colorants for resin molded articles. Among them, dyes have a wide variety of molecular structures, are easy in molecular design, and are capable of coloring the molded product and have a light transmittance that allows the contents to be visually recognized. Was used to. However, dyes are liable to migrate, so it has been difficult to use them in applications that dislike migration, such as food applications and medical applications.

  Therefore, Patent Document 1 discloses a resin composition containing a compound in which a salt is formed between a dye and an amine. Patent Document 2 discloses a resin composition containing a polymer obtained by grafting a dye structure to a polyolefin.

WO2004 / 072175 WO2016 / 002842

  However, it has been difficult for conventional resin compositions to suppress the migration of dyes to a level that can be used for medical applications, for example.

  An object of the present invention is to provide a molding resin composition capable of molding a molded body capable of suppressing migration of a dye, and a molded body.

  The molding resin composition of the present invention contains a thermoplastic resin (A) and a salt-forming compound (B) of a reaction product of an ionic resin and an ionic dye (provided that the thermoplastic resin (A) is a polyolefin, and The salt-forming compound (B) excludes the combination of monoazo dyes).

  According to the present invention described above, a molding resin composition capable of molding a molded article capable of suppressing migration of a dye, and a molded article can be provided.

  The molding resin composition of the present invention contains a thermoplastic resin (A) and a salt-forming compound (B) of a reaction product of an ionic resin and an ionic dye (provided that the thermoplastic resin (A) is a polyolefin, and The salt-forming compound (B) excludes the combination of monoazo dyes). It is preferable that the resin composition for molding is melted and kneaded, and then a molded article is prepared and used. Since the molded article can suppress migration of the salt forming compound (B), for example, when the molded article is used as a molded container for storing a medical compound, food, or the like, it is difficult to contaminate the contents, and the contents are easily visually recognized. . Further, adhesion of dust and the like due to components and the like migrated to the surface of the molded body can be suppressed.

<Thermoplastic resin (A)>
Examples of the thermoplastic resin (A) include polyolefins such as polyethylene and polypropylene, polystyrene, polyphenylene ether, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate, polyamide, polyacetal, polyester, polyvinyl chloride, and polymethylmeta. Polyacryl such as acrylate, and polyetherimide. Among these, polyolefins are preferred in consideration of moldability and mechanical strength of molded articles.

  Polyolefins include, for example, crystalline or amorphous polypropylene, polybutene-1, poly-4-methylpentene, low or high density polyethylene, random, block or graft copolymers of ethylene-propylene, α-olefins and ethylene or propylene. , An ethylene-vinyl acetate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and an ethylene-acrylic acid copolymer. Among them, crystalline or amorphous polypropylene, random, block or graft copolymers of ethylene-propylene are preferred, and propylene-ethylene block copolymers are more preferred. In addition, polypropylene is preferred from the viewpoint of being inexpensive and having a small specific gravity, so that a molded article can be reduced in weight.

  The thermoplastic resin (A) preferably has a melt flow rate (MFR) of 1 to 100 (g / 10 minutes). The MFR is determined based on JIS K-7210.

  The thermoplastic resin (A) can be used alone or in combination of two or more.

<Salt-forming compound (B) of reaction product of ionic resin and ionic dye>
The dye contained in the molding resin composition is obtained by including a salt forming compound (B) (hereinafter, simply referred to as “salt forming compound (B)”) of a reaction product of the ionic resin and the ionic dye. The molded body can suppress the mication. This makes it difficult for the contents of the molded body to be contaminated and also makes the contents easily visible.

(Ionic resin)
An ionic resin is a resin having an ionic group capable of forming a salt. The salt-forming compound (B) that reacts the ionic group of the resin with the ionic group of the dye can suppress migration of the dye.

  The salt forming compound (B) is preferably a reaction product of a resin having a cationic group in a side chain and an anionic dye, or a reaction product of a resin having an anionic group in a side chain and a cationic dye.

(Resin having cationic group in side chain)
The resin having a cationic group in the side chain is preferably a resin having at least one onium base in the side chain. Examples of the onium salt include an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt. Among these, ammonium salts, iodonium salts, and sulfonium salts are preferable in terms of storage stability (thermal stability), and ammonium salts are more preferable.

The resin unit of the resin having a cationic group in the side chain is preferably an acrylic resin.
Further, the resin having a cationic group in the side chain preferably contains a unit represented by the following general formula (11).

(In the general formula (11), R ₁₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{12 to} R ₁₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, Represents an optionally substituted alkenyl group or an optionally substituted aryl group, and two of R _{12 to} R ₁₄ may combine with each other to form a ring, and Q represents an alkylene group, an arylene group, _{CONH-R 15 -, - COO} -R 15 - _{represents, R 15} is .Y- represents an alkylene group represents an inorganic or organic anion).

In Formula (11), R ₁₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₁₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

When the alkyl group represented by R ₁₁ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

R ₁₁ is particularly preferably a hydrogen atom or a methyl group.

In formula (11), R _{12 to} R ₁₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Can be

The alkyl group for R _{12 to} R ₁₄ is, for example, a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n- -Hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl) Etc.), cycloalkyl groups (such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl), and bridged cyclic alkyl groups (such as norbornyl, adamantyl and pinanyl). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

The alkenyl group for R _{12 to} R ₁₄ is, for example, a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1- And propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

The aryl group for R _{12 to} R ₁₄ is, for example, a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl) and an aromatic heterocyclic hydrocarbon group (Thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (derived from xanthone) And a 9-oxothioxanthenyl (a group derived from thioxanthone).

