JP2016151078A - Composition for fixation, manufacturing method of printing substrate, and printing substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for fixation inhibiting degradation of a printing part by washing, maintaining high working efficiency when manufacturing a printing substrate, and suitable for users' needs in a printing field.SOLUTION: A compound for fixation for fixing a coloring agent on a substrate is constituted by dispersing an organic solution containing an organic solvent and a polyvalent isocyanate dissolved in the organic solvent and an emulsifier in a water soluble solvent. The polyvalent isocyanate is at least one of an adduct product of hexamethylene diisocyanate, an isocyanurate product of hexamethylene diisocyanate, and an oligomer of hexamethylene diisocyanate. The flash point of the organic solution is higher than 60°C.SELECTED DRAWING: None

Description

  The present invention relates to a fixing composition, a method for producing a printed fabric, and a printed fabric.

  In a textile processed product (for example, clothing or a bag) having a print portion, deterioration of the print portion due to washing (for example, a decrease in color of the print portion or peeling of the print portion from the fabric) is known. In order to improve this, a fixing composition is usually used. Specifically, the fixing composition is added to the main agent (including the binder resin and the colorant) to produce a printing ink, and the printing ink is printed on the fabric. Thereby, since the colorant is fixed to the cloth, it is possible to prevent the print portion from being deteriorated due to washing.

  As the fixing composition, an ethyleneimine-based compound has been used, but a rash sometimes occurs in the user during work. Therefore, in recent years, various alternatives to ethyleneimine compounds have been proposed. For example, Patent Document 1 describes the use of a hydrophobic block polyisocyanate as a fixing composition.

JP 2014-172979 A

  However, in the method described in Cited Document 1, it is necessary to cancel the protection of the isocyanate group (NCO group) by the blocking agent at the time of production of printing ink, etc., and this cancellation is a heat treatment at a high temperature (for example, 120 ° C. or higher). Is required. Depending on the type of fiber or colorant constituting the fabric, the fabric or colorant may be deteriorated by heat treatment at a high temperature.

  On the other hand, when a polyvalent isocyanate whose NCO group is not protected by a blocking agent is used as a fixing composition, heat treatment at a high temperature becomes unnecessary. However, since such polyvalent isocyanate is rich in reactivity, the pot life of printing ink is shortened.

  Further, it is conceivable to use a compound containing a carbodiimide group or an oxazoline compound as the fixing composition. However, since these compounds are expensive, they do not meet user needs in the printing field. Furthermore, the fixing composition is also required to have low odor during operation.

  In addition, overseas manufacturers are mainstream in the textile printing field, and there are many textile manufacturers in Southeast Asia and South Asia. Therefore, the fixing composition is required to reduce not only the material cost but also the transportation cost.

  The present invention has been made in view of the above points, and its purpose is to prevent deterioration of the printed portion due to washing, to maintain high work efficiency during the production of the printed fabric, and to meet the needs of users in the textile printing field. It is to provide a fixing composition adapted to the above.

  A fixing composition for fixing a colorant to a cloth is composed of an organic solution containing an organic solvent and a polyisocyanate dissolved in the organic solvent, and an emulsifier dispersed in a water-soluble solvent. The polyvalent isocyanate is at least one of an adduct of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, and an oligomer of hexamethylene diisocyanate. The flash point of the organic solution is higher than 60 ° C.

  In the present specification, “the emulsifier is dispersed in the water-soluble solvent” means that the emulsifier is not only dissolved in the water-soluble solvent but also present in the water-soluble solvent. The case where it exists in the water-soluble solvent in the state melt | dissolved in the solvent is also included.

  In the present specification, the “polyvalent isocyanate” means an isocyanate containing two or more NCO groups in the molecule.

  According to the present invention, it is possible to prevent deterioration of the printed part due to washing, maintain high work efficiency during the production of printed fabric, and further provide a fixing composition that meets user needs in the textile printing field.

[Configuration of Fixing Composition]
The fixing composition of the present invention is for fixing a colorant to a cloth, and includes an organic solution containing an organic solvent and a polyvalent isocyanate dissolved in the organic solvent (hereinafter referred to as “an organic solution of a polyvalent isocyanate”). And the emulsifier are dispersed in a water-soluble solvent (for example, water). The polyvalent isocyanate of the present invention includes at least one of an adduct of hexamethylene diisocyanate (hereinafter referred to as “HDI”, which is an abbreviation for hexamethylene diisocyanate), an isocyanurate of HDI, and an oligomer of HDI. It is. Further, the organic solution of the polyvalent isocyanate of the present invention has a flash point higher than 60. For these reasons, it is possible to prevent the printing portion from being deteriorated due to washing, and it is possible to maintain a high working efficiency when producing the printed fabric. Furthermore, the fixing composition of the present invention meets user needs in the textile printing field. Details are shown below.

