JP6119919B2 - Printing agents and fabrics - Google Patents

Description

  The present invention relates to a printing agent and a fabric using the same.

  A pigment printing method using an aqueous pigment printing agent is known as a printing method for printing images such as letters, pictures, and patterns on a fabric such as a woven fabric, a nonwoven fabric, and a knitted fabric. The pigment printing method is a method in which a pigment printing agent containing a color pigment and a binder resin is printed, and then fixed to a substrate through a drying and curing step as necessary. Examples of this printing method include a silk screen method (for example, see Patent Document 1) in which a pattern of a screen bag is continuously printed on a cloth, an ink jet recording method in which ink is ejected from a nozzle and adhered to the cloth (for example, see Patent Document 2). )It has been known.

Compared to dye-based printing methods, pigment printing methods do not require the selection of colorants depending on the fiber type, the processing method is simple, and there is no need for steaming, water washing or soaping processes, so there is no energy cost. . Moreover, since no waste liquid is generated, it is a safe processing method in terms of environment.
However, the pigment printing method is different from the printing method using a dye, and the pigment as the color material is physically fixed to the fabric with a binder resin, so that the printing portion is removed from the fabric by washing or external friction. There were problems such as peeling (fastness to washing) and poor texture. Further, since the binder resin is easily formed into a film, sometimes the binder resin is dried and fixed, and a water-insoluble resin film is stretched to cause a problem such as clogging of the screen flaw. In particular, when the pigment printing method is applied to a photographic pattern having a fine pattern (halftone dots or lines), the highlight portion is likely to be clogged because it dries quickly. In addition, when the printing operation is stopped with the pigment printing agent remaining on the plate, the pigment printing agent is dried on the plate, and when the printing operation is resumed, the dried and fixed pigment printing agent is easily dissolved again. (This is hereinafter referred to as re-dissolvability) is difficult to transfer, and printing is not possible.
In addition, depending on the type of binder resin, the storage stability of the pigment printing agent may decrease due to the compatibility with various solvents blended in the pigment printing agent. There is also a problem that it is difficult to obtain vivid colors such as dyes.
As described above, since the pigment printing agent is greatly affected by the binder resin to be blended, a binder resin suitable for the pigment printing agent has been developed.

Urethane resins have been studied as binder resins suitable for pigment printing agents. For example, in Patent Documents 3 and 4, textile printing inks for inkjet recording using a polyurethane resin using a polyether polyol as a binder resin are resistant to abrasion and dry. It describes that it is excellent in cleaning property and ejection stability.
Patent Document 5 describes that a pigment printing binder made of an aqueous dispersion of a polyurethane resin using a polycarbonate diol has a low heat blocking property and a good dry cleaning resistance.
Patent Document 6 describes that a white pigment ink jet recording printing ink using a urethane resin having a specific range of film elongation, tensile strength, and zeta potential is excellent in white ink color development and washing fastness. Has been.

  Patent Documents 3 to 6 describe knowledge about abrasion resistance, fastness to washing, and resistance to dry cleaning. However, there has been no disclosure of an example of studying a pigment printing agent that has both the storage stability of a pigment printing agent, the color developability when a colored pigment is used, and the physical properties, washing fastness and texture of the pigment printing agent.

JP 2007-332523 A JP 2009-215506 A JP 2011-246632 A JP 2011-246634 A JP 2007-270362 A JP 2009-30014 A

  An object of the present invention is to provide a printing agent that has excellent storage stability, good color developability when a colored pigment is used, and excellent texture.

  By using a polycarbonate-based urethane resin having specific physical properties as a binder resin, the present inventors can use the silk screen method or the inkjet recording method without any problem, storage stability, re-dissolvability. It has been found that a printing agent excellent in washing fastness, good texture and excellent color development (printing density) can be obtained.

  That is, the present invention provides a printing agent comprising a pigment, water, an organic solvent, and a binder resin, wherein the binder resin is a polycarbonate urethane resin having a breaking elongation of 300% or more. To do.

  The present invention also provides a fabric product obtained by printing the above-described printing agent on a fabric.

  The printing agent of the present invention is excellent in storage stability by using a polycarbonate-based urethane resin having specific physical properties as a binder resin, and the fabric obtained by printing the printing agent on the fabric has good color development and texture. Excellent. Further, the printing agent of the present invention can be used without any problem whether it is a silk screen method or an ink jet recording method.

(Pigment)
The pigment used in the present invention is not particularly limited, and any pigment that is usually used in pigment printing agents can be used without particular limitation. Specifically, known inorganic pigments and organic pigments that can be dispersed in water or water-soluble organic solvents can be used. Examples of the inorganic pigment include carbon black produced by a known method such as titanium oxide, iron oxide, a contact method, a furnace method, and a thermal method. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments), polycyclic pigments (for example, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazines). Pigments, thioindigo pigments, isoindolinone pigments, quinofullerone pigments, etc.), dye chelates (for example, basic dye chelate, acid dye chelate, etc.), nitro pigments, nitroso pigments, aniline black, and the like.

Specific examples of the pigment include carbon black, No. manufactured by Mitsubishi Chemical Corporation. 2300, no. 2200B, no. 900, no. 980, no. 33, no. 40, No, 45, No. 45L, no. 52, HCF88, MCF88, MA7, MA8, MA100, etc. are Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, Regal 400R, Regal 330R, Moul 660R, Regul 660R, Regul 660R 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are Color Black FW1, Made by Degussa, FW2, FW2V, FW18, FW200, 170, S160, S35, U, V, 1400U, Special lack 6, the 5, 4, 4A, NIPEX150, NIPEX160, NIPEX170, NIPEX180 and the like.
Specific examples of pigments used in 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 pigments used in magenta ink include C.I. I. Pigment violet 19, 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, and these Examples thereof include a mixture or a solid solution of at least two kinds of pigments selected from pigments.
Specific examples of pigments used for cyan ink include C.I. I. Pigment blue 1, 2, 3, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 63, 66, and the like.
Specific examples of the pigment used in the red ink include C.I. I. CI Pigment Red 17, 49: 2, 112, 149, 150, 177, 178, 179, 188, 254, 255, and 264 are preferably used.
Specific examples of pigments used in orange ink include C.I. I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, 64, 71, 73, 81, and the like.
Specific examples of pigments used in green ink include C.I. I. Pigment green 7, 10, 36, 58, 59, and the like.
Specific examples of pigments used in violet ink include C.I. I. Pigment violet 19, 23, 32, 33, 36, 38, 43, 50 and the like.