When the alkyl group, alkenyl group, or aryl group represented by R _{12 to} R ₁₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, and an alkoxycarbonyl group. And a substituent selected from a group, a carboxyl group, and a phenyl group. The substituent is preferably a halogen atom, a hydroxyl group, an alkoxyl group, or a phenyl group.

As R _{12 to} R ₁₄ , an alkyl group which may be substituted is preferable from the viewpoint of stability, and an unsubstituted alkyl group is more preferable.

In addition, R _{12 to} R ₁₄ may be such that two sites are bonded to each other to form a ring.

In the general formula (11), Q site connecting to a C-C backbone site and ammonium salt, an alkylene group, an arylene _{group, -CONH-R 15 -, -} COO-R 15 - _{represents, R 15} is an alkylene group Is mentioned. Among these, the polymerizable, for reasons of _{availability, -CONH-R 15 -, -} COO-R 15 - are preferred. R ₁₅ is preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group.

In the general formula (11), the Y-unit is preferably an inorganic or organic anion.
Examples of the anion include a hydroxide ion; a halide ion such as chloride ion, bromide ion and iodide ion; a carboxylate ion such as formate ion and acetate ion; a carbonate ion, a bicarbonate ion, a nitrate ion, and a sulfate ion. Complex ions such as sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion; and hexacyanoferrate (III) ion. Among these, a halogen ion and a carboxylate ion are preferable in terms of reactivity and stability, and a halogen ion is more preferable. When the anion is an organic anion such as a carboxylate ion, the organic anion in the resin may be covalently bonded to form an inner salt.

  The synthesis of a resin having a cationic group in the side chain is carried out, for example, by a method of copolymerizing a monomer having an ammonium group as a monomer component, a resin having an amino group copolymerized as a monomer component having an amino group. To form an ammonium salt by reacting an onium chlorinating agent.

  A monomer used for synthesizing a resin having a cationic group in a side chain will be described. The monomer is an ethylenically unsaturated group-containing monomer. “(Meth) acryl” includes “acryl, methacryl”. “(Meth) acryloyl” includes “acryloyl, methacryloyl”.

  Examples of the monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyloxyethylmethylmorpholinoammonium. Alkyl (meth) acrylate based quaternary ammonium salts such as chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, and alkyl (meth) acrylate such as (meth) acryloylaminoethyldimethylbenzylammonium chloride ) Acryloylamide quaternary ammonium salts, dimethyldiallylammonium Arm methylsulfate, trimethylammonium vinylphenyl ammonium chloride.

  Examples of the monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, and diisobutyl. Aminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, Dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) (Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as acrylamide, and styrene having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; diallylamine compounds such as diallylmethylamine and diallylamine; Examples include amino group-containing aromatic monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone, and N-vinylcarbazole.

  The onium salt is, for example, an alkyl sulfate such as dimethyl sulfate, diethyl sulfate or dipropyl sulfate, a sulfonate such as methyl p-toluenesulfonate or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or octyl. Examples thereof include alkyl chloride such as chloride, alkyl bromide such as methyl bromide, ethyl bromide, propyl bromide, and octyl clobromide, and benzyl chloride and benzyl bromide.

  The reaction between the monomer having an amino group and the onium chlorinating agent is usually performed by dropping an onium chlorinating agent in an equimolar amount or less with respect to the amino group into the monomer solution having the amino group. The temperature during the ammonium salt forming reaction is about 90 ° C. or less, and particularly preferably about 30 ° C. or less when a vinyl monomer is ammonium chlorided. The reaction time is about 1 to 4 hours.

Other onium chlorinating agents include alkoxycarbonylalkyl halides. The alkoxycarbonylalkyl halide is a compound represented by the following general formula (12).
ZR ₁₆ -COOR ₁₇ General formula (12)
(In the general formula (12), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₁₆ is an alkylene group having 1 to 6, preferably 1 to 5, and more preferably 1 to 3 carbon atoms. And R ₁₇ is an alkyl group having 1 to 6, preferably 1 to 3 carbon atoms.)

The reaction of a monomer having an amino group with an alkoxycarbonylalkyl halide for synthesizing the compound represented by the general formula (12) is carried out, for example, by converting an alkoxycarbonylalkyl halide in an equimolar amount or less with respect to the amino group in the same manner as the above onium chlorinating agent. After the reaction, the compound is obtained by hydrolyzing the above-mentioned -COOR ₁₇ to convert it into a carboxylate ion (-COO-). Thereby, a monomer having a carboxybetaine structure represented by the general formula (12) and having an ammonium base can be synthesized.

  Other monomers that can be used other than the structural unit represented by the general formula (11) include, for example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) acrylamide, Examples include vinyl ether, esters of vinyl alcohol, styrene, (meth) acrylonitrile, and monomers containing an acidic group.

(Meth) acrylates include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, T-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, (T) 2- (2-methoxyethoxy) ethyl acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol (meth) acrylate monomethyl ether, diethylene glycol (meth) acrylate Monoethyl ether, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, (meth) ) Β-phenoxyethoxyethyl acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopent (meth) acrylate Tenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate , Tribromophenyloxyethyl (meth) acrylate and the like.

Crotonic esters include, for example, butyl crotonate, hexyl crotonate and the like.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. The maleic acid diester includes, for example, dimethyl maleate, diethyl maleate, dibutyl maleate and the like.

Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Examples of the itaconic acid diester include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(Meth) acrylamide is, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetoneacrylamide and the like.

Examples of the vinyl ether include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrene include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and chloromethylstyrene. And hydroxystyrene, methyl vinylbenzoate, and α-methylstyrene protected with a group that can be deprotected by an acidic substance (eg, t-Boc).

Examples of the acidic group-containing monomer include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. An unsaturated dicarboxylic acid such as citraconic acid, citraconic anhydride, and mesaconic acid or an acid anhydride thereof; a trivalent or higher unsaturated polycarboxylic acid or an acid anhydride thereof; mono (2-acryloyloxyethyl succinate), Mono-((meta) of a di- or higher-valent polycarboxylic acid such as mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate ) Acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone Both terminal carboxy polymers Roh methacrylate include mono (meth) acrylate.

  Examples of the synthesis of a resin having a cationic group in a side chain include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Of these, free radical polymerization and living radical polymerization are preferred.

  Preferably, the free radical polymerization uses a polymerization initiator. As the polymerization initiator, for example, an azo compound or a peroxide is preferable. The azo compounds include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. The peroxide is, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate , T-butyl peroxy neodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

  The polymerization initiators can be used alone or in combination of two or more.

  The reaction temperature is preferably from 40 to 150C, more preferably from 50 to 110C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In living radical polymerization, side reactions occurring in general radical polymerization are suppressed, and furthermore, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight (a resin having a narrow molecular weight distribution) can be easily synthesized. .

The atom transfer radical polymerization method using living halide polymerization, which uses an organic halide or a sulfonyl halide compound as an initiator, and uses a transition metal complex as a catalyst, can be applied to a wide range of monomers and can be applied to existing equipment. This is preferable in that a polymerization temperature can be adopted. The atom transfer radical polymerization method can be performed by the methods described in References 1 to 8 and the like below.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev .. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866.
(Reference 5) WO 96/030421 (Reference 6) WO 97/018247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A 8-41117

  For the synthesis of a resin having a cationic group in the side chain, it is preferable to use an organic solvent. Organic solvents include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like can be mentioned.

  The organic solvents can be used alone or in combination of two or more.

  The preferred content of the unit represented by the general formula (11) is preferably 4 to 74% by mass, more preferably 8 to 48% by mass, based on 100% by mass of the total of the monomers used for forming the main chain of the resin.

  The weight average molecular weight (Mw) of the resin having a cationic group in the side chain is preferably from 1,000 to 500,000, more preferably from 3,000 to 15,000. In addition, Mw is measured by gel permeation chromatography (GPC).

(Anionic dye)
The anionic dye is a dye having an anionic group capable of ion-bonding with the resin having a cationic group in the side chain. The anionic dye has, for example, a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof as an anionic group.

  Anionic dyes, for example, anthraquinone-based anionic dye, disazo-based anionic dye, oxazine-based anionic dye, aminoketone-based anionic dye, xanthene-based anionic dye, quinoline-based anionic dye, triphenylmethane-based anionic dye And the like. Hereinafter, specific examples of the anionic dye are shown by color index numbers.

  Red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 8788, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 1 7, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177,181,229,231,237,239,240,241,242,249,252,253,255,257,260,263,264,266,267,274,276,280,286,289,299 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 1 8, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like.

Yellow dyes include C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 32, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 etc. It is below.

C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

Orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1,
25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.

C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like.

The blue dye is C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 50, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 21 , It may also be mentioned, and the like 215,225,226,229,230,231,242,243,244,253,254,260,263.

The purple dye is C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Is mentioned.

C.I. I. Direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like.

The green dye is C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13
, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69 , 70, 71, 81, 84, 94, 95 and the like.

C.I. I. Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80 and the like.

(Salt formation)
The salt-forming compound (B) is prepared by stirring or vibrating an aqueous solution in which a resin having a cationic group in a side chain and an anionic dye are dissolved, or by mixing an aqueous solution of a resin having a cationic group in a side chain with an anionic solution. It can be easily obtained by mixing with an aqueous solution of the dye under stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these are ion-bonded, and the ion-bonded portion becomes water-insoluble and precipitates. Conversely, the salt comprising the counter anion of the resin and the counter cation of the acid dye is water-soluble and can be removed by washing with water or the like. The resin having a cationic group in the side chain and the anionic dye to be used can be used alone or in combination of two or more.

As the aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent can be used to dissolve a resin having a cationic group in a side chain and an anionic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Propylene glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene Recall monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, Methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexane Triol, tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like.

The amount of the salt forming compound (B) is preferably 1 to 20% by weight based on the aqueous solution used for salt formation.

Of the aqueous solution used for salt formation, the amount of the water-soluble organic solvent is preferably 5 to 50% by weight, more preferably 5 to 20% by weight.

The ratio of the resin having a cationic group in the side chain to the anionic dye is preferably from 10/1 to 1/4 in a molar ratio of all cation units of the resin to all anionic groups of the anionic dye, and 2 / 1 to 1/2 is more preferable.

(Resin having anionic group in side chain)
The resin having an anionic group in the side chain is preferably a resin containing a unit represented by the following general formula (21).

(In the general formula (21), R ₂₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
U is an alkylene group, an arylene _{group, -CONH-R 22 -, -} COO-R 22 - _{represents, R 22} represents an alkylene group. P ^- is, -SO ₃ - represents a or COO-. Z ⁺ represents an inorganic or organic cation. )

In the general formula (2), R ₂₅ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₂₅ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable.

