JP6650126B2 - Textiles and fabrics - Google Patents

Description

  The present invention relates to a printing agent particularly suitable for use in printing on a fabric, and a printing agent and a fabric using the same.

  2. Description of the Related Art A pigment printing method using an aqueous pigment ink is known as a printing method for printing an image such as a character, a picture, or a pattern on a fabric such as a woven fabric, a nonwoven fabric, or a knitted fabric. The pigment printing method is a method of printing a printing agent, which is a pigment composition composed of a color pigment and a binder resin, and then fixing the printing agent to a substrate through a drying and curing step as necessary. Examples of the printing method include a silk screen method in which a pattern of a screen gauze is continuously printed on a fabric (for example, see Patent Document 1), an ink jet recording method in which ink is ejected from a nozzle to adhere to the fabric (for example, see Patent Document 2). )It has been known.

  Pigment printing does not require the selection of a colorant depending on the type of fiber, is simpler in processing, and does not require a steaming process, washing, or soaping compared to printing using dyes, so it does not require energy costs. . Moreover, since no waste liquid is generated, this is an environmentally safe processing method. However, the pigment printing method differs from the printing method using a dye in that the pigment, which is a coloring material, is physically fixed to the cloth with a binder resin. There are problems such as peeling from the fabric (referred to as fixability and fastness) and damage to the original texture of the fabric.

  It is known to use a general-purpose urethane resin or an acrylic copolymer as a binder resin for a pigment printing method (for example, see Patent Documents 1 to 4). For example, in Patent Document 3, at least ethyl acrylate is used as a monomer constituent component. At least 70% by weight of an alkyl (meth) acrylate and / or cyclic alkyl (meth) acrylate, (meth) acrylic acid, and an ethylenically unsaturated monomer having a saturated or unsaturated ring. An acrylic copolymer having a glass transition temperature of 0 ° C. or less and an acid value of 50 mg KOH / g or less is used for printing which is excellent in coloring property and fixing property, and excellent in ejection stability and clogging recovery property. An inkjet recording ink is disclosed. Patent Literature 4 discloses that by using a polyurethane resin composed of a polyol in which polycarbonate diol is 90% by weight or more as a binder resin, both heat blocking resistance and solvent resistance can be achieved. Further, in Patent Document 5, when a dispersion in which a pigment is dispersible in water contains an acrylic copolymer resin and a urethane resin, and contains specific acrylic fine particles as polymer fine particles, and is printed on a cloth. It is disclosed that the friction fastness of dry friction and wet friction and the ejection stability of ink are improved.

  The above-mentioned document discloses that it is possible to improve the fixing property and the fastness of the printed portion to the fabric, the heat blocking property and the like. However, there is no particular disclosure as to excellent washing fastness and friction fastness and maintaining the original texture of the fabric.

JP 2007-332523 A JP-T-2003-518560 JP 2011-74318 A JP 2007-270362 A JP 2011-07319 A

  An object of the present invention is to provide a printing agent which is excellent in washing fastness and friction fastness and can impart an excellent texture to a printed fabric.

  By using a binder resin in which an acrylic copolymer having a specific structure and a urethane resin are used in combination, the present inventors have excellent washing fastness and friction fastness and an excellent texture for a printed fabric. And a printing agent that can be used without any problem by the silk screen method or the ink jet recording method.

  That is, the present invention is a printing agent containing a pigment, water, an organic solvent, and a binder resin, wherein the binder resin is a combination of an acrylic copolymer (A) and a urethane resin (B). The acrylic copolymer (A) is 0.1% by mass based on the total amount of the polymerizable monomer (a1) having a carboxyl group and the polymerizable monomer serving as a raw material of the acrylic copolymer (A). 0.1% by mass to 3.5% by mass based on the total amount of the polymerizable monomer (a2) having an epoxy group of from 5.0 to 5.0% by mass and the raw material of the acrylic copolymer (A). % Of the polymerizable monomer having a hydrolyzable silyl group (a3) and 0.1% by mass to 5.0% by mass based on the total amount of the polymerizable monomer used as the raw material of the acrylic copolymer (A). At least one polymerizable monomer selected from the group consisting of polymerizable monomers having an amide group (a4) Providing a printing agent, which is a acrylic copolymer of a polymerizable monomer obtained by polymerization and a tetramer.

  In addition, the present invention provides a fabric obtained by printing the above-described printing agent on a fabric.

  The printing agent of the present invention comprises a polymerizable monomer (a1) having a carboxyl group as a specific acrylic copolymer, a polymerizable monomer (a2) having an epoxy group, and a polymerizable monomer having a hydrolyzable silyl group. An acrylic copolymer (A) containing at least one polymerizable monomer selected from the group consisting of a monomer (a3) and a polymerizable monomer having an amide group (a4) as an essential polymerization component, and urethane Since the binder resin used in combination with the resin (B) is used, the obtained printed matter is excellent in washing fastness and friction fastness. Further, the printed fabric of the present invention has an excellent texture of the printed fabric, and can be suitably used as a printing agent for inkjet recording.

(Pigment)
The pigment used in the present invention is not particularly limited, and those usually used as pigments for screen recording inks or aqueous inkjet recording inks can be used as colorants. Specifically, known inorganic or organic pigments that can be dispersed in water or a water-soluble organic solvent can be used. Examples of the inorganic pigment include titanium oxide, iron oxide, carbon black produced by a known method such as a contact method, a furnace method, and a thermal method. Examples of organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelated azo pigments, etc.) and polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines) Pigments, thioindigo pigments, isoindolinone pigments, quinoflurone pigments, etc., dye chelates (eg, basic dye type chelates, acidic dye type chelates, etc.), nitro pigments, nitroso pigments, aniline black and the like can be used.

  As a specific example of the pigment, carbon black No. 2300, no. No. 2200B, No. 900, No. 980, no. 33, no. 40, No. 45, No. 45L, No. 52, HCF88, MCF88, MA7, MA8, MA100, etc. are Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, etc., manufactured by Columbia Corporation, and Regal 400R, Regal GL, Regal GL, 660R, Raven 1255, Raven 700, etc. 700, Monarch 880, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. were manufactured by Degussa Color Black FW1, FW2, FW2V, FW18, FW200, S150, SP, S150, SP, S160, S160, and S160. U, V, 1400U, SPESc ial Black 6, 5, 4, and 4A, NIPESX150, NIPESX160, NIPESX170, NIPESX180, and the like.

  Specific examples of the pigment used for the yellow ink include C.I. I. Pigment Yellow 1, 2, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 129, 138, 150, 151, 154, 155, 174, 180, 185 and the like.

  Specific examples of the pigment used in the magenta ink include C.I. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 112, 122, 123, 146, 168, 176, 184, 185, 202, 209, 269, etc. No.

  Specific examples of the pigment used for the cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 3, 15: 4, 16, 22, 60, 63, 66 and the like.

Specific examples of the pigment used for the red ink include C.I. I. Pigment Red 17, 49: 2, 112, 149, 177, 178, 179, 188, 254, 255, 264, and the like.

  In the present invention, a so-called self-dispersion pigment (surface-treated pigment) having a water-dispersibility imparting group on the surface of the pigment and capable of stably maintaining a dispersed state even without a dispersant may be used. The pigment may be a so-called capsule pigment (a pigment containing a water-dispersible polymer) which can stably maintain a dispersed state without a dispersant, or a pigment dispersed with a dispersant may be used.

  As the pigment used in the present invention, any of dry powder and wet cake can be used. These pigments may be used alone or in combination of two or more.

The pigment used in the present invention is preferably a pigment having a particle diameter of 25.0 μm or less, and particularly preferably a pigment having a particle diameter of 1.0 μm or less. When the particle size is in this range, sedimentation of the pigment hardly occurs, and the pigment dispersibility becomes good.
For the measurement of the particle size, for example, a value measured using a transmission electron microscope (TEM) or a scanning electron microscope (SEM) can be adopted.

(water)
As the water used in the present invention, pure water such as ion-exchanged water, ultrafiltration water, reverse osmosis water, and distilled water, or ultrapure water can be used. It is also preferable to use water sterilized by irradiation with ultraviolet light or addition of hydrogen peroxide, since mold or bacteria can be prevented from being generated when the ink composition is stored for a long period of time.

  The water functions as a medium for the pigment and the binder resin in the printing agent. In the case of aqueous printing agents, the medium is mostly water, and in many cases a water-soluble solvent is partially added. For example, it is common to use a ratio of water: water-soluble solvent in the range of 4: 1 to 1: 1.

(Organic solvent)
As the organic solvent used in the present invention, any of those conventionally used in screen recording inks for textile printing and aqueous ink jet recording inks can be used. Organic solvents are broadly classified into those that function as humectants and those that function as penetrating solvents.