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

  As the pigment used in the present invention, either dry powder or wet cake can be used. Moreover, these pigments may be used independently and may be used in combination of 2 or more types.

The pigment used in the present invention is preferably a pigment having a particle size of 25 μm or less, and particularly preferably a pigment having a particle size of 1 μm or less. When the particle diameter is within this range, pigment settling hardly occurs and the pigment dispersibility is good.
For the measurement of the particle diameter, 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 exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used. In addition, the use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold or bacteria can be prevented when the ink composition is stored for a long period of time.

  The water functions as a medium for a pigment or a binder resin in a printing agent. In the case of a water-based printing agent, the medium is mostly water, and a partly water-soluble solvent is often added. For example, the ratio of water: water-soluble solvent is generally used 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 printing and water-based inkjet 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)), diglycerin, polyglycerin, ethylene glycol, propylene glycol, 1, 3-propanediol, diethylene glycol, triethylene glycol, polyethylene glycol (specific examples: “# 200”, “# 300”, “# 400”, “# 4000”, “# 6000” manufactured by Wako Pure Chemical Industries, Ltd.), 2- Examples include pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolinone, thiodiglycol, sulfolane, dimethyl sulfoxide, neopentyl alcohol, trimethylolpropane, and 2,2-dimethylpropanol. 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, ketoalcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, polyalkylene glycols, propylene. Glycol, dipropylene glycol, polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-hexanediol 1,6-hexanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2,6-hexanetriol, Polyols such as trimethylolpropane and pentaerythritol, diethyleneglycol Polyhydric alcohol alkyl ethers such as dimethyl monobutyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monobutyl ether , Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether and polyhydric alcohol aralkyl ethers, lactams such as 2-pyrrolidone, N-methyl-2-pyrrolidone, and ε-caprolactam, 3-Dimethylimidazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone M-butyrolactone, polyoxyalkylene adduct of glycerin, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolane, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, diacetone alcohol, dimethylformamide propylene glycol monomethyl ether, and the like. These organic solvents can be used alone or in combination of two or more. From the viewpoint of re-solubility, at least one selected from 1,2-propanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, triethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether It is preferable to use 3-methyl-1,5-pentanediol.

  The content of the penetrant in the printing agent is preferably 3 to 15% by mass with respect to the total amount of the printing agent. If it is less than 3% by mass, the re-solubility may be lowered, and if it exceeds 15% by mass, the water resistance of the printed part may be insufficient, which may affect washing fastness. .

(Binder resin)
In the present invention, a polycarbonate urethane resin having a breaking elongation of 300% or more is used as the binder resin. In the present invention, the polycarbonate-based urethane resin means a urethane resin having a carbonate bond, and specifically means a urethane resin having a polycarbonate structure of the general formula (1).

（１）

(1)

In formula (1), R represents an arbitrary group, and n represents the number of repetitions.
By using the polycarbonate-based urethane resin, even when various solvents are blended in the printing agent, the storage stability is hardly lowered, and the color developability when a colored pigment is used is excellent.

(Elongation at break)
When a polycarbonate urethane resin having a breaking elongation of 300% or more is used, a printed part having particularly excellent texture can be obtained.
In order to ensure washing / friction fastness and texture for substrates that are easily stretchable, such as fabrics, and leathers that are required to be flexible, it is easy to stretch the printed part. That is, the elongation at break (film elongation) is important. By using a polycarbonate-based urethane resin with a breaking elongation of 300% or more, the printed part can be expanded and contracted following the expansion and contraction of the fabric, preventing the printed part from breaking and cracking, and improving the washing and friction fastness and texture. Can be secured. On the other hand, if the elongation of the polycarbonate-based urethane resin exceeds 2000%, the adhesion of the printed part to the substrate is decreased, and the washing / friction fastness is decreased, which is not preferable.
Among them, the elongation at break of the polycarbonate-based urethane resin is preferably 300% to 1000%, more preferably 410% to 800%, and most preferably 410% to 600%.

  In the present invention, the elongation at break was measured as follows. Universal tensile testing machine (Shimadzu Corporation) sampled into a rectangular shape with a length of 50 mm in the direction perpendicular to the main shrinkage direction (film width direction) and a length of 5 mm in the main shrinkage direction (film longitudinal direction). Manufactured by Autograph (registered trademark)), grasping both ends (both ends in the longitudinal direction) of the test piece, conducting a tensile test under the condition of a tensile speed of 300 mm / min, and determining the elongation at break as the elongation at break did.

(Polycarbonate urethane resin)
The polycarbonate urethane resin used in the present invention can be used without particular limitation as long as it is a polycarbonate urethane resin having a breaking elongation of 300% or more. Among these, a polycarbonate-based urethane resin having a hydrophilic group is preferable from the viewpoint of ease of dispersibility in water, which is a solvent for printing agents.

  Specifically, a polycarbonate polyol (a1-1) and a polyol (a1-2) having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group. The polycarbonate-type urethane resin (A) which has the structural unit derived from the polyol (a1) to contain and the structural unit derived from polyisocyanate (a2) is mentioned.

(Polyol (a1))
The polyol (a1) is used by appropriately selecting a polyol usually used as a raw material for polyurethane. The polycarbonate polyol (a1-1) and an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene- It is preferable to use a polyol (a1-2) having a hydrophilic group which is a polyoxypropylene group.

(Polycarbonate polyol (a1-1))
As said polycarbonate polyol (a1-1), the polycarbonate polyol (a1-1) which has the structural unit derived from a carbonate ester and the structural unit derived from a polyol, for example is preferable. This can be obtained, for example, by reacting a carbonate ester with a polyol, preferably an aliphatic diol, as raw materials.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

Examples of the low molecular weight polyol 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-cyclohexanedimethanol, etc. Aliphatic diols, hydroquinone, resorcin, Aromatic diols such as Sphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate Polyester polyols such as polycaprolactone can be used.
Among them, a relatively low molecular weight aliphatic chain diol is preferably used. Preferred aliphatic chain diols 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 and the like. The number average molecular weight is preferably 50 to 250.