When the alkyl group represented by R ₂₅ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among them, R ₂₅ is preferably a hydrogen atom or a methyl group.

The component of P in the general formula (21) is preferably, for example, a sulfonic acid group or a carboxyl group. Also, P ^- is, -SO ₃ - represents a or COO-.

In the general formula (21), acrylic site and P ^- U for connecting is an alkylene group, an arylene _{group, -CONH-R 22 -, -} COO-R 22 - _{represents, R 22} represents an alkylene group. Among these, the polymerizable, for reasons of _{availability, -CONH-R 22 -, -} COO-R 22 - are preferred. R ₂₂ is preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group.

Z ⁺ in the general formula (21) represents an inorganic or organic cation. Z ⁺ includes hydrogen, an alkali metal, an alkaline earth metal, an ammonium compound and the like. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium and magnesium. The ammonium compound is NH ₄ ⁺ or a compound in which a hydrogen atom thereof is substituted with a hydrocarbon group or the like.

Examples of the resin containing the unit represented by the general formula (21) include a method of copolymerizing a monomer having a sulfonic acid group and / or a carboxyl group.

Examples of the monomer having a carboxyl group (including an acid anhydride group-containing monomer) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride, and itaconic anhydride.

The monomer having a sulfonic acid group is preferably a monomer represented by the following general formula (IV) and a water-soluble salt thereof. The water-soluble salt is preferably an alkali metal salt, more preferably a potassium salt, a sodium salt, and an ammonium salt.
_{R 26 (R 27) C =} C (R 28) -X-SO 3 H Formula (IV)
[Wherein, R ₂₆ , R ₂₇ and R ₂₈ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear or branched carbon number of 2 to 12 carbon atoms. A monounsaturated or polyunsaturated alkenyl group, wherein the latter two groups are unsubstituted or substituted by one or more groups -NH2, -OH or -COOH; COOH or —COOR ₂₉ , and R ₂₆ is XSO ₃ H; R ₂₉ is a saturated or unsaturated linear or branched C 2-12 hydrocarbon; X is a single bond, is _{n = 1~4 - (CH 2)} n-, phenylene, (preferably 1,4) preferably _{1,4-phenylene,} -CH 2 -O- phenylene (preferably 1,4), - CH ₂ —O—CH ₂ —CH (OH) —CH ₂ - is the _{k = 1~6 -COO- (CH 2)} k -, - CO-NH-, -CO-NH-CR'R is _{m = 0~3 '' - (CH} 2) m or - _{CO-NH-CH 2 -CH (} OH) -CH 2 - and is; R 'is -H, a -CH ₃ or _-C 2 _{H 5} and R''is -H or -CH ₃ . Here, m is an integer. ]

Examples of the sulfonic acid group-containing monomer include 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, and 2-acrylamido-2-methyl. Propanesulfonic acid, 2-methacrylamide-2-methyl-1-propanesulfonic acid, 3-methacrylamide-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid (2-methyl-2-propene-1) -Sulfonic acid), allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, styrenesulfonic acid, p-styrenesulfonic acid, vinylsulfonic acid, isoprenesulfonic acid Acid, 3-sulfopropylacrylic Over DOO, 3-sulfopropyl methacrylate, sulfo methacrylamide and sulfomethyl methacrylamide, and salts thereof, as well as esters thereof. Among them, 2-acrylamido-2-methyl-1-propanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid and styrenesulfonic acid are preferred.

The monomer having a sulfonic acid group is preferably a sulfonic acid group-containing monomer that has formed a salt. The salt is preferably an alkali metal salt and an alkaline earth metal salt, more preferably a sodium salt and a potassium salt.

Monomers having a carboxyl group and monomers other than a monomer having a sulfonic group that can be used in the synthesis of a resin having an anionic group in the side chain include, for example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester , Fumaric acid diester, itaconic acid diester, (meth) acrylamide, vinyl ether, vinyl alcohol ester, styrene and (meth) acrylonitrile. These can use the monomers already illustrated.

In addition, a monomer having an acid group may be used.

Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride Unsaturated dicarboxylic acids such as citraconic acid, citraconic anhydride and mesaconic acid or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof; mono (2-acryloyloxyethyl succinate), Mono-((meta) of a di- or higher-valent polycarboxylic acid such as mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate ) Acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolact Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

The resin containing the unit represented by the general formula (21) can be synthesized by the same method as the resin containing the unit represented by the general formula (17).

For the resin having an anionic group in the side chain, it is preferable to use a total of 5 to 35% by mass of a monomer having a carboxyl group and a monomer having a sulfonic acid group in the monomers used for copolymerization, and 10 to 30% by mass. More preferred. When it is used in an amount of 5 to 35% by mass, a salt formation reaction easily occurs, and heat resistance is further improved.

The weight average molecular weight of the resin having an anionic group in the side chain is preferably from 1,000 to 500,000, more preferably from 3,000 to 15,000.

(Cationic dye)
The cationic dye is a dye having a cationic group capable of ion-bonding with the resin having an anionic group in the side chain.

Cationic dyes, for example, anthraquinone-based cationic dyes, disazo-based cationic dyes, oxazine-based cationic dyes, aminoketone-based cationic dyes, among the xanthene-based cationic dyes rhodamine-based cationic dyes, quinoline-based cationic dyes, tria Reel methane-based cationic dyes, diarylmethane-based cationic dyes, thiazine-based cationic dyes, acridine-based cationic dyes, azine-based cationic dyes, methine-based cationic dyes, and the like.