  Specific examples of the humectant include, for example, glycerin, ethylene glycol adducts of glycerin (specific examples: Liponic EG-1 (manufactured by Lipochemical), etc.), diglycerin, polyglycerin, ethylene glycol, propylene glycol, 1, and the like. 3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol (specific examples: “# 200”, “# 300”, “# 400”, “# 4000”, “# 6000”, manufactured by Wako Pure Chemical Industries), 2- Pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, thiodiglycol, sulfolane, dimethylsulfoxide, neopentyl alcohol, trimethylolpropane, 2,2-dimethylpropanol and the like. These organic solvents can be used alone or in combination of two or more.

  Specific examples of the penetrating solvent include monohydric or polyhydric alcohols, amides, ketones, keto alcohols, cyclic ethers, glycols, lower alkyl ethers of polyhydric alcohols, polyalkylene glycols, and propylene. Glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, Polyols such as 2,6-hexanetriol, trimethylolpropane, and pentaerythritol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, Polyhydric alcohol alkyl ethers such as propylene glycol monomethyl ether, tripropylene glycol monomethyl ether and propylene glycol monobutyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; and polyhydric alcohol aralkyl ethers , 2-pyrrolidone, N-methyl-2-pyrrolidone, lactams such as ε-caprolactam, 1,3-dimethylimidazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone, m-butyrolactone, polyoxyalkylene of glycerin Adduct, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolan, propylene glycol monomethyl ether acetate, dimethyl sulfoxide Cid, diacetone alcohol, dimethylformamide propylene glycol monomethyl ether and the like. These organic solvents can be used alone or in combination of two or more.

  Further, the printing agent of the present invention preferably contains a surfactant in addition to the penetrant. The surfactant used at this time is preferably one having good compatibility with other components present in the printing agent of the present invention. Further, a surfactant having high permeability and being stable is preferable.

  Specifically, it is preferable to use an amphoteric surfactant or a nonionic surfactant. Preferred examples of the amphoteric surfactant include betaine lauryl dimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyl dimethylamino acetate betaine, polyoctyl polyaminoethyl glycine, and others. And imidazoline derivatives.

  Preferred examples of the nonionic surfactant include an acetylene glycol-based surfactant, an acetylene alcohol-based surfactant, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and polyoxyethylene alkyl. Ethers such as allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, and polyoxyethylene distearate , Sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, polyoxye Ren monooleate, polyoxyethylene stearate, etc. esters, silicone surface active agents dimethylpolysiloxane, other fluorine alkyl esters, fluorine-containing surfactants such as perfluoroalkyl carboxylic acid salts, and the like.

  Particularly, an acetylene glycol-based surfactant and an acetylene alcohol-based surfactant are preferable. When these surfactants are added to a printing agent, they are preferred because they have a low foaming property and an excellent defoaming function. Specific examples of the acetylene glycol-based surfactant and the acetylene alcohol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne- 3,6-diol, 3,5-dimethyl-1-hexyn-3-ol, and the like. It is also available as a commercial product, and includes, for example, Surfynol 61, 82, 104, 440, 465, 485, and TG from Air Products (UK), and Olfin STG and Olfin E1010 from Nissin Chemical Industry Co., Ltd. Can be

  The addition amount of the surfactant is preferably 0.01% by weight or more and 10.0% by weight or less based on the total amount of the printing agent, more preferably 5.0% by weight, and more preferably 5.0% by weight. The value is 0.5% by weight.

(Binder resin)
The present invention is characterized in that a specific acrylic copolymer (A) and a urethane resin (B) are used in combination.

(Acrylic copolymer (A))
The acrylic copolymer (A) used in the present invention is 0.1% based on the total amount of the polymerizable monomer (a1) having a carboxyl group and the total amount of the polymerizable monomer used as the raw material of the acrylic copolymer (A). 0.1 to 3.5% by mass of the polymerizable monomer (a2) having an epoxy group of 0.1 to 3.5% by mass based on the total amount of the polymerizable monomer used as a raw material of the acrylic copolymer (A). The polymerizable monomer (a3) having a hydrolyzable silyl group and the amide group having 0.1 to 5.0% by mass based on the total amount of the polymerizable monomer serving as a raw material of the acrylic copolymer (A) An acrylic copolymer obtained by polymerizing a polymerizable monomer containing at least one polymerizable monomer selected from the group consisting of polymerizable monomers (a4).

  As a combination of the polymerizable monomer, a polymer having a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a2) having an epoxy group as essential polymerization components may be used, A polymer containing a polymerizable monomer (a1) having a carboxyl group and a polymerizable monomer (a3) having a hydrolyzable silyl group as essential polymerization components may be used, or a polymerizable monomer having a carboxyl group may be used. A polymer containing the polymer (a1) and the polymerizable monomer (a4) having an amide group as essential polymerization components, or a polymerizable monomer (a1) having a carboxyl group and a polymer having an epoxy group And a polymerizable monomer (a3) having a hydrolyzable silyl group-containing polymerizable monomer (a3) as an essential polymerization component, or a carboxyl group-containing polymerizable monomer (a1). , A polymerizable monomer having an epoxy group a2) and a polymer having an amide group-containing polymerizable monomer (a4) as an essential polymerization component, or a polymer having a carboxyl group-containing polymerizable monomer (a1) and a hydrolyzable silyl group. A polymer having the polymerizable monomer (a3) and the polymerizable monomer (a4) having an amide group as essential polymerization components may be used, or the polymerizable monomer (a1) having a carboxyl group and an epoxy resin may be used. The polymerizable monomer having a group (a2), the polymerizable monomer having a hydrolyzable silyl group (a3), and the polymerizable monomer having an amide group (a4) are all essential polymerization components. It may be a polymer.

  The polymerizable monomer (a1) is a polymerizable monomer having a carboxyl group. For example, (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic anhydride, citraconic acid, and the like are used. can do.

  The polymerizable monomer (a2) is a polymerizable monomer having an epoxy group. For example, glycidyl (meth) acrylate, glycidyl allyl ether, or the like can be used.

  The polymerizable monomer (a3) is a polymerizable monomer having a hydrolyzable silyl group. Examples of the polymerizable monomer include vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltris (2-methoxyethoxy). ) Vinylsilane compounds such as silane; 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxy (Meth) acryloyloxyalkylsilane compounds such as propylmethyldiethoxysilane can be used. These polymerizable monomers (a3) can be used alone or in combination of two or more.

  The polymerizable monomer (a4) is a polymerizable monomer having an amide group, and uses an acrylamide compound such as (meth) acrylamide, N, N-dimethylacrylamide, isopropylacrylamide, and diacetone acrylamide. be able to.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acrylic acid”. ") Acryloyl" refers to one or both of methacryloyl and acryloyl.

  The polymerizable monomer having a carboxyl group (a1), the polymerizable monomer having an epoxy group (a2), the polymerizable monomer having a hydrolyzable silyl group (a3), and the polymerizable monomer having an amide group Examples of the polymerizable monomer (a5) that can be used as a raw material of the polymer (A) other than the monomer (a4) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl ( Alkyl (meth) acrylates such as meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meth) acrylate, and isobutyl (meth) acrylate; aromatic (meth) acrylates such as benzyl (meth) acrylate ) Acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acryle And hydroxyl group-containing monomers such as methoxypolyethylene glycol mono (meth) acrylate and methoxypolypropylene glycol mono (meth) acrylate; and fluorine-based monomers such as perfluoroalkylethyl (meth) acrylate. (Meth) acrylate; styrene, styrene derivatives (p-dimethylsilylstyrene, (p-vinylphenyl) methylsulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyldimethylsiloxystyrene, o-methylstyrene, aromatic vinyl compounds such as p-methylstyrene, p-tert-butylstyrene, α-methylstyrene), vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene; glycidyl (meth) a Acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-dia Acryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl ( (Meth) acrylate compounds such as meth) acrylate, tris (acryloxy) isocyanurate and urethane (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (Meth) acrylates having an alkylamino group such as ruaminopropyl (meth) acrylate; vinylpyridine compounds such as 2-vinylpyridine, 4-vinylpyridine and naphthylvinylpyridine; 1,3-butadiene, 2-methyl-1, Examples thereof include conjugated dienes such as 3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and 1,3-cyclohexadiene. These polymerizable monomers (a4) can be used alone or in combination of two or more.

  In the present invention, the polymerizable monomer having an epoxy group (a2), the polymerizable monomer having a hydrolyzable silyl group (a3), or the polymerizable monomer having an amide group (a4) Is used, in the case of the polymerizable monomer (a2) having an epoxy group, from 0.1% by mass to the total amount of the polymerizable monomer used as a raw material of the acrylic copolymer (A). 5.0% by mass, and in the case of the polymerizable monomer (a3) having a hydrolyzable silyl group, 0.1% based on the total amount of the polymerizable monomer used as a raw material of the acrylic copolymer (A). In the case of the polymerizable monomer (a4) having an amide group, it is 0.1% by mass based on the total amount of the polymerizable monomer used as a raw material of the acrylic copolymer (A). % To 5.0% by mass.