  It is preferable to use the said polycarbonate polyol (a1-1) in the range of 80-99 mass% with respect to the total mass of the polyol (a1) used for manufacture of a polycarbonate-type urethane resin (A), More preferably. It is 85-99 mass%.

  Moreover, the said polycarbonate polyol (a1-1) is used in 10-90 mass% with respect to the total mass of the polyol (a1) and polyisocyanate (a2) used for manufacture of polycarbonate-type urethane resin (A). It is preferable to do.

(Polyol (a1-2) having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group)
The polycarbonate-based urethane resin (A) used in the present invention preferably has an anionic group, a cationic group, or a nonionic group for imparting dispersion stability in a printing agent, and among them, an anionic group or a cationic group. It preferably has a functional group. (Hereinafter, the polyol (a1-2) having a hydrophilic group which is an anionic group, a cationic group, a polyoxyethylene group or a polyoxyethylene-polyoxypropylene group may be simply referred to as “polyol (a1-2)”. is there.)

Examples of the anionic group include a carboxyl group, a carboxylate group, a sulfonic acid group, and a sulfonate group. Among these, a carboxylate group or a sulfonate group partially or wholly neutralized with a basic compound or the like is preferable for maintaining good water dispersibility.
Examples of basic compounds that can be used when neutralizing part or all of the carboxyl group and sulfonic acid group as the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, An alkanolamine such as ethanolamine, a metal base compound containing Na, K, Li, Ca, or the like can be used. 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 dry film.

  Moreover, as said cationic group, a tertiary amino group etc. are mentioned, for example. Examples of the acid that can be used when neutralizing part or all of the tertiary amino group include formic acid and acetic acid. As a quaternizing agent that can be used when quaternizing a 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. Is mentioned. Of these, a polyoxyalkylene group having an oxyethylene unit is preferable for further improving the hydrophilicity.

  As the polyol (a1-2), for example, an anionic group-containing polyol, a cationic group-containing polyol, and a nonionic group-containing polyol other than the above-described polycarbonate polyol (a1-1) can be used. Especially, 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.

Examples of the anionic group-containing polyol include a carboxyl group-containing polyol and a sulfonic acid group-containing polyol.
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 acids thereof. Examples thereof include a carboxyl group-containing polyester polyol obtained by reacting with an acid. Of these, 2,2′-dimethylolpropionic acid is preferred.

  Examples of the cationic group-containing polyol include a tertiary amino group-containing polyol. Specifically, the reaction of N-methyl-diethanolamine or a compound having two epoxies in one molecule with a secondary amine. The polyol which is a thing is mentioned.

  Examples of the nonionic group-containing polyol include polyalkylene glycol having a structural unit derived from ethylene oxide.

  The polyol (a1-2) is preferably used in the range of 0.3% by mass to 15.0% by mass with respect to the total amount of the polyol (a1) used for the production of the polycarbonate-based urethane resin (A). .

  In the range of 150 mmol / kg to 1000 mmol / kg, the hydrophilic group imparts better water dispersibility when present in an amount of 100 mmol / kg to 1200 mmol / kg with respect to the entire polycarbonate-based urethane resin (A). More preferably.

  Moreover, when the said hydrophilic group is an anionic group, it is preferable that the acid value is the range of 15-50 mgKOH / g, and it is still more preferable that it is the range of 20-45 mgKOH / g. In addition, the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said polycarbonate-type urethane resin (A).

In addition to the polycarbonate polyol (a1-1) and the polyol (a1-2), the polyol (a1) can be used in combination with other polyols as long as the effects of the present invention are not impaired.
As said other polyol, the polyol used as a raw material of polycarbonate polyol (a1-1) can be used, for example.

(Polyisocyanate (a2))
Examples of the polyisocyanate (a2) capable of reacting with the polyol (a1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, Contains aromatic polyisocyanates such as naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, etc. Use polyisocyanate It can be.

  In the polyisocyanate (a2), it is preferable to use an aliphatic polyisocyanate such as hexamethylene diisocyanate or an aliphatic cyclic structure-containing polyisocyanate such as isophorone diisocyanate from the viewpoint of suppressing yellowing of the printed portion.

  The polyisocyanate (a2) is composed of the polyol (a1) and the polyisocyanate (a2) used in the production of the polycarbonate urethane resin (A) because the polycarbonate urethane resin (A) has a breaking elongation of 300% or more. It is preferable to use in the range of 12-30 mass% with respect to the total mass of.

(Chain extender)
As described above, the polycarbonate-based urethane resin (A) has a polycarbonate polyol (a1-1) and a hydrophilic group that is an anionic group, a cationic group, a polyoxyethylene group, or a polyoxyethylene-polyoxypropylene group. Although it has a structural unit derived from the polyol (a1) containing the polyol (a1-2) and a structural unit derived from the polyisocyanate (a2), it may have a structural unit derived from a chain extender in some cases. Good.

As the chain extender, polyamine, other active hydrogen atom-containing compounds and 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, 1,4-cyclohexanediamine, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine, dihydrazisuccinate , Adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 , 5-trimethylcyclohexane can be used.

  The chain extender is preferably 3 parts by mass or less with respect to the total mass of the polyol (a1), polyisocyanate (a2) and chain extender used in the production of the polycarbonate-based urethane resin (A). More preferably, it is used in the range of 5% by mass or less, and more preferably in the range of 0.5% by mass or less.

Moreover, the printing agent of this invention may use the crosslinking agent (F) mentioned later for the purpose of improving wash fastness and friction fastness further. When the crosslinking agent (F) is used, the polycarbonate urethane resin (A) may be one having a functional group [X] capable of crosslinking reaction with the functional group of the crosslinking agent (F). 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 or the like contributes to the water dispersion stability of the polycarbonate-based urethane resin (A) in an aqueous medium, and when they undergo a crosslinking reaction, they also act as the functional group [X], and the crosslinking agent ( F) can be partially crosslinked.
When a carboxyl group or the like is used as the functional group [X], the polycarbonate urethane resin (A) preferably has an acid value of 2 to 55, and has an acid value of 15 to 50. It is preferable to improve the fastness to washing and friction fastness. In addition, the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a carboxyl group containing polyol used for manufacture of the said polycarbonate-type urethane resin (A).