  Since the fixing composition of the present invention contains the organic solvent, the polyvalent isocyanate, and the emulsifier, the fixing composition of the present invention is emulsified with an emulsifier in a state where the polyvalent isocyanate is dissolved in the organic solvent. Conceivable. Therefore, since the polyvalent isocyanate of the present invention reacts with the binder resin by mixing the fixing composition of the present invention and the main agent (including the binder resin and the colorant), heat treatment is performed at 120 ° C. or higher. Even if it is not, the polyvalent isocyanate of the present invention reacts with the binder resin. This is also true during the reaction of the polyvalent isocyanate of the present invention with the dough. Therefore, since the colorant is fixed to the fabric without deteriorating the main agent (for example, the colorant) and the fabric, the fixing strength of the colorant to the fabric can be ensured. Therefore, it is possible to prevent the print portion from being deteriorated due to washing. This effect is also obtained when the polyvalent isocyanate of the present invention is at least one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer.

  If a polyisocyanate whose NCO group is not protected by a blocking agent is added to the main agent without emulsification, the NCO group may react directly with the main agent or water, leading to an increase in the overall viscosity or gelation. . That is, it may not be suitable for printing on the fabric. However, it is considered that the fixing composition of the present invention is emulsified with an emulsifier in a state where the polyvalent isocyanate is dissolved in an organic solvent. Therefore, since the fixing composition of the present invention can moderately suppress the reactivity of the polyvalent isocyanate during storage, it is excellent in storage stability. Therefore, it is possible to maintain a high work efficiency when manufacturing the printed fabric.

  Further, since the polyvalent isocyanate of the present invention is at least one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer, the polyvalent isocyanate of the present invention has a low polarity. For this reason, the reactivity of the polyisocyanate at the time of production of the printing ink is lowered, so that the pot life of the printing ink can be prolonged. This also makes it possible to maintain high work efficiency during the production of the printed fabric.

  Since the polyvalent isocyanate of the present invention is at least one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer, the material cost of the fixing composition of the present invention is reduced. Thereby, the fixing composition of the present invention meets the user needs in the printing field.

  In addition, since the polyvalent isocyanate of the present invention is at least one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer, an organic solvent for dissolving the polyvalent isocyanate of the present invention (of the present invention) The flash point of the organic solvent tends to increase. In general, an organic solvent has a low odor when its flash point becomes high. Therefore, a low odor organic solvent can be used in the fixing composition of the present invention, and thus low odor properties during operation can be realized. Therefore, the work environment can be improved. Also by this, the fixing composition of the present invention meets the user needs in the printing field.

  Furthermore, since the flash point of the organic solvent of the present invention tends to be high, the flash point of the organic solution of polyvalent isocyanate is higher than 60 ° C. in the present invention. As a result, according to the provisions of the International Maritime Dangerous Goods Regulation, the fixing composition of the present invention can be transported by ship as normal cargo. Therefore, the transportation cost of the fixing composition of the present invention is reduced. Also by this, the fixing composition of the present invention meets the user needs in the printing field.

<Organic solvent>
The organic solvent of the present invention dissolves the polyvalent isocyanate of the present invention. Therefore, examples of the organic solvent of the present invention include a solvent having a boiling point of 180 ° C. or higher, or a solvent having a flash point higher than 60 ° C. (more preferably, a solvent having a flash point of 70 ° C. or higher). For example, the organic solvent of the present invention includes at least one of n-undecane, n-dodecane, n-tridecane, trade name “Isopar L” manufactured by TonenGeneral Sekiyu KK, and trade name “Isopar M” manufactured by the same company. It is preferable to use one.

  In the present invention, the ratio of the mass of the organic solvent to the total mass of the organic solvent and the polyvalent isocyanate is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 50% by mass or less. If the said ratio is 5 mass% or more and 50 mass% or less, the polyvalent isocyanate of this invention will be easily melt | dissolved in the organic solvent of this invention, and will be easily emulsified in a water-soluble solvent.

<Polyvalent isocyanate>
The polyvalent isocyanate of the present invention is at least one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer. Therefore, the polyvalent isocyanate of the present invention may be any one of an HDI adduct, an HDI isocyanurate, and an HDI oligomer. The polyisocyanate of the present invention may comprise an HDI adduct of 10% by mass to 90% by mass and an HDI isocyanurate of 10% by mass to 90% by mass of 10% by mass or more. It may consist of 90% by mass or less of HDI isocyanurate and 10% by mass to 90% by mass of HDI oligomer, 10% by mass to 90% by mass of HDI adduct, and 10% by mass to 90% by mass. It may be composed of an isocyanurate of HDI of not more than mass% and an oligomer of HDI of not less than 10 mass% and not more than 90 mass%.