Among these, cationic dyes include triarylmethane-based basic dyes, xanthene-based basic dyes, preferably rhodamine-based basic dyes, flavin-based basic dyes, auramine-based basic dyes, safranin-based basic dyes, and phloxine-based base dyes. Preferred are a basic dye, a thiazine basic dye, an acridine basic dye, an azine basic dye, a methine basic dye, and a methylene blue basic dye.

Triarylmethane-based cationic dyes include C.I. C. I. Basic Violet 1 (methyl violet), 3 (crystal violet), 14 (Magenta), C.I. C. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue Bconc.), C.I. I. Basic Green 1 (Brilliant Green GX), and 4 (Malachite Green). Among these, C.I. I. It is preferable to use Basic Blue 7, Green 4, Violet 1, and Violet 3. Rhodamine-based cationic dyes include C.I. C. I. Basic Red 1 (rhodamine 6G, 6GCP), 3, 8 (rhodamine G), C.I. And I. Basic Violet 10 (rhodamine B). Among these, C.I. It is preferable to use I. Basic Red 1 and Violet 10. Flavin-based cationic dyes include C.I. C. I. Basic Yellow 1; I. Basic Yellow 2, 3; Safranine-based cationic dyes include C.I. I. Basic Red 2: Phloxine cationic dyes include C.I. C. I. Basic Red 12; I. Basic Yellow 5; Oxazine-based cationic dyes include C.I. C. I. Basic Blue 3: Thiazine-based cationic dyes include C.I. C. I. Basic Blue 24; CI Basic Red 12, C.I. I. Basic Yellow 11, 21 and 28; methylene blue cationic dyes include C.I. I. Basic Blue 9 (methylene blue FZ, methylene blue B), 25 (basic blue GO) and 24 (new methylene blue NX). Among these, C.I. I. Basic Yellow 1, Blue 9, Red 24 and Red 25 are preferred.
Further, it is preferable to use a triarylmethane-based cationic dye, a rhodamine-based cationic dye, or a methylene blue-based cationic dye from the viewpoint of good color developability. In forming a red pixel, a flavin-based cationic dye as a complementary color is preferable.

(Salt formation)
The salt forming compound (B) is prepared by stirring or vibrating an aqueous solution in which a resin having an anionic group in a side chain and a cationic dye are dissolved, or by mixing an aqueous solution of a resin having an anionic group in a side chain with a cationic solution. It can be easily obtained by mixing with an aqueous solution of the dye under stirring or vibration. In the aqueous solution, the anionic group of the resin and the cationic group of the dye are ionized, and these are ion-bonded, and the ion-bonded portion becomes insoluble in water and precipitates. Conversely, the salt comprising the counter cation of the resin and the counter anion of the basic dye is water-soluble and can be removed by washing with water or the like. The resin having an anionic group in the side chain and the cationic dye to be used may each be used alone or in combination of two or more with different structures.

In the preparation of the salt forming compound (B), a resin having an anionic group in a side chain and a cationic dye are mixed in an aqueous solution to obtain a salt forming compound (B), and then the side chain of a by-product is obtained. It is preferable to remove a salt composed of a counter cation of a resin having an anionic group and a counter anion of a cationic dye.

As the aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve a resin having an anionic group in a side chain and a cationic dye. As the water-soluble organic solvent, the compounds described above can be used. The amount of the water-soluble organic solvent used is the same as described above. Further, the ratio of the salt forming compound (B) in the aqueous solution used at the time of salt formation is the same as described above.

The ratio of the resin having an anionic group in the side chain to the cationic dye is preferably 10/1 to 1/4 in terms of the molar ratio of all anion units of the resin to all cationic groups of the cationic dye, and 2 / 1 to 1/2 is more preferable.

(UV absorber)
In the present specification, an ultraviolet absorber may be further contained. This further improves the light resistance of the molded body. Although a known compound can be used as the ultraviolet absorber, it is preferable to use a salt forming compound. Examples of the salt forming compound of the ultraviolet absorber include a reaction product of a resin having a cationic group in a side chain and an anionic ultraviolet absorber.

The anionic ultraviolet absorber includes, for example, an ultraviolet absorber 1 having the following chemical structure. It is possible to prepare a salt-forming compound of the ultraviolet absorbent 1 and the resin having a cationic group in the side chain already described. The salt-forming compound can suppress migration similarly to the salt-forming compound (B) described above.

(UV absorber 1)

In the present specification, a wax can be further contained. This makes it easier to disperse the salt forming compound (B) during the production of the molded article.

Examples of the wax include polyethylene wax and polypropylene wax. The melting point of the wax is preferably from 50 to 180C, more preferably from 80 to 170C, even more preferably from 90 to 140C. The melting point of the wax is measured using a differential scanning calorimeter under a nitrogen atmosphere.

The number average molecular weight of the wax is preferably from 500 to 25,000, more preferably from 1,000 to 15,000. The number average molecular weight is a value measured according to JIS K2207: 1996 (Japanese Industrial Standard).

The addition amount of the wax is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).