  In addition, you may make the active hydrogen containing compound which can react with the said polyisocyanate (a2) react within the range which does not impair the effect of this invention.

  The weight average molecular weight of the polycarbonate-based urethane resin (A) is preferably 5000 to 200000, more preferably 20000 to 100000 from the viewpoints of wash fastness, friction fastness, texture, and re-solubility. More preferably, it is 30000-70000.

  The polycarbonate-based urethane resin (A) is produced, for example, by reacting the polyol (a1) with the polyisocyanate (a2) in the absence of a solvent or in the presence of an organic solvent. Then, when there is a hydrophilic group in the polycarbonate-based urethane resin (A), a neutralized part or all of the hydrophilic group as necessary is mixed in an aqueous medium to make it aqueous. Can be manufactured. In addition, when using the said chain extender as needed, the polycarbonate-type urethane resin (A) by which chain extension was carried out can be manufactured by mixing with an aqueous medium in the case of the said aqueous | water-based.

  In the reaction of the polyol (a1) and the polyisocyanate (a2), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. Preferably, it is carried out in the range of 0.9 to 1.5.

  Examples of the organic solvent that can be used in producing the polycarbonate urethane resin (A) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; and acetates such as ethyl acetate and butyl acetate. Nitriles such as acetonitrile; amides such as dimethylformamide and N-methylpyrrolidone can be used alone or in combination of two or more.

  In addition, the polycarbonate-based urethane resin (A) produced by the above method is made hydrophilic, for example, by hydrophilicity of the aqueous polycarbonate-based urethane resin (A) obtained by reacting the polyol (a1) with the polyisocyanate (a2). After neutralizing or quaternizing part or all of the sex group, water can be added and dispersed in water. In that case, you may use an emulsifier as needed. In addition, when dissolving or dispersing water, a machine such as a homogenizer may be used as necessary.

  Examples of the emulsifier include nonionic emulsifiers 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, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. It is.

  Examples of the aqueous medium include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water 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; lactams such as N-methyl-2-pyrrolidone, and the like. In the present invention, only water may be used, 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 load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The polycarbonate urethane resin (A) thus obtained is in a state in which the polycarbonate urethane resin (A) is dispersed in an aqueous medium. When adjusting as a printing agent, it is preferable that the polycarbonate-based urethane resin (A) is in the form of an aqueous dispersion dispersed in an aqueous medium. In this case, the aqueous medium is contained in the range of 20% by mass to 90% by mass with respect to the total amount of the composition of the polycarbonate-based urethane resin (A). Is preferable in obtaining.

  The particle size of the aqueous dispersion of the polycarbonate-based urethane resin (A) is preferably in the range of 3 nm to 1000 nm, more preferably 5 nm to 400 nm. The particle size means “average particle size D50” of an aqueous dispersion of polycarbonate urethane resin (A) diluted to a solid content of 5%, and a particle size distribution meter (“Microtrack UPA150” manufactured by Nikkiso Co., Ltd.). The average value of D50 (indicating that 50% of the particles are smaller than or equal to this particle size) in the particle size distribution measured three times in (3) is defined as the average particle size D50.

The ratio of the polycarbonate-based urethane resin and the pigment may be a ratio in a range usually used for a screen recording ink or an inkjet recording ink. For example, a ratio of the urethane resin and the pigment is in a range of 1: 3 to 8: 1. preferable.
As described above, the fastness to washing and the fastness to friction contribute to the molecular weight of the urethane resin used, and the higher the molecular weight of the urethane resin, the better the fastness to washing and the fastness to friction. However, when applied to ink for ink jet recording, excessive use of a high molecular weight urethane resin in the ink leads to higher viscosity, so it is preferable to determine the amount used in consideration of the balance with viscosity.

(Binder resin addition amount)
The urethane resin used in the present invention is a binder resin for fixing the pigment on the fiber. However, if the amount of the binder resin in the printing agent is large, the wash fastness and friction fastness are improved, but the texture of the fiber is improved. It becomes hard. Therefore, the ratio of the binder resin to the pigment in the printing agent is generally used in the range of 1: 3 to 8: 1, preferably 1: 1 to 8: 1, and 1: 1 to 5: 1. Most preferred.

(Printing agent manufacturing method)
The textile printing agent of the present invention can be prepared by preparing a high-concentration aqueous dispersion (pigment paste) of the pigment, diluting it with water, and adding the binder resin and other additives as required. it can.

  The method for obtaining the pigment paste by dispersing the pigment in the water 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.

  The pigment dispersant is preferably an aqueous resin, and preferable examples include polyvinyl alcohols, polyvinylpyrrolidones, acrylic resins such as acrylic acid-acrylic acid ester copolymers, styrene-acrylic acid copolymers, 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 Examples thereof include acrylic resins, styrene-maleic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-acrylic acid copolymers, and salts of the aqueous resins.

The compounds for forming the copolymer salt include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and diethylamine, ammonia, ethylamine, triethylamine, propylamine, isopropylamine, Examples include propylamine, butylamine, isobutylamine, triethanolamine, diethanolamine, aminomethylpropanol, and morpholine. The amount of the compound used to form these salts is preferably equal to or greater than the neutralization equivalent of the copolymer.
Of course, it is also possible to use a commercial item. As a commercially available product, Ajinomoto Fine Techno Co., Ltd. product Ajisper PB series, Big Chemie Japan Co., Ltd. Disperbyk series, BYK-series, Ciba Specialty Chemicals EFKA series, etc. can be used.

Moreover, as a dispersion method, the following (1)-(3) can be shown, for example.
(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 two rolls or a mixer, and the resulting kneaded product is added to an aqueous medium containing water, and the pigment is then mixed using a stirring / dispersing device. A method of preparing a paste.
(3) After adding a pigment to a solution obtained by dissolving a pigment dispersant in an organic solvent compatible with water such as methyl ethyl ketone and tetrahydrofuran, the pigment is added to the organic solution using a stirring / dispersing device. And then phase-emulsifying using an aqueous medium, and then the organic solvent is distilled off 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.
Also, the stirring / dispersing device 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 disperse mat, an SC mill, and a nanomizer.
One of these may be used alone, or two or more devices may be used in combination.