  Further, the amount of the polymerizable monomer (a2) having an epoxy group or the polymerizable monomer (a4) having an amide group is based on the total amount of the polymerizable monomer serving as a raw material of the acrylic copolymer (A). The proportions are each independently in the range of 0.1% by mass to 5.0% by mass, but the fabric printed with the printing agent of the present invention can impart an excellent texture, and the printed portion has higher washing fastness. In order to be able to impart the degree and the fastness to friction, a range of 0.2% to 3.5% by mass is independently preferable, and a range of 0.3% to 2.0% by mass is more preferable. .

  The ratio of the polymerizable monomer (a3) having a hydrolyzable silyl group to the total amount of the polymerizable monomer serving as a raw material of the acrylic copolymer (A) is 0.1% by mass to 3.% by mass. Although the content is in the range of 5% by mass, the fabric printed with the printing agent of the present invention can impart an excellent texture, and can impart high washing fastness and friction fastness to the printed portion. The range is preferably from 2.5 to 2.5% by mass, more preferably from 0.3 to 2.0% by mass.

  The ratio of the polymerizable monomer (a1) having a carboxyl group to the total amount of the polymerizable monomer serving as the raw material of the acrylic copolymer (A) is such that the printing agent of the present invention has a better dispersion in water. From 0.5% by mass to 5.0% by mass, and preferably from 1.0% by mass to 4.0% by mass, since the ink can impart high wash fastness and friction fastness to the printed portion. Is more preferable, and the range of 1.0% by mass to 3.0% by mass is still more preferable.

  As a method for producing the acrylic copolymer (A) used in the present invention, for example, a known emulsion polymerization method can be used.

  The particle size of the emulsion obtained by the emulsion polymerization method of the acrylic copolymer (A) used in the present invention is preferably in the range of 10 nm to 300 nm, and more preferably in the range of 50 nm to 250 nm, from the viewpoint of the ejection properties of the inkjet ink. It is even more preferred.

  The glass transition temperature (hereinafter sometimes referred to as Tg) of the acrylic copolymer (A) is preferably in the range of −50 to 30 ° C., and particularly, the glass transition temperature of −40 to 20 ° C. The range is preferred, and the range of -30 to 10C is still more preferred.

In the present invention, the glass transition temperature refers to a value based on theoretical calculation by the following FOX formula.
<FOX formula> 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wi / Tgi +... + Wn / Tgn [The FOX formula indicates the glass transition temperature of the homopolymer of each monomer constituting the polymer composed of n kinds of monomers. Tgi (K), the mass fraction of each monomer is Wi, and (W1 + W2 + ... + Wi + ... Wn = 1). ]

(Urethane resin (B))
The urethane resin (B) used in the present invention can be used without particular limitation as long as it is a urethane resin that can be dissolved or dispersed in water.

  The polyurethane resin is not particularly limited, and a polyurethane resin obtained by reacting a diisocyanate compound with a diol compound can be used. Among them, a polyester polyurethane resin or a polycarbonate polyurethane resin is preferable because the fastness of a printed material can be obtained when used as a printing agent.

(Polyester polyurethane resin)
A preferred resin as the polyester polyurethane resin used in the present invention is, for example, a polyester polyol (b1-1) obtained by reacting a polycarboxylic acid and a polyol as the polyol (b1), an anionic group, a cationic group, A urethane resin obtained by reacting a polyol having a hydrophilic group that is an ethylene group or a polyoxyethylene-polyoxypropylene group with a polyisocyanate (b2) is exemplified. (Hereinafter referred to as urethane resin (B-PES))

  The polyester structure has an aliphatic, alicyclic or aromatic structure having an ester bond. The polyester structure is preferably used in a range of 10 to 90% by mass based on the total mass of the polyol (b1) and the polyisocyanate (b2) used for producing the urethane resin (B-PES).

  In the case of a urethane resin (B-PE) having a polyether structure instead of the polyester structure, washing fastness and friction fastness may be slightly inferior.

  The polyester structure is preferably a structure derived from a polyester polyol obtained by an esterification reaction between a polycarboxylic acid and a low-molecular-weight polyol, and further has an aromatic structure, which has washing fastness and friction. It is preferable for improving the fastness.

Further, the urethane resin (B-PES) has a hydrophilic group for imparting dispersion stability in a printing agent.
As the hydrophilic group, those generally referred to as an anionic group, a cationic group, and a nonionic group can be used, and among them, it is preferable to use an anionic group or a cationic group.

  As the anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group and the like can be used, and among them, a carboxylate group partially or wholly neutralized by a basic compound or the like can be used. It is preferable to use a sulfonate group in order to maintain good water dispersibility.

  Examples of the basic compound that can be used for neutralizing the carboxyl group or sulfonic acid group as the anionic group include, for example, ammonia, triethylamine, pyridine, organic amines such as morpholine, alkanolamines such as monoethanolamine, Na, Examples thereof include metal base compounds containing K, Li, Ca, and the like. Among them, it is preferable to select an organic amine having a boiling point of 100 ° C. or less from the viewpoint of reducing the residue on the dried film.

Further, as the cationic group, for example, a tertiary amino group or the like can be used.
As the acid that can be used when neutralizing a part or all of the tertiary amino group, for example, formic acid, acetic acid and the like can be used. As the quaternizing agent that can be used when quaternizing part or all of the tertiary amino group, for example, dialkyl sulfates such as dimethyl sulfate and diethyl sulfate can be used.

  Examples of the nonionic group include polyoxyalkylene groups such as a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly (oxyethylene-oxypropylene) group, and a polyoxyethylene-polyoxypropylene group. Can be used. Among them, it is preferable to use a polyoxyalkylene group having an oxyethylene unit in order to further improve the hydrophilicity.

  The hydrophilic group is present in the urethane resin (B-PES) in an amount of 100 mmol / kg to 1200 mmol / kg to give a better water dispersibility, and the hydrophilic group is present in the range of 150 mmol / kg to 1000 mmol / kg. More preferably, there is.

  The presence of the hydrophilic group in the urethane resin (B-PES) in an amount of from 0.5 to 30% gives even better water dispersibility, and is in the range of from 1.0 to 20%. Is more preferable.

Further, the printing agent of the present invention may use a crosslinking agent (F) described below for the purpose of further improving the washing fastness and the rub fastness. When the cross-linking agent (F) is used, the urethane resin (B-PES) having a functional group [X] capable of performing a cross-linking reaction with the functional group of the cross-linking agent (F) may be used. preferable.
Examples of the functional group [X] include a carboxyl group and a carboxylate group that can be used as the hydrophilic group. The carboxyl group and the like contribute to the aqueous dispersion stability of the urethane resin (B-PES) in the aqueous medium (C), and when they undergo a crosslinking reaction, also act as the functional group [X]. Partial crosslinking reaction of the crosslinking agent (F) may occur.
When a carboxyl group or the like is used as the functional group [X], the urethane resin (B) preferably has an acid value of 2 to 50, and has a acid value of 5 to 40. It is preferable to improve washing fastness and friction fastness. The acid value in the present invention is a theoretical value calculated based on the amount of an acid group-containing compound such as a carboxyl group-containing polyol used in the production of the urethane resin (B).

The urethane resin (B-PES) can be produced, for example, by reacting a polyol (b1), a polyisocyanate (b2), and, if necessary, a chain extender.
As the polyol (b1), a polyester polyol (b1-1) is used from the viewpoint of imparting a polyester structure to the urethane resin (B-PES), and a hydrophilic group is added to the urethane resin (B-PES). From the viewpoint of providing, a polyol having a hydrophilic group is used.

(Polyester polyol (b1-1))
Examples of the polyester polyol (b1-1) include those obtained by an esterification reaction of a low molecular weight polyol and a polycarboxylic acid, and polyesters obtained by a ring opening polymerization reaction of a cyclic ester compound such as ε-caprolactone. Alternatively, these copolymerized polyesters and the like can be used.

  Examples of the low molecular weight polyol include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3-butane having a molecular weight of about 50 to 300. Aliphatic polyols such as diols, aliphatic cyclic structure-containing polyols such as cyclohexanedimethanol, bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof can be used. .

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic anhydride, naphthalene-2,6-dicarboxylic acid, and the like. Naphthalene dicarboxylic acids such as naphthalene-2,7-dicarboxylic acid and naphthalene-1,5-dicarboxylic acid; aromatic polycarboxylic acids such as dimethyl terephthalate and orthophthalic acid; and anhydrides or ester-forming derivatives thereof. Can be used.