(Production method of molding resin composition)
The method for producing the resin composition for molding is preferably, for example, produced as a master batch in which a salt-forming compound (B) of a reaction product of an ionic resin and an ionic dye is blended at a high concentration. The masterbatch is preferably formed by melt-kneading the salt forming compound (B) and the thermoplastic resin (A), and then molding it into an arbitrary shape. Next, the master batch and the dilution resin (thermoplastic resin (A)) are melt-kneaded to form a molded article having a desired shape. The salt-forming compound (B) can be more highly dispersed by preparing a master batch and then forming a molded body than by forming a molded body by melt-kneading the materials at once and then forming a molded body.

Examples of the shape of the master batch include a pellet, a powder, and a plate. For the melt kneading, it is preferable to use, for example, a single-screw kneading extruder, a twin-screw kneading extruder, or a tandem twin-screw kneading extruder. The melt-kneading temperature varies depending on the type of the thermoplastic resin (A), but is usually about 150 to 250 ° C.
In addition, from the viewpoint of suppressing aggregation of the salt forming compound (B), a preliminary dispersion in which the salt forming compound (B) and the wax are melt-kneaded in advance is prepared, and then the melted mixture is melted together with the thermoplastic resin (A). It is preferable to produce the resin composition for molding by kneading. In addition, it is preferable to use, for example, a blend mixer or a three-roll mill for producing the preliminary dispersion.

In preparing the master batch, the amount of the salt forming compound (B) used is preferably 0.05 to 30 parts by mass, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the thermoplastic resin (A). The mass ratio between the master batch and the dilution resin is preferably 1/5 to 1/100. When used in an appropriate ratio, the degree of coloring and the mechanical strength of the molded product can be both highly compatible. The dilution resin is not limited to the thermoplastic resin (A) used for the masterbatch, and may be any thermoplastic resin having good compatibility with the resin.

The resin composition for molding of the present invention can contain an antioxidant, a light stabilizer, a dispersant, and the like as optional components other than the thermoplastic resin (A) and the salt forming compound (B).

The molded article of the present specification is produced by molding a molding resin composition.
Examples of the molding method include extrusion molding, injection molding, and blow molding. Extrusion molding includes, for example, compression molding, pipe extrusion molding, laminate molding, T-die molding, inflation molding, melt spinning, and the like.

The molding temperature of the molded body is usually about 160 to 240 ° C.

The molded article of the present specification can be produced by high-speed extrusion molding (a molding machine screw rotation speed: about 150 rpm), which has a higher molding speed than ordinary extrusion molding, or compression molding having a long non-shearing area, and can produce uneven color and color. Less likely to break apart. In particular, even in high-speed compression molding (production speed of 500 pieces / min or more, sometimes 700 to 900 pieces / min), which is a molding speed about 10 times as high as that of injection molding, excellent effect of preventing color unevenness and color separation from occurring in the molded product. Is obtained.

  Compression molding will be described as an example of the method for producing a molded article in the present specification. First, a step of melt-mixing the molding resin composition of the present invention, putting the mixture into a compression molding machine, and applying a pushing force by compression without applying a shearing force in the compression molding machine to obtain a molded product, comprising: It is a method of manufacturing a product. Here, when a force for extruding by compression is applied without applying a shearing force, the molding resin composition is in a state where no mixing force is applied to the molding resin composition, that is, the molding resin composition exists in the non-shear region. This molded product is preferably, for example, a plastic cap of a PET bottle. In the present specification, a molded article is obtained by charging a resin into a mold to obtain an article. The molded article includes an article obtained without using a mold such as a plastic film and a molded article.

The molded article of the present specification is preferably used for, for example, food packaging materials, pharmaceutical packaging materials, and lighting applications. For a food packaging material or a pharmaceutical packaging material, it is preferable to use, for example, polyolefin or polyester for the thermoplastic resin. These molded articles have improved flexibility and visibility, and can suppress deterioration of the contents. For lighting applications (for example, fluorescent lamp lighting, LED lighting, OLED lighting, etc.), it is preferable to use, for example, polyacryl or polycarbonate for the thermoplastic resin. These molded products facilitate visibility, suppression of dust adhesion, and easy adjustment of the color tone of illumination light.

  The molded article of the present specification may be used in addition to the above-mentioned applications, for example, other medical agents, cosmetic packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, housing materials, etc. It can be widely used in applications such as toiletries.

  Hereinafter, the present invention will be described in more detail, but the present invention is not limited to these examples unless departing from the technical idea of the present invention. Hereinafter, “parts” means “parts by mass” and “%” means “% by mass”.

The thermoplastic resins used in the examples are shown below.
(A-1) Polyethylene (Suntech LDM2270, MFR = 7g / 10min, manufactured by Asahi Kasei Chemicals Corporation)
(A-2) Polyethylene (Novatec UJ790, MFR = 50 g / 10 min, manufactured by Nippon Polyethylene)
(A-3) Polypropylene (Novatech PPFA3EB, MFR = 10.5g / 10min, manufactured by Nippon Polypro)
(A-4) Polypropylene (Prime Polypro J226T, MFR = 20 g / 10 min, manufactured by Prime Polymer Co., Ltd.)
(A-5) Polycarbonate (Iupilon S3000, MFR = 15g / 10min, manufactured by Mitsubishi Engineering-Plastics Corporation)
(A-6) Polymethacrylic resin (Acrypet MF, MFR = 14 g / 10 min, manufactured by Mitsubishi Rayon Co., Ltd.)