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

  Further, since coarse particles cause deterioration in image characteristics, it is preferable to remove coarse particles by centrifugation or filtration before and after ink preparation.

  After the dispersion step, an impurity removal step by ion exchange treatment or ultrafiltration treatment may be performed, followed by post treatment. Ion exchange treatment can remove ionic substances such as cations and anions (divalent metal ions, etc.), and by ultra-treatment, impurities dissolved substances (residual substances during pigment synthesis, excess components in dispersion composition) , Resin not adsorbed to the organic pigment, mixed foreign matter, etc.) can be removed. In the ion exchange treatment, a known ion exchange resin is used. The ultratreatment uses a known ultrafiltration membrane and may be either a normal type or a double capacity up type.

  After preparing the pigment paste, it is diluted as appropriate and additives as required are added to obtain a printing agent suitable for a preferred processing method such as dip dyeing or printing depending on the fiber to be colored.

For example, printing agents for screen recording use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. as final additives, and final pigments The 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, printing agents for dyeing use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, and binder resins as additives, The final pigment concentration is preferably in the range of 1 to 10% by mass. The viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa · s to 100 mPa · s. In addition, for example, the use of a printing agent for spray printing uses a binder resin as a viscosity modifier, a pH adjuster, a chelating agent, a plasticizer, an antioxidant, an ultraviolet absorber, etc. as an additive. The pigment concentration is preferably in the range of 1 to 10% by mass. The viscosity is arbitrarily set in accordance with the apparatus in the range of 1 mPa · s to 100 mPa · s.

  In addition, for example, printing agents for ink jet recording use preservatives, viscosity modifiers, pH adjusters, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, crosslinking agents, etc. as additives. The pigment concentration is preferably 1 to 20% by mass in order to obtain a sufficient image density and to ensure the dispersion stability of the pigment in the ink. In such a case, the additive is preferably added together with the binder resin.

  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 from 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, boric acid and the like.

  Specific examples of chelating agents include ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramildiacetic acid, Examples include 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 ultraviolet absorbers include allophanates such as allophanate and methyl allophanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, L-ascorbic acid and its salts, etc. manufactured by Ciba Geigy Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, or the like, or a lanthanide oxide or the like.

  The method for adding the diluent and additives can be carried out by a generally used method without any particular limitation. For example, the pigment paste is mixed with a binder resin, a surfactant, a viscosity modifier, an antifoaming agent, an antioxidant or an ultraviolet absorber, an antiseptic, and the like as additives. Examples thereof include a method of dispersing and mixing using a machine 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 ultrahigh pressure homogenizer, or a pearl mill. If necessary, various additives may be further added thereafter.

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

  Examples of the water-soluble solvent include mono- or polyhydric alcohols, amides, ketones, ketoalcohols, cyclic ethers, glycols, polyhydric alcohol lower alkyl ethers, 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 Polyols such as 6-hexanetriol, trimethylolpropane, 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 , Ε-caprolactam and other lactams, 1,3-dimethyli Midazolidinone acetone, ethyl acetate, N-methyl-2-pyrrolidone, m-butyrolactone, polyoxyalkylene adduct of glycerin, methyl acetate, tetrahydrofuran, 1,4-dioxane, dioxolane, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, di 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 include monosaccharides and polysaccharides, in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. 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 in this case is preferably one having good compatibility with other components present in the printing agent of the present invention. Further, a surfactant having high penetrability and stability is preferable.

Specifically, it is preferable to use amphoteric surfactants and nonionic surfactants.
Preferred examples of amphoteric surfactants include lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and others Examples include imidazoline derivatives.

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

  The addition amount of the surfactant is preferably 0.01 wt% or more and 10 wt% or less with respect to the total amount of the printing agent, and a more preferable upper limit value is 5.0 wt%, and a preferable lower limit value is 0.5% by weight.

  Furthermore, when the textile printing agent of the present invention is applied to the ink jet recording method, the surface tension is preferably adjusted to 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, More preferably, it is 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, when it exceeds 60 mN / m, there is a tendency that the non-absorbing base material is easily repelled. The viscosity is preferably 1.2 mPa · s or more and 20.0 mPa · s or less, more preferably 2.0 mPa · s or more and less than 15.0 mPa · s, and further preferably 3.0 mPa · s or more and 12 or more. Less than 0.0 mPa · s. When the viscosity is within this range, it is possible to achieve excellent dischargeability and good jetability over a long period of time. The surface tension can be appropriately adjusted by the surfactant.

  Further, for example, a crosslinking agent having two or more groups having reactivity with the crosslinkable functional groups of the dispersion resin and the binder resin may be added. As cross-linking agents, amino resins such as melamine resin, benzoguanamine resin, urea resin, phenol resin such as trimethylolphenol and its condensate, tetramethylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, xylylene diisocyanate Polyisocyanates such as modified isocyanates and blocked isocyanates, aliphatic amines, aromatic amines, N-methylpiperazine, amines such as triethanolamine, morpholine, dialkylaminoethanol, benzyldimethylamine, polycarboxylic acids, anhydrous Phthalic acid, maleic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, Acid anhydrides such as tylene glycol bis trimellitate, bisphenol A type epoxy resin, phenolic epoxy resin, glycidyl methacrylate copolymer, glycidyl ester resin of carboxylic acid, epoxy compound such as alicyclic epoxy, polyether polyol, polybutadiene glycol And alcohols such as polycaprolactone polyol and trishydroxyethyl isocyanate.

  As the addition amount to the printing agent of the present invention, it is necessary to add an amount commensurate with the number of crosslinkable functional groups of the dispersing resin and binder resin to be reacted, preferably 20% by mass or less, more preferably 10% by mass or less. More preferably, it is 5% by mass or less. When the blending amount is large, the texture of the fiber becomes hard, and when it is small, the fastness is deteriorated.