  In the present invention, the ratio of the mass of the polyvalent isocyanate to the total mass of the organic solvent and the polyvalent isocyanate is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 95% by mass. . When the ratio is 50% by mass or more and 95% by mass or less, the content of the polyvalent isocyanate in the fixing composition of the present invention can be ensured, so that the fixing strength of the colorant to the cloth can be increased.

(HDI adduct body)
The “HDI adduct” means a product obtained by a reaction (addition reaction) between HDI and trimethylolpropane (hereinafter referred to as “TMP”, which is an abbreviation for trimethylolpropane). Specifically, the HDI adduct is obtained by reacting all of the hydroxyl groups (OH groups) of TMP with one NCO group of HDI, and thus HDI and TMP are (HDI). : (TMP) = 3: 1 (molar ratio). Therefore, the adduct body of HDI contains three HDIs in the molecule. Here, in the above reaction, the other NCO group of HDI does not react with the OH group of TMP. Therefore, the adduct body of HDI contains three NCO groups in the molecule.

  The HDI adduct may be synthesized by a known method or may be a commercially available product. As a commercial item of the adduct body of HDI, the brand name "D-160N" by Mitsui Chemicals Polyurethane Co., Ltd., the brand name "Duranate AE700-100" by Asahi Kasei Co., Ltd., etc. are mentioned, for example. In the present invention, these may be used in combination.

(HDI isocyanurate)
The “isocyanurate form of HDI” means a trimer of HDI. Specifically, the isocyanurate of HDI is obtained by the reaction (addition reaction) of one NCO group contained in each of three molecules of HDI, and has a cyclic structure. Here, in the above reaction, the other NCO group contained in each of the three molecules of HDI does not react. Therefore, the isocyanurate form of HDI contains three NCO groups in the molecule.

  The isocyanurate of HDI may be synthesized by a known method or may be a commercially available product. Examples of commercially available isocyanurate bodies of HDI include, for example, trade names “D-170N”, “D-170HN”, “D-172N” or “D-177N” manufactured by Mitsui Chemicals Polyurethane Co., Ltd., or Asahi Kasei Corporation A product name “Duranate TSA-100” manufactured by the company can be used. In the present invention, these may be used in combination.

(HDI oligomer)
The “HDI oligomer” is obtained by the reaction (addition reaction) of NCO groups with each other in adjacent HDI. The oligomer of HDI may be synthesized by a known method or may be a commercially available product. As a commercial item of the oligomer of HDI, Asahi Kasei Corporation brand name "Duranate A-201H", "Duranate D101", "Duranate D201", etc. are mentioned, for example. In the present invention, these may be used in combination.

<Emulsifier>
The fixing composition of the present invention is obtained by mixing and stirring an oil phase containing an organic solution of a polyisocyanate and an aqueous phase containing a water-soluble solvent, and the emulsifier is at least one of the oil phase and the aqueous phase. It may be added to one. The emulsifier of the present invention may be a conventionally known water-soluble surfactant, but may be a water-soluble polymer or surfactant added to the aqueous phase in order to facilitate emulsification and dispersion. It may be a surfactant added to the phase.

  Examples of the water-soluble polymer include naturally-derived water-soluble polymers such as gelatin, modified gelatin, starch, modified starch, casein, cellulose derivatives, arabic gum, and sodium alginate. Examples of the water-soluble polymer include polyvinyl alcohol (hereinafter referred to as “PVA”. PVA is an abbreviation of “polyvinyl alcohol”), modified PVA, a polyacrylic acid derivative, a styrene / maleic anhydride copolymer or a derivative thereof, Polyvinyl pyrrolidone, polyacrylamide or derivatives thereof, ethylene / vinyl acetate copolymer, isobutylene / maleic anhydride copolymer, ethylene / acrylic acid copolymer, or vinyl acetate / acrylic acid copolymer can also be used. . Partially saponified PVA, gelatin, modified gelatin, starch or the like is preferably used.

  As the surfactant, a well-known emulsifying surfactant can be used, and in general, an anionic surfactant or a nonionic surfactant is used. Examples of the anionic surfactant include alkyl sulfate compound salts, higher fatty acid salts, alkyl sulfonates, alkyl benzene sulfonates, amide sulfonates, and dialkyl oxalates. Examples of nonionic surfactants include perfluoroalcohol, polyethylene glycol or an adduct thereof, or a polyhydric alcohol fatty acid compound. Details of these are described in Seisho (Tokiyuki Yoshida et al., “New Edition Surfactant Handbook” Engineering Books Co., Ltd. (1987), etc.).

  The emulsifier is preferably contained in an amount of 2% by mass to 12% by mass with respect to the total mass of the organic solvent and the polyvalent isocyanate. If the emulsifier is contained in an amount of 2% by mass to 12% by mass with respect to the total mass, the organic solution of the polyvalent isocyanate of the present invention can be effectively dispersed in the water-soluble solvent.