The wax used in the examples is shown below.
(D-1) Polyethylene wax (Sunwax 131-P, number average molecular weight 3500, melting point 105 ° C, manufactured by Sanyo Chemical Industries, Ltd.)
(D-2) Polyethylene wax (high wax 405MP, number average molecular weight 4500, melting point 120 ° C, manufactured by Mitsui Chemicals, Inc.)
(D-3) Polypropylene wax (High wax NP056, number average molecular weight 7200, melting point 130 ° C, manufactured by Mitsui Chemicals, Inc.)

[Production Example of Salt-Forming Compound (B) of Reaction Product of Ionic Resin and Ionic Dye]
In the following procedure, the ionic resin and the ionic dye were reacted to prepare a salt-forming compound (B) of a reaction product of the ionic resin and the ionic dye.

<Production Example of Resin (X1) Having Cationic Group in Side Chain>
100.0 parts of isopropyl alcohol was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 45.0 parts of methyl methacrylate, 45.0 parts of isostearyl acrylate, 10.0 parts of dimethylaminoethyl methyl chloride methacrylate, 10.0 parts of 2.2'-azobis (methyl isobutyrate), and isopropyl alcohol After uniformly mixing 40.0 parts, the mixture was charged into a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50 ° C. In this way, a resin X1 having a non-volatile content of 40% by weight and having a cationic group in a side chain was obtained. The ammonium salt value of the obtained resin was 27 mgKOH / g.

<Production Example of Resin (X2) Having Cationic Group in Side Chain>
100.0 parts of isopropyl alcohol was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 27.0 parts of methyl methacrylate, 25.5 parts of butyl methacrylate, 20.0 parts of 2-ethylhexyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, dimethylaminoethyl methyl methacrylate methyl salt After uniformly mixing 10.0 parts, 10.0 parts of 2.2′-azobis (methyl isobutyrate), and 40.0 parts of isopropyl alcohol, the mixture was charged into a dropping funnel and attached to a four-neck separable flask. It was added dropwise over 2 hours. Two hours after completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50 ° C. Thus, a resin X2 having a cationic group in the side chain having a nonvolatile content of 40% by weight was obtained. The ammonium salt value of the obtained resin was 27 mgKOH / g.

<Production Example of Resin (Y1) Having Anionic Group in Side Chain>
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 10.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 45.0 parts of methyl methacrylate, 45.0 parts of isostearyl acrylate, 10.0 parts of 2.2′-azobis (methyl isobutyrate), and After uniformly mixing 40.0 parts of isopropyl alcohol, the mixture was charged into a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50 ° C. Thus, a resin Y1 having an anionic group in a side chain having a nonvolatile content of 40% by weight was obtained.

<Production example of resin (Y2) having an anionic group in side chain>
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 10.0 parts of 2-acrylamido-2-methylpropanesulfonic acid, 27.0 parts of methyl methacrylate, 25.5 parts of butyl methacrylate, 20.0 parts of 2-ethylhexyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate , 2.5 parts of methacrylic acid, 10.0 parts of 2.2'-azobis (methyl isobutyrate) and 40.0 parts of isopropyl alcohol were uniformly mixed, and then charged into a dropping funnel, followed by a four-neck separable flask. And dripped over 2 hours. Two hours after completion of the dropwise addition, it was confirmed from the solid content that the polymerization yield was 98% or more, and the mixture was cooled to 50 ° C. Thus, a resin Y2 having an anionic group in a side chain having a nonvolatile content of 40% by weight was obtained.

<Method for producing salt-forming compound>
(Salt-forming compound (BA-1))
The C.I. I. A salt forming compound (BA-1) comprising Acid Violet 43 and Resin X1 having a cationic group in a side chain was produced.
To 2000 parts of water and 1000 parts of N-methylpyrrolidone, 50 parts of a resin X1 having a cationic group in a side chain are added, and sufficiently stirred and mixed. On the other hand, 50 parts of N-methylpyrrolidone has C.I. I. 4.3 parts of Associated Violet 43 was dissolved, and 100 parts of water was further added to prepare an aqueous solution. This solution was added dropwise little by little to the previously prepared aqueous solution containing the resin X1 having a cationic group in the side chain. After the completion of the dropwise addition, the reaction was carried out with sufficient stirring. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was determined that a salt-forming compound was obtained, with the end point at which bleeding disappeared as the end point. Thereafter, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 21 parts of C.I. I. A salt forming compound (BA-1) of Acid Violet 43 and Resin X1 having a cationic group in a side chain was obtained.

(Salt-forming compound (BA-2 to 14))
Except having changed the material of the salt forming compound (BA-1) into the material of Table 1, it carried out similarly to the salt forming compound (BA-1) and produced the salt forming compound (BA-2-14), respectively.

(Salt-forming compound (BC-1))
The C.I. I. A salt forming compound (BC-1) comprising Basic Yellow 1 and a resin Y1 having an anionic group in a side chain was produced.
To 2000 parts of water and 1000 parts of N-methylpyrrolidone, 50 parts of a resin Y1 having a cationic group in a side chain were added, and sufficiently stirred and mixed. On the other hand, 50 parts of N-methylpyrrolidone has C.I. I. An aqueous solution was prepared by dissolving 5.1 parts of Basic Yellow 1 and further adding 100 parts of water. This solution was added dropwise little by little to the previously prepared aqueous solution containing the resin Y1 having a cationic group in the side chain. After the completion of the dropwise addition, the reaction was carried out with sufficient stirring. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and it was determined that a salt-forming compound was obtained, with the end point at which bleeding disappeared as the end point. Thereafter, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried with a dryer to remove water, and 22 parts of C.I. I. A salt forming compound (BC-1) of Basic Yellow 1 and a resin Y1 having an anionic group in a side chain was obtained.