(Adherent)
The printing agent of the present invention can print on fabric, artificial leather, natural leather and the like. Particularly excellent for printing on fabrics. It is also possible to print on general-purpose adherends such as paper.
The fabric used in the present invention is preferably a medium composed of fibers, and may be a non-woven fabric or a non-woven fabric. As the material, a cloth made of any natural or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, polyurethane, or rayon can be used.

  Hereinafter, although the effect of the present invention is concretely explained using an example and a comparative example, the present invention is not limited to these examples. In the following description, parts and% indicate parts by mass.

<Measurement method of weight average molecular weight (Mw)>
It measured by the gel permeation chromatography (GPC) method on the following conditions.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (THF solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

<Measurement method of elongation at break>
Universal tensile testing machine (Shimadzu Corporation) sampled into a rectangular shape with a length of 50 mm in the direction perpendicular to the main shrinkage direction (film width direction) and a length of 5 mm in the main shrinkage direction (film longitudinal direction). Manufactured by Autograph (registered trademark)), grasping both ends (both ends in the longitudinal direction) of the test piece, conducting a tensile test under the condition of a tensile speed of 300 mm / min, and determining the elongation at break as the elongation at break did.

<Method for measuring acid value>
The acid value was calculated based on the use amount of an acid group-containing compound such as a carboxyl group-containing polyol used for the synthesis of the urethane resin.

<Synthesis of urethane resin>
(Production Example 1)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; , 2-dimethylolpropionic acid 39.5 parts by mass and methyl ethyl ketone 440 parts by mass were added and mixed uniformly. Next, after adding 121.0 parts by mass of isophorone diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-1” (acid value) having a weight average molecular weight of 46000 was obtained. 25) of an organic solvent solution was obtained.
Thereafter, cooling to 50 ° C., adding 31.3 parts by mass of triethylamine and 2169 parts by mass of water, removing methyl ethyl ketone at a temperature of 40 ° C. to 60 ° C. under reduced pressure, and adjusting the concentration by adding water, A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 480%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 2)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; , 2-Dimethylolpropionic acid 37.4 parts by mass and methyl ethyl ketone 420 parts by mass were added and mixed uniformly. Next, after adding 89.0 parts by mass of hexamethylene diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 6 hours, whereby polyurethane “PUD-2” (acid Of 20) was obtained.
Thereafter, cooling to 50 ° C., adding 29.7 parts by mass of triethylamine and 2057 parts by mass of water, removing methyl ethyl ketone at a temperature of 40 ° C. to 60 ° C. under reduced pressure, and adjusting the concentration by adding water, A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 500%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 3)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; Then, 37.7 parts by mass of 2-dimethylolpropionic acid and 420 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 92.4 parts by mass of tolylene diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-3” (acid) An organic solvent solution having a value of 25) was obtained.
Then, it is cooled to 50 ° C., 29.8 parts by mass of triethylamine and 2069 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 320%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 4)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; , 2-Dimethylolpropionic acid 21.2 parts by mass and methyl ethyl ketone 395 parts by mass were added and mixed uniformly. Next, after adding 71.1 parts by mass of tolylene diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-4” (acid) having a weight average molecular weight of 34,000 was obtained. 15) of an organic solvent was obtained.
Then, it is cooled to 50 ° C., 16.8 parts by mass of triethylamine and 1957 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 330%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 5)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; Then, 37.7 parts by mass of 2-dimethylolpropionic acid and 420 parts by mass of methyl ethyl ketone were added and mixed uniformly. Subsequently, 92.4 parts by mass of tolylene diisocyanate was added, 0.1 parts by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 15 hours, whereby polyurethane “PUD-5” (acid) An organic solvent solution having a value of 25) was obtained.
Then, it cooled to 50 degreeC and added 29.8 mass parts of triethylamine and 2069 mass parts of water. Methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water was added to adjust the concentration, whereby the urethane resin was dispersed in an aqueous medium at 23% by mass (breaking elongation: 300%). ) Resin composition was obtained.

(Production Example 6)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; , 29.2 parts by mass of 2-dimethylolpropionic acid and 456 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 137.3 parts by mass of isophorone diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-6” (acid value) having a weight average molecular weight of 54,000 was obtained. 30) of an organic solvent solution was obtained.
Then, it is cooled to 50 ° C., 39.0 parts by mass of triethylamine and 2588 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 530%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 7)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; , 2-dimethylolpropionic acid 59.8 parts by mass and methyl ethyl ketone 475 parts by mass were added and mixed uniformly. Next, after adding 154.8 parts by mass of isophorone diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-7” having a weight average molecular weight of 51000 (acid value) 35) of an organic solvent solution was obtained.
Then, it is cooled to 50 ° C., 47.4 parts by mass of triethylamine and 2689 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 500%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 8)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; Then, 71.2 parts by mass of 2-dimethylolpropionic acid and 496 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 173.8 parts by mass of isophorone diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 7 hours, whereby polyurethane “PUD-8” (acid value) having a weight average molecular weight of 50000 40) of an organic solvent solution was obtained.
Then, it is cooled to 50 ° C., 56.4 parts by mass of triethylamine and 2795 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation of 460%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 9)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; Then, 36.5 parts by mass of 2-dimethylolpropionic acid and 436 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 118.2 parts by mass of tolylene diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 3 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end. Obtained.
After adding 41.3 parts by mass of triethylamine to the methylethylketone solution of the urethane prepolymer obtained above and neutralizing the carboxyl group in the urethane prepolymer, 1504 parts by mass of water was added. Next, 17.3 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water was added to adjust the concentration, whereby the urethane resin was dispersed in an aqueous medium at 23% by mass (breakage) A polyurethane “PUD-9” (acid value 23) resin composition having a weight average molecular weight of 150,000 having an elongation of 400% was obtained.