  As the aromatic structure-containing polyester polyol that can be used as the polyester polyol (b1-1), for example, as the combination of the low-molecular-weight polyol and the polycarboxylic acid, those having an aromatic structure in one or both of them are used. Can be manufactured.

  Specifically, as the aromatic structure-containing polyester polyol, an aliphatic polyol such as ethylene glycol, diethylene glycol, and 1,4-butanediol, and an aromatic polycarboxylic acid such as terephthalic acid, isophthalic acid, and phthalic acid are used. Those obtained by performing a combination reaction can be used. Further, it can also be produced by reacting an aromatic structure-containing polyol such as bisphenol A with the aliphatic polycarboxylic acid.

  The aromatic polycarboxylic acid is a total of at least one selected from the group consisting of orthophthalic acid, phthalic anhydride, naphthalenedicarboxylic acid and esterified products thereof in a total amount of 5.0% by mass based on the total amount of the polycarboxylic acid. It is preferable to use one containing 100% by mass, more preferably one containing 30% by mass to 100% by mass, and one containing 50% by mass to 100% by mass. It is preferred to use

  One or more of the orthophthalic acid and the phthalic anhydride are preferably used in a total amount of from 0.5% by mass to 30% by mass relative to the total amount of the aromatic polycarboxylic acid, and from 0.5% by mass to It is more preferably used in the range of 20% by mass, and still more preferably used in the range of 1% to 8% by mass. In addition, at least one selected from the group consisting of naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and their esterified products has a total of 70% by mass to 99.5% by mass based on the total amount of the aromatic polycarboxylic acid. It is preferably contained in the range, more preferably used in the range of 92% by mass to 99% by mass, and used in the range of 80% by mass to 99.5% by mass, It is more preferable to obtain a printing agent having excellent rub fastness.

  As the polycarboxylic acid, other than the aromatic polycarboxylic acid, for example, an aliphatic polycarboxylic acid and the like may be used in combination, but the aromatic polycarboxylic acid is 90% by mass with respect to the total amount of the polycarboxylic acid. It is preferably used in the above range, and more preferably in the range of 95% by mass to 100% by mass.

  The aromatic structure-containing polyol is obtained by subjecting a polyether polyol obtained by adding an alkylene oxide to a bisphenol compound to an esterification reaction with an aromatic polycarboxylic acid.

  The aromatic structure-containing polyol can be produced by subjecting an alkylene oxide adduct obtained by adding an alkylene oxide to a hydroxyl group of a bisphenol compound to an esterification reaction with an aromatic polycarboxylic acid.

  The alkylene oxide adduct is a polyether polyol in which an alkylene oxide is added to a hydroxyl group of a bisphenol compound, and can be produced by adding an alkylene oxide by a known and common method using the bisphenol compound as an initiator.

Examples of the bisphenol compound include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, 4,4-bis (hydroxyphenyl) sulfide, bis (4-hydroxy Phenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) amine, tricyclo [5,2,1,0 ^2,6 ] decanediphenol and the like can be used. Among them, the use of bisphenol A is preferred for improving the washing fastness and the rub fastness.

  As the alkylene oxide that can be added to the hydroxyl group of the bisphenol compound, for example, ethylene oxide, propylene oxide, or the like can be used, and it is preferable to use one or more selected from the group consisting of ethylene oxide and propylene oxide.

  As the alkylene oxide adduct, one in which 1 mol to 20 mol of alkylene oxide is added to one molecule of the bisphenol compound is preferably used, and one in which 1 mol to 10 mol of alkylene oxide is added is used. It is more preferable to use a resin to which 2 to 4 mol of alkylene oxide is added, without lowering the aromatic ring concentration in the urethane resin, and having excellent washing fastness and friction fastness. It is more preferable to obtain an aqueous urethane resin composition.

  In producing the polyetherester polyol, other polyols (b1-2) and the like can be used in combination with the alkylene oxide adduct of the bisphenol compound and the aromatic polycarboxylic acid.

  Examples of the other polyol (b1-2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3. -Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7- Heptanediol, neopentyl glycol and the like can be used.

  The other polyol (b1-2) is 1.0% by mass to 30% by mass based on the total mass of the alkylene oxide adduct of the bisphenol compound, the aromatic polycarboxylic acid, and the other polyol (b1-2). May be used.

(Reaction between polyol and polycarboxylic acid)
The reaction between the polyol and the polycarboxylic acid can be performed by performing an esterification reaction between a hydroxyl group of the polyol and a carboxyl group of the polycarboxylic acid.

  Specifically, the polyol and the polycarboxylic acid can be reacted at normal pressure or reduced pressure in a reactor in which an inert gas such as nitrogen is substituted in the presence of a catalyst if necessary. The reaction is preferably performed at a temperature in the range of 100 ° C to 300 ° C.

  As the catalyst, for example, an alkali metal or alkaline earth metal acetate, a compound containing zinc, manganese, cobalt, antimony, germanium, titanium, tin, zirconium and the like can be used. Among them, it is preferable to use a tetraalkyl titanate or tin oxalate which is effective for a transesterification reaction or a polycondensation reaction.

  The catalyst is preferably used in the range of 0.005% by mass to 1.0% by mass based on the total mass of the various raw materials used for producing the polyetherester polyol.

  It is preferable to use a polyester polyol (b1-1) having a number average molecular weight in the range of 200 to 5,000. Among them, the aromatic structure-containing polyester polyol having a number average molecular weight of 250 to 3000 is preferably used.

(Polyol having hydrophilic group)
In addition, as the polyol having a hydrophilic group, for example, an anionic group-containing polyol, a cationic group-containing polyol, and a nonionic group-containing polyol other than the above-described polyester polyol (b1-1) can be used. Among them, it is preferable to use an anionic group-containing polyol or a cationic group-containing polyol, and it is more preferable to use an anionic group-containing polyol.

As the anionic group-containing polyol, for example, a carboxyl group-containing polyol and a sulfonic acid group-containing polyol can be used.
Examples of the carboxyl group-containing polyol include 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid, 2,2'-dimethylolbutyric acid, 2,2'-dimethylolvaleric acid, and dicarboxylic acid and dicarboxylic acid. A carboxyl group-containing polyester polyol obtained by reacting with an acid can be used. Among them, it is preferable to use 2,2'-dimethylolpropionic acid.

It is preferable that a part or all of the anionic group is neutralized by a basic compound or the like in order to exhibit good water dispersibility.
Examples of the basic compound that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or more, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine; NaOH, KOH, and LiOH. And the like can be used. From the viewpoint of improving the aqueous dispersion stability of the obtained coating agent, the basic compound is preferably used in a range of basic compound / anionic group = 0.5 to 3.0 (molar ratio), More preferably, it is used in a range of 0.5 to 2.0 (molar ratio).

Further, as the cationic group-containing polyol, for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule and a secondary amine Can be used.
The cationic group is preferably partially or entirely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, and adipic acid.
The tertiary amino group as the cationic group is preferably partially or entirely quaternized. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and it is preferable to use dimethyl sulfate.

  Further, as the nonionic group-containing polyol, a polyalkylene glycol having a structural unit derived from ethylene oxide or the like can be used.

  The hydrophilic group-containing polyol is preferably used in the range of 0.3% by mass to 20% by mass based on the total amount of the polyol used for producing the urethane resin (B-PES).

(Other polyols)
As the other polyol, for example, a polyether polyol, a polyester polyol, a polycarbonate polyol, or the like can be used in addition to the hydrophilic group-containing polyol.

  As the polyether polyol that can be used for the other polyols, for example, those obtained by subjecting an alkylene oxide to addition polymerization using ethylene glycol, propylene glycol, or the like as an initiator can be used.

  As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like can be used.

  Examples of the polyester polyol that can be used for the other polyols include, for example, fats obtained by esterifying ethylene glycol or propylene glycol with a polycarboxylic acid such as orthophthalic acid, isophthalic acid, adipic acid or sebacic acid. Polyesters obtained by ring-opening polymerization of cyclic ester compounds such as aromatic polyester polyols, aromatic polyester polyols, and ε-caprolactone, and copolymerized polyesters thereof can be used.

  Further, as the polycarbonate polyol that can be used as the other polyol, for example, those obtained by reacting a carbonate ester with various polyols, and those obtained by reacting phosgene with bisphenol A or the like can be used. .

  In addition, as the other polyol, in addition to those described above, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, Relatively low molecular weight polyols such as 7,7-heptanediol and neopentyl glycol can also be used.