(Salt-forming compound (BC-2-10))
Except having changed the material of the salt forming compound (BC-1) into the material of Table 2, it carried out similarly to the salt forming compound (BC-1) and produced salt forming compounds (BC-2-10), respectively.

(Salt-forming compound 1)
The following salt-forming compound 1 was synthesized based on Japanese Patent No. 4639148.

Salt-forming compound 1

(Example 1)
[Manufacture of master batch]
20 parts of the salt-forming compound (BA-1) is mixed with 100 parts of the wax (D-1), and the mixture is heated and kneaded at 160 ° C. in a three-roll mill to prepare a dispersion of the salt-forming compound (BA-1). Obtained. Next, 10 parts of the obtained dispersion was mixed with 100 parts of polyolefin (A-1) using a Henschel mixer, melt-kneaded at 180 ° C. with a single-screw extruder having a screw diameter of 30 mm, and using a pelletizer. The mixture was cut into pellets to prepare a molding resin composition (master batch).

[Film molding]
10 parts of the obtained resin composition for molding was mixed with 100 parts of polyolefin (A-1) as a diluting resin, and melt-mixed at a temperature of 180 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A 250 μm thick film was formed.

(Examples 2 to 21, Comparative Examples 1 to 7)
Examples 2 to 21 and Comparative Examples 1 to 7 were carried out in the same manner as in Example 1 except that the materials of Example 1 were changed as described in Table 3, respectively, to prepare a master batch, -A die film was prepared.

(Example 22)
[Manufacture of master batch]
100 parts of the polycarbonate (A-5) and 2 parts of the salt forming compound (BA-8) are fed into the twin screw extruder (manufactured by Nippon Steel Works) having a screw diameter of 30 mm from the same supply port, and are melt-kneaded at 280 ° C. After that, the mixture was cut into pellets using a pelletizer to prepare a molding resin composition (master batch).

[Film molding]
To 100 parts of the diluted resin polycarbonate (A-5), 10 parts of the obtained molding resin composition was mixed, and melt-mixed at 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki). A 250 μm thick film was formed.

(Examples 23 to 33, Comparative Examples 8 to 14)
Examples 23 to 33 and Comparative Examples 8 to 14 were carried out in the same manner as in Example 23, except that the materials of Example 22 were changed as described in Table 4, respectively. -A die film was prepared.

(Example 34)
[Manufacture of master batch]
100 parts of polymethacrylic resin (A-6) and 2 parts of salt-forming compound (BA-8) are charged into a twin-screw extruder (manufactured by Nippon Steel Works) having a screw diameter of 30 mm from the same supply port and melted at 240 ° C. After kneading, the mixture was cut into pellets using a pelletizer to prepare a molding resin composition (master batch).

[Film molding]
To 100 parts of the methacrylic resin (A-6) as a diluting resin, 10 parts of the obtained resin composition for molding was mixed and melt-mixed at 280 ° C. using a T-die molding machine (manufactured by Toyo Seiki). Then, a film having a thickness of 250 μm was formed.

(Examples 35 to 45, Comparative Examples 15 to 21)
Examples 35 to 45 and Comparative Examples 15 to 21 were carried out in the same manner as in Example 35, except that the materials of Example 34 were changed as described in Table 5, respectively, to prepare a master batch, -A die film was prepared.

  The obtained T-die film was evaluated as follows.

[Transparency evaluation]
The transparency of the obtained film was visually evaluated.
：: No turbidity was observed at all. Good: slightly turbid. Practical range x: Many turbidities are observed. Impractical

[Migration evaluation]
The upper and lower sides of the obtained T-die film were sandwiched between soft vinyl chloride sheets having a thickness of 500 μm containing titanium oxide, pressed at 100 g / cm ² using a hot press machine, and heated and pressed at 170 ° C. for 30 seconds. Then, the T-die film was immediately removed, and the color transfer of the dye to the soft vinyl chloride sheet was visually confirmed, and evaluated according to the following criteria.
：: No migration was observed. Good: migration was slightly observed. Practical range x: There was much migration. Impractical

[Extractability evaluation]
The obtained T-die film was cut into 2 × 2 cm, placed in 50 g of ion-exchanged water, extracted at 80 ° C. for 24 hours, and the absorbance of the ion-exchanged water was measured and evaluated according to the following criteria. In addition, the elution of the sample having no absorbance into the ion-exchanged water can be suppressed.
：: No absorbance. Good: Absorbance of 0.2 or less. Practical range x: Absorbance of 0.2 or more. Impractical

Claims (5)

  Includes a thermoplastic resin (A) and a salt forming compound (B) of a reaction product of an ionic resin and an ionic dye (provided that the thermoplastic resin (A) is a polyolefin and the salt forming compound (B) is a monoazo dye). Resin composition for molding).   The salt forming compound (B) is a reaction product (B1) of a resin having a cationic group in a side chain and an anionic dye, or a reaction product (B2) of a resin having an anionic group in a side chain and a cationic dye. The molding resin composition according to claim 1, wherein   The molding resin composition according to claim 1 or 2, wherein the salt forming compound (B) is contained in the molding resin composition in an amount of 0.05 to 30 parts by mass.   The molding resin composition according to any one of claims 1 to 3, wherein the ionic resin is an acrylic resin.   A molded product comprising the resin composition for molding according to claim 1.