(Production Example 10)
500 parts by mass of a polycarbonate polyol (number average molecular weight 2000) obtained by reacting 1,6-hexanediol and methyl carbonate in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer; Then, 36.5 parts by mass of 2-dimethylolpropionic acid and 436 parts by mass of methyl ethyl ketone were added and mixed uniformly. Next, after adding 118.2 parts by mass of tolylene diisocyanate, 0.1 parts by mass of dibutyltin dilaurate was added and reacted at 80 ° C. for 3 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having an isocyanate group at the molecular end. Obtained.
After adding 41.3 parts by mass of triethylamine to the methylethylketone solution of the urethane prepolymer obtained above and neutralizing the carboxyl group in the urethane prepolymer, 1502 parts by mass of water was added. Next, 15.3 parts by mass of ethylenediamine was added and reacted. After completion of the reaction, methyl ethyl ketone was removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water was added to adjust the concentration, whereby the urethane resin was dispersed in an aqueous medium at 23% by mass (breakage) A polyurethane “PUD-10” (acid value 23) resin composition having a weight average molecular weight of 40000 in elongation of 330% was obtained.
(Production Example 11)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 500 parts by mass of polyoxytetramethylene glycol (number average molecular weight: 2,000), 2.2'-dimethylolpropionic acid 33. 0 parts by mass and 281 parts by mass of methyl ethyl ketone were added and mixed uniformly, and then 117.8 parts by mass of isophorone diisocyanate was added, then 0.1 part by mass of dibutyltin dilaurate was added, and the mixture was allowed to react at 80 ° C. for about 15 hours. An organic solvent solution of polyurethane “PUD-H1” (acid value 21) having a molecular weight of 100,000 was obtained.
Then, it is cooled to 50 ° C., 26.1 parts by mass of triethylamine and 2340 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 500%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 12)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 500 parts by mass of polyoxytetramethylene glycol (number average molecular weight: 2,000), 2.2'-dimethylolpropionic acid 33. 0 parts by mass and 281 parts by mass of methyl ethyl ketone were added and mixed uniformly, then 89.3 parts by mass of tolylene diisocyanate was added, then 0.1 parts by mass of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for about 15 hours. An organic solvent solution of polyurethane “PUD-H2” (acid value 22) having an average molecular weight of 100,000 was obtained.
Then, it is cooled to 50 ° C., 26.1 parts by mass of triethylamine and 2340 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 570%) in which the urethane resin was dispersed in an aqueous medium was obtained.

(Production Example 13)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 500 parts by mass of polyoxytetramethylene glycol (number average molecular weight: 2,000), 107 parts of 2.2′-dimethylolpropionic acid And 366 parts by weight of methyl ethyl ketone and mixed uniformly, then 107 parts by weight of isophorone diisocyanate was added, then 0.1 part by weight of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for about 5 hours, and the weight average molecular weight was 35,000. An organic solvent solution of polyurethane “PUD-H3” (acid value 52) was obtained.
Then, it is cooled to 50 ° C., 84.7 parts by mass of triethylamine and 3000 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A resin composition having a nonvolatile content of 23% by mass (breaking elongation: 850%) in which the urethane resin was dispersed in an aqueous medium was obtained.

Abbreviations in Tables 1 to 3 will be described below.
PUD-1: Urethane resin PUD-2 obtained in Production Example 1: Urethane resin PUD-3 obtained in Production Example 2: Urethane resin PUD-4 obtained in Production Example 3: Urethane resin PUD- obtained in Production Example 4 5: Urethane resin PUD-6 obtained in Production Example 5: Urethane resin PUD-7 obtained in Production Example 6: Urethane resin PUD-8 obtained in Production Example 7: Urethane resin PUD-9 obtained in Production Example 8: Urethane resin PUD-10 obtained in Production Example 9: Urethane resin PUD-H2 obtained in Production Example 10: Urethane resin PUD-H2 obtained in Production Example 11: Urethane resin PUD-H3 obtained in Production Example 12: Production Example Urethane resin obtained in 13

<Preparation of pigment paste (A)>
Styrene-maleic acid half ester (product name “DSS-25” manufactured by Gifu Shellac Manufacturing Co., Ltd., acid value: 116 mg KOH / g, weight average molecular weight: 42,000, SP: 11.0) 15 parts, hydroxylated 1.6 parts of potassium (an amount corresponding to 0.9 equivalent with respect to the total amount of acidic groups in the styrene-maleic acid half ester) and 83.4 parts of water are mixed and stirred at 70 ° C. using a stirrer. As a result, a translucent resin dispersion was obtained. 80 parts of the resin dispersion and 20 parts of copper phthalocyanine pigment (product name FASTOGEN BLUE 5327 WET manufactured by DIC) (solid content conversion) were mixed and stirred. After adding 500 parts of 0.3 mmφ ceramic beads to this mixture, Grinding with a cylindrical sand grinder for 6 hours. After grinding, the ceramic beads were separated to obtain a mill base. The mill base obtained above was subdivided for 3 hours using an ultrasonic homogenizer at an output of 600 W to obtain a pigment paste.

<Preparation of pigment paste (B)>
A pigment paste was obtained in the same manner as the pigment paste (A), except that the copper phthalocyanine pigment of the pigment paste (A) was changed to a quinacridone pigment (product name Fastogen Super Magenta RG manufactured by DIC).

<Preparation of pigment paste (C)>
A pigment paste was obtained in the same manner as the pigment paste (A), except that the copper phthalocyanine pigment of the pigment paste (A) was changed to a disazo pigment (product name Novoperperm Yellow 4G01 manufactured by Clariant).

<Preparation of pigment paste (D)>
A pigment paste was obtained in the same manner as the pigment paste (A) except that the copper phthalocyanine pigment of the pigment paste (A) was changed to carbon black (product name # 40 manufactured by Mitsubishi Chemical Corporation).

<Preparation of printing agent>
20 parts of the pigment paste (A), a solvent (water, water-soluble solvent, oil-soluble solvent, etc.), and 4 parts of PUD-1 (in terms of solid content) as a urethane resin were added to obtain the printing agent of the example. . The composition of each printing agent is shown in the attached table. At the time of addition of each example, the mixture was sufficiently stirred with a dispersion stirrer (TK Homo Disper L manufactured by Tokushu Kika Kogyo Co.).