(Polyisocyanate (b2))
Examples of the polyisocyanate (b2) that reacts with the polyol (b1) to form a urethane resin (B-PES) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate, and hexamethylene diisocyanate. Aliphatic or aliphatic cyclic structure-containing diisocyanates such as lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc., are used alone or in combination of two or more. be able to. Among them, the use of an aliphatic cyclic structure-containing diisocyanate is more preferred for imparting excellent washing fastness and friction fastness.

(Polycarbonate polyurethane resin)
Preferred resins for the polycarbonate polyurethane resin used in the present invention include, for example, a polycarbonate polyol (b3-1) as the polyol (b3) and an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group. And a urethane resin obtained by reacting a polyol (b3-2) having a hydrophilic group with a polyisocyanate. (Hereinafter referred to as urethane resin (B-PC)).
The polycarbonate polyurethane resin used in the present invention comprises a polycarbonate polyol (b3-1) as a polyol (b3) instead of the polyester polyol (b1-1) which is a raw material of the polyester polyurethane resin (B-PES), The same as the polyester polyurethane resin (B-PES) except that a polyol (b3-2) having a hydrophilic group, which is a group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group, is used. Obtainable.

  The polycarbonate structure is preferably used in a range of 10 to 90% by mass based on the total mass of the polyol (b3) and the polyisocyanate (b2) used for producing the polycarbonate urethane resin (B-PC). .

  As the polycarbonate polyol (b3-1), for example, those obtained by reacting a carbonate ester with a low molecular weight polyol, preferably a linear aliphatic diol, can be used.

  Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

  Examples of the low molecular weight polyol capable of reacting with the carbonate include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4 -Cyclohexane dimethanol, hydroquinone, resorci , Bisphenol-A, bisphenol-F, 4,4'-biphenol, etc., relatively low molecular weight dihydroxy compounds, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, poly Polyester polyols such as hexamethylene succinate and polycaprolactone can be used.

  It is more preferable that the hydrophilic group that can be introduced into the polycarbonate-based urethane resin (B-PC) be present in an amount of 100 mmol / kg to 1200 mmol / kg with respect to the entire polycarbonate-based urethane resin (B-PC). It is more preferable that the content is in the range of 150 mmol / kg to 1000 mmol / kg.

  The hydrophilic group-containing polyol that can be introduced into the polycarbonate-based urethane resin (B-PC) is 0.3% by mass to 15.0% based on the total amount of the polyol used for producing the polycarbonate-based urethane resin (A). It is preferable to use it in the range of mass%.

(Production method of urethane resin (B))
The urethane resin (B) can be manufactured by a known method. For example, in the case of a urethane resin (B-PES), in the absence of a solvent or in the presence of an organic solvent, the polyol (b1) containing the polyetherester polyol (b1-1) and the polyisocyanate (b2), If necessary, it can be produced by reacting with a chain extender. Alternatively, in the case of the urethane resin (B-PC), a polyol (b3) containing a polycarbonate polyol (b3-1) may be used instead of the polyol (b1) containing a polyetherester polyol (b1-1). What is necessary is just to manufacture similarly.

  When the organic solvent is used, when the urethane resin (B) is dispersed in the aqueous medium (B) or the like, it is preferable to remove the organic solvent by a method such as distillation as necessary. Examples of usable organic solvents include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide; Pyrrolidone and the like can be used alone or in combination of two or more.

  In the reaction between the polyol (b1) or (b3) and the polyisocyanate (b2), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (b2) to the hydroxyl group of the polyol (b1) or (b3) is as follows: It is preferably performed in the range of 0.8 to 2.5, and more preferably in the range of 0.9 to 1.5.

  The chain extender that can be used when producing the urethane resin (B) can be used for the purpose of increasing the molecular weight of the urethane resin (B) and improving the washing fastness and friction fastness.

  As a chain extender that can be used in producing the urethane resin (B), a polyamine, another active hydrogen atom-containing compound, or the like can be used.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine; N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine; dihydric succinate Radid, adipic dihydrazide, glutaric dihydrazide, sebacic dihydrazide, isophthalic dihydrazide; β-semicarbazide propionic hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5 5-trimethylcyclohexane can be used, preferably ethylene diamine.

  Examples of the other active hydrogen-containing compounds include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as pentyl glycol, saccharose, methylene glycol, glycerin and sorbitol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone Phenols, water, and the like.

  The chain extender is, for example, a urethane prepolymer obtained by reacting the polyol (b1) or (b3) with the polyisocyanate (b2) in an equivalent amount of the amino group and the active hydrogen atom-containing group of the chain extender. It is preferably used within a range of 1.9 or less (equivalent ratio) with respect to the isocyanate group equivalent of the polymer, and more preferably within a range of 0.3 to 1.0 (equivalent ratio).

  The chain extender can be used when reacting the polyol (b1) or (b3) with the polyisocyanate (b2) or after the reaction. Further, when the urethane resin (B) obtained above is dispersed in an aqueous medium (B) to make it aqueous, the above-mentioned chain extender can be used.

  Further, when producing the urethane resin (B), a curing accelerator can be used in combination from the viewpoint of shortening the reaction time.

  As the curing accelerator, for example, a tertiary amine catalyst or an organometallic catalyst can be used. As the tertiary amine catalyst, for example, triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N, N-dimethylethanolamine, ethylmorpholine and the like can be used. As the organometallic catalyst, for example, stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, sodium bicarbonate and the like can be used.

  The urethane resin (B-PES) obtained by the above method preferably has a weight average molecular weight in the range of 5,000 to 200,000 from the viewpoint of washing fastness and friction fastness. It is more preferred to use one having a weight average molecular weight in the range of 000 to 100,000.

The urethane resin (B-PC) obtained by the above method preferably has a weight average molecular weight in the range of 5,000 to 200,000 from the viewpoint of washing fastness and friction fastness, and is preferably 20,000 to 100,000. It is more preferable to use those having a weight average molecular weight in the range of

  As the urethane resin (B) obtained by the above method, it is preferable to use a urethane resin having a hydrophilic group as described above, but use a urethane resin (B) having no hydrophilic group as described above. You can also. In such a case, it is preferable to use a surfactant, which will be described later, as a material that can contribute to the dispersion of the urethane resin (B). Even when a hydrophilic group-containing urethane resin is used as the urethane resin (B), a similar surfactant may be used as necessary from the viewpoint of further improving the water dispersion stability. .

  Examples of such surfactants include nonionics such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkane sulfonates, alkyl diphenyl ether sulfones Anionic surfactants such as sodium acid salts; cations such as alkylamine salts, alkyltrimethylammonium salts and alkyldimethylbenzylammonium salts It can be used system surfactant. Among them, it is preferable to use an anionic or nonionic surfactant from the viewpoint of improving the dispersion stability of the urethane resin of the present invention.

  When the surfactant is used, it is preferable to use the surfactant in the range of 0% by mass to 5.0% by mass with respect to the total amount of the urethane resin (B) from the viewpoint of washing fastness and friction fastness.

  Examples of the method of dispersing the urethane resin (B) obtained by the above method in the aqueous medium (B) include the following methods 1 and 2.

  [Method 1] When a hydrophilic group-containing urethane resin is used as the urethane resin (B), a part or all of the hydrophilic groups of the urethane resin obtained by the method may be replaced with the basic compound as necessary. A method of obtaining an aqueous dispersion of a urethane resin (B) by mixing and stirring the mixture neutralized or quaternized with the aqueous medium (B).

  [Method 2] When a urethane resin having no hydrophilic group is used as the urethane resin (B), the urethane resin obtained by the method is mixed with a surfactant described below under stirring conditions. A method of obtaining an aqueous dispersion of a urethane resin (B) by emulsifying and dispersing by adding an aqueous medium (B), or by forcibly emulsifying and dispersing using an emulsifier or the like.

  When the production of the urethane resin (B) is carried out in the presence of an organic solvent instead of without a solvent, after producing an aqueous dispersion of the urethane resin (B) by the methods 1 and 2, if necessary, It is preferable to remove the organic solvent by a method such as distillation.

  Examples of the aqueous medium (B) serving as a solvent for the urethane resin (B) include water, an organic solvent miscible with water, and a mixture thereof. Examples of the water-miscible organic solvent include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; Alkyl ethers; N-methyl-2-pyrrolidone; In the present invention, only water may be used, or a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and environmental load, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.

  In any of the above methods 1 and 2, when dispersing the urethane resin (B) in the aqueous medium (B) with water, a machine such as a homogenizer can be used as necessary.

  The urethane resin (B) thus obtained is in a state where the urethane resin (B) is dispersed in an aqueous medium. When adjusting as a printing agent, it is preferable that the urethane resin (B) is an aqueous dispersion in which the urethane resin (B) is dispersed in an aqueous medium. At this time, the aqueous medium is contained in the range of 30% by mass to 90% by mass with respect to the total amount of the composition of the urethane resin (B) to obtain a resin composition having excellent water dispersion stability. Above.