<Evaluation of storage stability>
20 ml of the printing agent obtained in Examples and Comparative Examples was sealed in a glass container and allowed to stand at 50 ° C. for 4 weeks, and then evaluated as follows.
○: Change rate from initial viscosity ± 10% or less Δ: Change rate from initial viscosity ± 10 to less than 15% ×: Change rate from initial viscosity ± 15% or more

<Evaluation of re-solubility>
30 μL of the obtained printing agents of Examples and Comparative Examples were applied on a slide glass and allowed to stand at 50 ° C. for 10 minutes at an experimental room temperature to prepare a test plate. Thereafter, it was immersed in water at room temperature for 60 seconds, and it was visually confirmed whether it was dissolved again.
◎: After immersion for 30 seconds, after taking out, no coloring components were confirmed on the slide glass, and no granular undissolved content was confirmed in the immersion liquid. ○: Some undissolved residue was confirmed in the slide glass or immersion liquid. △: The slide glass or the immersion liquid has an undissolved substance x: The slide glass or the immersion liquid has an extremely undissolved substance. Note that the printing agent that can be judged as “good” in this experiment is It exhibits re-solubility in the screen recording method, or in the ink jet recording method, it can be easily discharged by a cleaning operation after a long pause of printing.

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

<Fabrication for fastness evaluation_Screen printing>
Printing evaluation was performed by a screen printing method using an auto screen printing machine (manufactured by Sakurai Dyeing Machine Co., Ltd.). Each ink was printed on a polyester / cotton fabric on a 135 mesh striped screen, dried at 120 ° C. for 2 minutes, and then subjected to heat treatment at 150 ° C. for 2 minutes. As a result of visual inspection of the printed material, all the products were of good quality.

<Production of Evaluation Fabric_Inkjet Printing>
The ink cartridge of an inkjet printer (Seiko Epson Co., Ltd., MJ-510C) was filled and printed. Each ink was printed on a polyester / cotton fabric, dried at 120 ° C. for 2 minutes, and heat-treated at 150 ° C. for 2 minutes. As a result of visual inspection of the printed material, all the products were of good quality.

<Print density evaluation method>
Fabrication of the evaluation fabric_printed fabric produced by screen printing was measured with a spectral densitometer (528 manufactured by X-Rite Co., Ltd.), and the color developability was evaluated by the OD value.

<Dry and wet friction fastness evaluation method>
A printed material obtained by screen printing is subjected to a dry type and a wet type test using a Gakushin type friction fastness tester according to JIS L 0849: 2004, and then a change of JIS L 0801: 2004 is performed. The grades were judged from 1st to 5th grades according to the criteria of visual sense using the gray scale for fading. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

<Method for evaluating washability fastness>
For printed matter obtained by screen printing, the test was repeated 30 times in accordance with the A-4 method of JIS L 0844: 2005, and then the visual method using the gray scale for fading color of JIS L 0801: 2004 The grades were judged from grades 1 to 5 in accordance with the judgment criteria of No. 1. In addition, as for the grade, 1st grade has the largest fading, and the closer to 5th grade, the less fading.

<Texture evaluation method>
The evaluation fabric obtained above was evaluated by the tentacles according to the following criteria.
○: The touch between the printed surface and the fabric is not felt or is slightly felt.
(Triangle | delta): It is the tactile sensation in which the boundary of a printed surface and cloth is felt.
X: A firm tactile sensation in which the boundary between the printed surface and the fabric is clearly felt.
As another texture evaluation method, in accordance with JIS L 1913: 2010, using a bending resistance tester (cantilever method, Gurley method, handle ohm method, etc.) Evaluation is preferred. The texture becomes softer as the bending resistance is smaller, and the texture becomes harder as it is larger.

  Tables 4 to 6 show the compositions of the printing agents of Examples and Comparative Examples and various evaluation results. The unit of blending in the table is part.

Abbreviations in Tables 4 to 6 will be described below.
PC: polycarbonate polyol PE: polyoxytetramethylene glycol DMPA: 2,2-dimethylolpropionic acid IPDI: isophorone diisocyanate HDI: hexamethylene diisocyanate TDI: tolylene diisocyanate BTG: triethylene glycol monobutyl ether MPD: 3-methyl 1,5 -Pentanediol Mw: PC content (%) in the weight average molecular weight polyol:% by mass of the polycarbonate polyol with respect to the total mass of all polyols used in the production of the polycarbonate-based urethane resin
NCO content (%): mass% of polyisocyanate with respect to the total mass of all polyols and polyisocyanate used in the production of polycarbonate-based urethane resin
NH content (%): Mass% of chain extender with respect to the total mass of all polyols, polyisocyanate and chain extender used in the production of polycarbonate urethane resin

  From the results of Tables 4 to 6, printing agents using the polycarbonate-based urethane resin (A) having specific physical properties of the present invention (Examples 1 to 15) all show good storage stability and re-solubility. Furthermore, the fabrics using the printing agent of the present invention all exhibited good color developability, various fastnesses (washing resistance, friction resistance (dry type, wet type)), and texture. On the other hand, Comparative Examples 1 to 6 using a urethane resin other than the polycarbonate-based urethane resin are insufficient in any of the storage stability, re-dissolvability, washing resistance, friction resistance and texture of the printing agent. It was.

Claims (7)

A pigment, a water, an organic solvent, containing a binder resin, said binder resin is a weight average molecular weight at 300% to 600% elongation at break is Ri polycarbonate-based urethane resin der of 30,000 to 70,000, the organic solvent a printing agent containing penetrants, textile printing agents, wherein the penetrating agent is characterized Rukoto contains 3 to 15 wt% based on the total amount of the printing agent. The penetrant is at least one selected from the group consisting of 1,2-propanediol, 3-methyl-1,5-pentanediol, 1,2-hexanediol, triethylene glycol monomethyl ether and dipropylene glycol monomethyl ether. The printing agent according to claim 1 . The printing agent according to claim 1 or 2 , wherein the polycarbonate-based urethane resin is a polycarbonate-based urethane resin having a structural unit derived from an aliphatic polyisocyanate or an aliphatic cyclic structure-containing polyisocyanate. The printing agent according to any one of claims 1 to 3 , wherein an acid value of the polycarbonate-based urethane resin is in a range of 15 to 50 mgKOH / g. The printing agent according to any one of claims 1 to 4 , wherein a ratio of the polycarbonate-based urethane resin to the pigment is 1: 3 to 8: 1. The printing agent according to any one of claims 1 to 5 , which is used for an ink jet recording method. The manufacturing method of the fabric thing which prints the textile printing agent in any one of Claims 1-6 on a fabric.