  When used as an inkjet ink, the particle size of the aqueous dispersion of the urethane resin (B) is preferably from 5 nm to 1000 nm, more preferably from 10 nm to 400 nm, from the viewpoint of dischargeability.

(Amount of binder resin used)
In the present invention, the acrylic copolymer (A) and the urethane resin (B) are used in combination. Although the weight ratio is not particularly limited, for example, the weight ratio is preferably in the range of 10/90 to 90/10, and more preferably in the range of 15/85 to 85/15.
In addition, since the acrylic copolymer (A) itself contributes to texture (flexibility), it is preferable to use, for example, the acrylic copolymer (A): pigment = 1: 1 to 8: 1. Further, since the urethane resin (B) itself contributes to the washing fastness and the friction fastness, it is preferable to use the urethane resin (B): pigment = 1: 1 to 8: 1, for example.

  Further, with respect to the total amount of the printing agent, the amount of the binder used contributes to the washing fastness and the rub fastness. Therefore, in order to obtain higher washing fastness and the rub fastness, the total amount of the binder is from 0.3% by mass to 12%. It is preferably used in the range of 1.0% by mass, more preferably 1.0% by mass to 10% by mass, and most preferably 3.0% by mass to 9.0% by mass. However, excessive use of a high molecular weight binder resin leads to an increase in viscosity. Therefore, when applied to an inkjet recording ink, it is preferable to determine the amount of the binder to be used in consideration of the balance with the viscosity.

  In addition, a resin known as a binder resin such as a styrene resin or a polyester resin may be used, but the range is preferably set so as not to impair the effects of the present invention.

(Production method of printing agent)
The printing agent of the present invention prepares a high-concentration aqueous dispersion (pigment paste) of the pigment, dilutes it with a water-soluble solvent and / or water, and uses the acrylic copolymer (A) and the urethane as binder resins. It can be prepared by adding the resin (B) and other additives as necessary.

The method for dispersing the pigment in the water-soluble solvent and / or water to obtain a pigment paste is not particularly limited, and it is preferable to use a known dispersion method. The dispersant used at this time may be dispersed in water using a known pigment dispersant, or a surfactant may be used.
As the pigment dispersant, an aqueous resin is preferable, and preferable examples are polyvinyl alcohols, polyvinyl pyrrolidone, acrylic resins such as acrylic acid-acrylate copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid. Styrene such as acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid-acrylic acid ester copolymer An acrylic copolymer, a styrene-maleic acid copolymer, a styrene-maleic anhydride copolymer, a vinylnaphthalene-acrylic acid copolymer, and a salt of the aqueous resin are exemplified.
Examples of the compound for forming a salt of the copolymer include alkali metals such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, and diamine. Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, morpholine and the like. The amount of the compound used to form these salts is preferably equal to or more than the neutralization equivalent of the copolymer.
Of course, it is also possible to use a commercially available product. As commercially available products, Ajisper PB series manufactured by Ajinomoto Fine Techno Co., Ltd., DisPESrbyk series and BYK-series manufactured by BYK Japan KK, and EFKA series manufactured by Ciba Specialty Chemicals can be used.

Further, as the dispersion method, for example, the following (1) to (3) can be shown.
(1) A method of preparing a pigment paste by adding a pigment to an aqueous medium containing a pigment dispersant and water, and then dispersing the pigment in the aqueous medium using a stirring / dispersing device.
(2) The pigment and the pigment dispersant are kneaded using a kneader such as a two-roll mill or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is dispersed using a stirring / dispersing apparatus. How to prepare a paste.
(3) After the pigment is added to a solution obtained by dissolving the pigment dispersant in an organic solvent compatible with water such as methyl ethyl ketone, tetrahydrofuran, etc., the pigment is added to the organic solution using a stirring / dispersing device. And then performing phase inversion emulsification using an aqueous medium, and then distilling off the organic solvent to prepare a pigment paste.

The kneader is not particularly limited, and examples thereof include a Henschel mixer, a pressure kneader, a Banbury mixer, and a planetary mixer.
The stirring / dispersing apparatus is not particularly limited, and examples thereof include an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, and a nanomizer. One of these may be used alone or two or more of them may be used in combination.

  The amount of the pigment in the pigment paste is preferably 5.0 to 60% by mass, more preferably 10 to 50% by mass. When the amount of the pigment is less than 5% by mass, coloring of the aqueous ink prepared from the pigment paste is insufficient, and a sufficient image density tends not to be obtained. On the other hand, when it is more than 60% by mass, the dispersion stability of the pigment in the pigment paste tends to decrease.

  In addition, since coarse particles cause nozzle clogging and other deterioration of image characteristics, it is preferable to remove coarse particles by centrifugation, filtration, or the like before and after ink preparation.

  After the dispersing step, a post-treatment may be performed after an impurity removing step by an ion exchange treatment or an ultra-fine treatment. Ion exchange treatment can remove ionic substances (such as divalent metal ions) such as cations and anions, and ultra-fine treatment can dissolve impurities (residual substances during pigment synthesis, excess components in the dispersion liquid composition). , A resin not adsorbed on the organic pigment, a contaminant foreign matter, etc.) can be removed. For the ion exchange treatment, a known ion exchange resin is used. The ultra-treatment is performed by using a known ultra-filtration membrane, and may be either a normal type or a double-up type.

  After preparing the pigment paste, it is appropriately diluted and an additive is added as necessary to obtain a printing agent suitable for the purpose. The form of the printing agent is arbitrarily selected according to a preferable treatment method such as dip dyeing or printing according to the fiber to be colored. For example, for screen recording inks whose application is suitable for printing, additives such as preservatives, viscosity regulators, pH regulators, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, and cross-linking agents are used. However, the final pigment concentration is preferably in the range of 1 to 10% by mass. In such a case, the additive is preferably added together with the binder resin.

  Further, for example, when the application is a printing agent for dyeing, as an additive, a preservative, a viscosity adjuster, a pH adjuster, a chelating agent, an antioxidant, an ultraviolet absorber, a flame retardant, a crosslinking agent, and a binder resin. And the final pigment concentration is preferably in the range of 1.0 to 10% by mass. The viscosity is arbitrarily set in the range of 1.0 mPa · s to 100 mPa · s according to the device. In addition, for example, the use of a printing agent for spray printing uses, as an additive, a viscosity adjusting agent, a pH adjusting agent, a chelating agent, a plasticizer, an antioxidant, an ultraviolet absorber, and a binder resin. The pigment concentration is preferably in the range of 1.0% by mass to 10% by mass. The viscosity is arbitrarily set in the range of 1.0 mPa · s to 100 mPa · s according to the device.

  In addition, for example, in an ink jet recording ink suitable for use in textile printing, additives such as preservatives, viscosity modifiers, pH regulators, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, cross-linking agents, etc. The final pigment concentration is preferably 1.0 to 20% by mass in order to obtain a sufficient image density and to secure the dispersion stability of the pigment in the ink. In such a case, the additive is preferably added together with the binder resin. The dilution ratio can be adjusted to the required concentration in consideration of the concentration of the surfactant aqueous solution, and then subjected to ultrasonic treatment, whereby the ink for inkjet recording can be adjusted.

  Specific examples of preservatives or fungicides include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3-. ON (Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, Proxel DL of Arch Chemicals) and the like.

  Specific examples of the viscosity modifier include mainly water-soluble natural or synthetic polymers such as carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic and starch.

  Specific examples of the pH adjuster include collidine, imidazole, phosphoric acid, 3- (N-morpholino) propanesulfonic acid, tris (hydroxymethyl) aminomethane, and boric acid.

  Specific examples of the chelating agent include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramildiacetic acid, 1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid, and salts thereof (including hydrates).

  Specific examples of antioxidants or UV absorbers include allohanates, allohanates such as methyl allohanate, biuret, dimethyl biuret, biuret such as tetramethyl biuret, L-ascorbic acid and salts thereof, and the like, manufactured by Ciba Geigy. Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, etc., or oxides of lanthanides.

  The method of the dilution and the addition of the additive can be performed by a method generally used conventionally without any particular limitation. For example, after mixing the pigment paste, a binder resin, a surfactant as an additive, a viscosity modifier, an antifoaming agent, an antioxidant or an ultraviolet absorber, a preservative, and the like, a solvent according to a dilution ratio, and then various dispersions. Examples thereof include a method of dispersing and mixing using a mixer or a stirrer, such as a bead mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, an ultra-high pressure homogenizer, and a pearl mill. If necessary, various additives may be further added after this.

  Further, a water-soluble organic solvent may be further added for the purpose of stably dissolving or dispersing and holding the additive, the pigment, the pigment dispersant, and the urethane resin.

  Examples of the water-soluble solvent include monohydric or polyhydric alcohols, amides, ketones, keto alcohols, cyclic ethers, glycols, lower alkyl ethers of polyhydric alcohols, polyalkylene glycols, and glycerin. , N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2- Pentanediol, 1,2 6-hexanetriol, trimethylolpropane, polyols such as pentaerythritol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene Polyhydric alcohol alkyl ethers such as glycol monobutyl ether; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether; and polyhydric alcohol aralkyl ethers, 2-pyrrolidone, N-methyl-2-pyrrolidone , Lactams such as ε-caprolactam, 1,3-dimethylimidane Dazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone, m-butyrolactone, polyoxyalkylene adduct of glycerin, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolan, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, Acetone alcohol, dimethylformamide propylene glycol monomethyl ether and the like. These may be used alone or in combination of two or more.

  Furthermore, saccharides can be used for the same purpose. Examples thereof include monosaccharides and polysaccharides, glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitolose, maltose, cellobiose, sucrose, trehalose, maltotriose and the like. Alginic acid and its salts, cyclodextrins, and celluloses can be used.

  Further, the printing agent of the present invention may contain a surfactant in order to control its permeability. The surfactant used at this time is preferably one having good compatibility with other components present in the printing agent of the present invention. Further, a surfactant having high permeability and being stable is preferable.

Specifically, it is preferable to use an amphoteric surfactant or a nonionic surfactant.
Preferred examples of the amphoteric surfactant include betaine lauryl dimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyl dimethylamino acetate betaine, polyoctyl polyaminoethyl glycine, and others. And imidazoline derivatives.

  Preferred examples of the nonionic surfactant include an acetylene glycol-based surfactant, an acetylene alcohol-based surfactant, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, and polyoxyethylene alkyl. Ethers such as allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene oleate, and polyoxyethylene distearate , Sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, polyoxye Ren monooleate, ester-based surfactants such as polyoxyethylene stearate, silicon-based surfactants such as dimethylpolysiloxane, other fluorine-containing alkyl esters, and fluorine-containing surfactants such as perfluoroalkylcarboxylates. In particular, acetylene glycol-based surfactants and acetylene alcohol-based surfactants are preferred. When these surfactants are added to the ink composition, they are preferable because they have low foaming properties and excellent defoaming functions. Specific examples of the acetylene glycol-based surfactant and the acetylene alcohol-based surfactant include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 3,6-dimethyl-4-octyne- Examples thereof include 3,6-diol and 3,5-dimethyl-1-hexyne-3ol, which are also commercially available. For example, Surfynol 61, 82, 104, 465 manufactured by Air Products (UK). , 485, TG, Olfin STG, Olfin E1010 of Nissin Chemical Industry Co., Ltd. and the like.

  The addition amount of the surfactant is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the printing agent, more preferably 5.0% by weight, and more preferably 5.0% by weight. 0.5% by weight.

  Further, when the textile printing agent of the present invention is applied to the ink jet recording method, it is preferable to adjust the surface tension to be 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN / m or more and 45 mN / m or less, and still more preferably 20 mN / m or more and 40 mN / m or less. If the surface tension is less than 20 mN / m, the liquid may overflow on the nozzle surface and printing may not be performed normally. On the other hand, if it exceeds 60 mN / m, repelling tends to occur on the non-absorbing substrate. The viscosity is preferably from 1.2 mPa · s to 20.0 mPa · s, more preferably from 2.0 mPa · s to less than 15.0 mPa · s, and still more preferably from 3.0 mPa · s to 12 mPa · s. 2.0 mPa · s. When the viscosity is in this range, it is possible to achieve excellent ejection properties and good ejection properties over a long period of time. The surface tension can be appropriately adjusted by the surfactant.

(Adherend)
When the textile printing agent obtained by the production method of the present invention is used as various inks, printing can be performed not only on general-purpose adherends such as paper, but also on cloth, artificial leather, natural leather, and the like. In particular, it is particularly excellent in printing on fabric.
The fabric used in the present invention is preferably a medium composed of fibers, and may be a nonwoven fabric or a nonwoven fabric. As a material, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, rayon and the like can be used.

  Hereinafter, the effects of the present invention will be specifically described using examples and comparative examples, but the present invention is not limited to these examples. In the following description, parts and% indicate parts by mass.

<Production example of acrylic copolymer>
(Production Example 1: Synthesis of acrylic copolymer (A-1))
280.0 parts by mass of n-butyl acrylate (hereinafter abbreviated as “BA”), 90.0 parts by mass of methyl methacrylate (hereinafter abbreviated as “MMA”), styrene (hereinafter, “St”) 70.0 parts by mass, 2-hydroxyethyl methacrylate (hereinafter abbreviated as "HEMA") 6.0 parts by mass, and acrylic acid (hereinafter abbreviated as "AA") 13.0 parts by mass. Glycidyl methacrylate (hereinafter abbreviated as “GMA”) 6.0 parts by mass, water 40.0 parts by mass, and a nonionic emulsifier (“Neugen EA-207D” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene) After mixing 10 parts by mass of (distyrenated phenyl ether), the mixture was emulsified using a homogenizer ("TK homodisper" manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a monomer emulsion.

  Then, 500.0 parts by mass of water was placed in a flask equipped with a stirrer, a nitrogen inlet tube and a reflux condenser, heated to 50 ° C. while stirring and mixing under a nitrogen gas atmosphere, and then ammonium persulfate (hereinafter “APS”). 2.0 parts by mass and 2.0 parts by mass of sodium metabisulfite (hereinafter, abbreviated as “SMS”) were added and dissolved in the flask. Thereafter, the monomer emulsion prepared above, 40.0 parts by mass of a 5% by mass APS aqueous solution, and 40.0 parts by mass of a 5% by mass SMS aqueous solution were dropped into the flask over 3 hours. The temperature in the flask during this dropping was controlled at 50 to 60 ° C. After completion of the dropwise addition, the mixture was further reacted at 60 ° C. for 1 hour to obtain an acrylic copolymer (A-1). Then, after cooling to room temperature, 7 parts by mass of aqueous ammonia of 25% by mass was added for neutralization, water was added so that the resin content was 45% by mass, and the mixture was mixed uniformly, and the acrylic copolymer (A- An aqueous resin emulsion 1) was obtained.

(Production Examples 2 to 4: Synthesis of Acrylic Copolymers (A-2) to (A-4))
Except that the raw materials shown in Table 1 below were used, the same procedure as in Production Example 1 was carried out to obtain aqueous resin emulsions of acrylic copolymers (A-2) to (A-4).

(Comparative Production Example 1: Synthesis of acrylic copolymer (RA-1))
Except that the raw materials shown in Table 1 below were used, the same procedure as in Production Example 1 was carried out to obtain a comparative aqueous resin emulsion of an acrylic copolymer (RA-1).

The abbreviations in Table 1 are described below.
BA: n-butyl acrylate EA: ethyl acrylate MMA: methyl methacrylate St: styrene AN: acrylonitrile HEMA: 2-hydroxyethyl methacrylate AA: acrylate IA: itaconic acid GMA: glycidyl methacrylate VSi: vinyl triethoxysilane DAAM : Acetone acrylamide APS: Ammonium persulfate SMS: Sodium metabisulfite

<Preparation of polyetherester polyol>
(Synthesis Example 1: Synthesis of polyetherester polyol (b1-1))
In a four-necked flask, 216.7 parts by mass of Newpole-BPES-20T (2 mol adduct of bisphenol A with ethylene oxide, manufactured by Sanyo Chemical Industries, Ltd.), 47.3 parts by mass of dimethyl 2,6-naphthalenedicarboxylate, 30.1 parts by mass of dimethyl terephthalate, 1.5 parts by mass of phthalic anhydride, and 0.01 parts by mass of tetrabutyl titanate are reacted under a nitrogen stream at 220 ° C. for 24 hours, and are polyetheresters which are yellow solids at room temperature. Polyol (b1-1) (acid value 0.08) was obtained.

<Synthesis of urethane resin>

(Production Example 4: Production of urethane resin (B-PES1))
In a reaction vessel, 100.0 parts by mass of the aromatic polyetherester polyol (b1-1) obtained in Synthesis Example 1 was dehydrated at 100 ° C. under reduced pressure, and then cooled to 80 ° C., and 90 parts by mass of methyl ethyl ketone was added. The mixture was stirred and dissolved, and 8.0 parts by mass of 2,2′-dimethylolpropionic acid and 0.5 part of neopentyl glycol were added. Then, 26.4 parts by mass of hexamethylene diisocyanate was added, and the mixture was reacted at 75 ° C. for 8 hours. .
Subsequently, the mixture was cooled to 50 ° C., neutralized by adding 6.1 parts by mass of triethylamine, and then made water-soluble by adding 700.0 parts by mass of water. After removing methyl ethyl ketone from the obtained transparent reaction product under reduced pressure at 40 ° C to 60 ° C, water is added to adjust the concentration, whereby a stable aqueous urethane resin (B- PES1) was obtained.

(Production Example 5: Production of urethane resin (B-PC1))
Polycarbonate polyol (b3-1) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer (number average molecular weight 2000) 50.0 parts by mass, 3.77 parts by mass of 2,2-dimethylolpropionic acid and 15.7 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 9.24 parts by mass of tolylene diisocyanate, 0.01 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours to obtain a polyurethane (B-PC1) having a weight average molecular weight of 37000 (acid This gave an organic solvent solution having a value of 25).
Thereafter, the mixture is cooled to 50 ° C., 2.98 parts by mass of triethylamine and 206.9 parts by mass of water are added, and methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and the concentration is adjusted by adding water. Thus, a stable aqueous urethane resin (B-PC1) resin composition having a nonvolatile content of 23% by mass in which the urethane resin was dispersed in an aqueous medium was obtained.

<Preparation of pigment paste>
15 parts of styrene-maleic acid half ester (acid value: 116 mgKOH / g, weight average molecular weight: 42,000), 1.57 parts of potassium hydroxide (0.1 part based on the total amount of acidic groups in styrene-maleic acid half ester). An amount equivalent to 90 equivalents) and 83.43 parts of water were mixed and stirred at 70 ° C. using a stirrer to obtain a translucent resin dispersion. 40 parts of the resin dispersion, 20 parts of copper phthalocyanine pigment (FASTOGEN BLUE 5327 WET manufactured by DIC) (in terms of solid content) and 40 parts of water are mixed and stirred, and 500 parts of 0.3 mmφ ceramic beads are added to the mixture. After that, the mixture was ground with a 6-tube sand grinder for 6 hours. After grinding, the ceramic beads were separated to obtain a mill base. 70 parts of the mill base and 30 parts of water obtained above were mixed and stirred, and the mixture was subdivided with an ultrasonic homogenizer at an output of 600 W for 3 hours to obtain a pigment paste.

<Example 1 Preparation of printing agent (1)>
20.0 parts of the pigment paste, a solvent (water, water-soluble solvent, oil-soluble solvent, etc.), 2.5 parts of an aqueous resin emulsion of acrylic copolymer (A-1) (solid content: 45% by mass), urethane resin 13.5 parts of (B-PES1) (solid content 23% by mass) was added (mass ratio [(A) / (B)] = 75/25) to obtain a printing agent (1) of Example. The composition of each printing agent is shown in Table 4. At the time of addition of each example, the mixture was sufficiently stirred with a dispersion stirrer (TK homodisper L manufactured by Tokushu Kika Kogyo KK).

<Examples 2 to 14 Preparation of printing agents (2) to (24)>
Except having used the raw materials shown in the following Tables 4-6, it carried out similarly to Example 1, and obtained the printing agents (2)-(24) of the example.

<Reference Examples 1-2 Preparation of printing agents (25)-(26)>
The same procedures as in Example 1 were carried out except for using the raw materials shown in Table 7 below, to thereby obtain printing agents (25) to (26) of Reference Examples.

<Comparative Example 1 Preparation of printing agent (R1)>
A printing agent (R1) of Comparative Example was obtained in the same manner as in Example 1 except that the raw materials shown in Table 7 below were used.

<Preparation of evaluation cloth>
Using the printing agents obtained in the above Examples, Reference Examples and Comparative Examples, printing was performed on the fabric surface by the following method to obtain various evaluation fabrics.

<Preparation of fabric for evaluation of fastness_Screen printing>
Printing evaluation was performed by a screen printing method using an automatic screen printing machine (manufactured by Tsujii Dyeing Machine Co., Ltd.). Each printing agent was printed on a polyester / cotton cloth on a 135 mesh screen with a stripe pattern, dried at 120 ° C. for 2 minutes, and subjected to a heat treatment at 150 ° C. for 2 minutes. As a result of visual inspection of the printed matter, the quality was good.

<Production of evaluation cloth_Inkjet printing>
Each printing agent was filled in an ink cartridge of an inkjet printer (MJ-510C, manufactured by Seiko Epson Corporation) and printing was performed. After printing each printing agent on polyester / cotton fabric, it was dried at 120 ° C. for 2 minutes and subjected to heat treatment at 150 ° C. for 2 minutes. As a result of visual inspection of the printed matter, the quality was good.

<Washing fastness evaluation method>
The printed material obtained by screen printing is repeatedly subjected to a test in accordance with JIS L 0844: 2005, A-4 method, 30 times, and then subjected to visual perception using a gray scale for discoloration according to JIS L 0801: 2004. According to the criterion of the above, the grade was judged from the first to fifth grade. As for the grade, the fading is the largest in the first grade, and the fading decreases as the grade approaches the fifth grade.

<Fastness evaluation method>
The printed matter obtained by the screen printing was subjected to dry and wet tests using a Gakushin type friction fastness tester in accordance with JIS L 0849: 2004, and then a change of JIS L 0801: 2004 was conducted. According to the criterion of the visual sensation method using the gray scale for fading, the grade was judged from the first grade to the fifth grade. As for the grade, the fading is the largest in the first grade, and the fading decreases as the grade approaches the fifth grade.

<Hand evaluation method>
The evaluation cloth obtained above was evaluated with a tentacle according to the following criteria.
：: Flexible touch with no border between the printed surface and the fabric.
：: The tactile sensation is such that the border between the printed surface and the fabric is slightly felt.
Δ: Hard touch feeling where the border between the printed surface and the fabric is felt.
X: Hard touch feeling in which the boundary between the printed surface and the fabric is clearly felt.
As another texture evaluation method, a stiffness calculated using a stiffness tester (a cantilever method, a Gurley method, a handle ometer method, etc.) in accordance with JIS L 1913: 2010 is used. Evaluation may be sufficient. In addition, the softer the softness, the softer the softer the softness.

  Tables 4 to 6 show the compositions and various evaluation results of the printing agents (1) to (26) and (R1) obtained in Examples 1 to 24, Reference Examples 1 and 2, and Comparative Example 1. In addition, the unit of the combination in the table is parts, and in fact, Examples, References are Reference Examples and ratios are Comparative Examples.

  Reference Examples 1 and 2 are examples in which the acrylic copolymer (A-1) and the urethane resin (B-PES1) were used at a mass ratio [(A) / (B)] of 100/0 or 0/100. However, the acrylic copolymer (A-1) has excellent washing fastness and friction fastness (dry and wet) and excellent texture, and the urethane resin (B-PES1) has good washing fastness and friction fastness (dry and wet). It was confirmed that it was excellent.

  By using the acrylic copolymer (A) and the urethane resin (B) together, the advantages of each other are utilized, and the washing fastness and friction fastness (dry and wet) are excellent, and the printed fabric has an excellent texture. Can be given.

  Comparative Example 1 is an example in which an acrylic copolymer (RB-1) having no functional group and a urethane resin (B-PES1) having a polyester structure were used in combination, but compared with the printing agent of the present invention. The visual results and texture of the printed matter were good, but both the washing fastness and the rub fastness (dry and wet) were inferior.

Claims (4)

A printing agent containing a pigment, water, an organic solvent, and a binder resin, wherein the binder resin is a combination of an acrylic copolymer (A) and a urethane resin (B); The polymer (A) is a polymerizable monomer (a1) having a carboxyl group and 0.1% by mass to 5.0% by mass based on the total amount of the polymerizable monomer serving as a raw material of the acrylic copolymer (A). % Of the polymerizable monomer (a2) having an epoxy group, and 0.1% to 3.5% by mass of the hydrolyzable monomer based on the total amount of the polymerizable monomer used as the raw material of the acrylic copolymer (A). Polymerization having an amide group in an amount of 0.1% by mass to 5.0% by mass based on the total amount of the polymerizable monomer (a3) having a silyl group and the polymerizable monomer used as a raw material of the acrylic copolymer (A) At least one polymerizable monomer selected from the group consisting of the functional monomers (a4) Inkjet printing textile printing agents, characterized in that polymerizable acrylic copolymer of monomers obtained by polymerizing. The textile printing agent for inkjet printing according to claim 1, wherein the acrylic copolymer (A) has a glass transition temperature in a range of -50 to 30C. The textile printing agent for inkjet printing according to claim 1 or 2, wherein the urethane resin (B) is a urethane resin containing a polyester polyol or a polycarbonate polyol as an essential reaction component. The textile printing agent according to any one of claims 1 to 3, wherein a weight ratio of the acrylic copolymer (A) to the urethane resin (B) is in a range of 15/85 to 85/15.