<Water-soluble solvent>
In the present invention, the water-soluble solvent is preferably water, for example, and is preferably contained in an amount of 50% by mass or more and 200% by mass or less based on the mass of the polyvalent isocyanate organic solution.

<Flash point>
The flash point of the organic solution of the polyvalent isocyanate of the present invention is higher than 60 ° C, preferably 70 ° C or higher, more preferably 70 ° C or higher and 100 ° C or lower. In this specification, the flash point of an organic solution of polyisocyanate is measured in accordance with the method described in JIS K 2265-2: 2007 (rapid equilibrium sealing method (also referred to as setter sealing method)). .

<Antifoaming agent>
The fixing composition of the present invention preferably further contains an antifoaming agent. Thereby, at the time of storage of the fixing composition of the present invention, foaming due to the reaction (decarboxylation) between the polyvalent isocyanate and the aqueous phase is suppressed. Therefore, the storage stability of the fixing composition of the present invention can be further enhanced. Therefore, it is possible to increase the work efficiency when manufacturing the printed fabric.

  As the antifoaming agent of the present invention, a conventionally known antifoaming agent can be used, but preferably at least of a silicon-based antifoaming agent, a mineral oil-based antifoaming agent, and an emulsifier having a low HLB (Hydrophile-Lipophile Balance). Use one.

  In the present invention, the antifoaming agent is preferably contained in an amount of 60 mass ppm or more and 6000 mass ppm or less, more preferably 200 mass ppm or more and 1000 mass ppm or less with respect to the mass of the aqueous phase. If the defoamer is contained in an amount of 60 mass ppm or more with respect to the mass of the aqueous phase, foaming due to the reaction (decarboxylation) between the polyvalent isocyanate and the aqueous phase can be effectively suppressed. When the antifoaming agent is contained in an amount of 6000 mass ppm or less with respect to the mass of the aqueous phase, it is possible to prevent the performance of the fixing composition from being deteriorated due to the addition of the antifoaming agent.

[Print fabric manufacturing method]
The method for producing a printed fabric of the present invention includes a step of preparing the fixing composition of the present invention, a step of preparing a printing ink containing at least the fixing composition of the present invention, a binder resin, and a colorant, Printing the printing ink on the fabric and fixing the colorant to the fabric. As described above, in the method for producing a printed fabric of the present invention, the printed fabric is produced using the fixing composition of the present invention. Therefore, it is possible to prevent deterioration of the print unit due to washing, and it is possible to maintain high work efficiency when producing printed fabric. In addition, the method for producing a printed fabric according to the present invention meets user needs in the textile printing field.

<Preparation of fixing composition of the present invention>
First, an oil phase containing an organic solution of a polyvalent isocyanate and an aqueous phase containing a water-soluble solvent are prepared. At this time, an emulsifier is added to at least one of the oil phase and the aqueous phase. Preferably, an antifoaming agent is added to the aqueous phase. Next, the oil phase and the aqueous phase are mixed and stirred. In this way, the fixing composition of the present invention is obtained. The materials and contents of the polyvalent isocyanate organic solution, the water-soluble solvent, the emulsifier, and the antifoaming agent are as described in the above [Configuration of Fixing Composition].

<Preparation of printing ink>
Printing ink can be produced by mixing the fixing composition of the present invention, a binder resin and a colorant. As such a mixing method, a conventionally known mixing method can be used as a mixing method used in the production of printing ink. In the produced printing ink, the fixing composition of the present invention is preferably contained in an amount of 2% by mass to 6% by mass, more preferably 3% by mass to 5% by mass with respect to the mass of the binder resin. It is. In the produced printing ink, the colorant is preferably contained in an amount of 2 to 10% by mass, more preferably 3 to 5% by mass, based on the mass of the binder resin.

  As the binder resin, a resin used as a binder resin at the time of producing a printed fabric can be used, but at least one of an acrylic resin, a polyester resin, a urethane resin, and a vinyl alkanoate resin is preferably used.

  As the colorant, a conventionally known colorant used at the time of producing the print fabric can be used, but it is preferably selected appropriately according to the color required for the print portion. For example, at least one of organic dyes such as phthalocyanine complexes or azo dyes and inorganic pigments such as titanium white, cobalt blue or ferrocyanide can be used.

  It is preferable to further add an acid to produce a printing ink. As a result, the activity of the polyvalent isocyanate in the printing ink of the present invention is maintained, so that the storage stability of the printing ink of the present invention can be increased, and thus the working efficiency during the production of printed fabrics can be increased. Can do. As the acid, a conventionally known acid can be used, but at least one of an organic acid such as oxalic acid, malic acid or citric acid, and an inorganic acid such as phosphoric acid is preferably used. In the produced printing ink, the acid is preferably contained in an amount of 0.05% by mass or more and 0.5% by mass or less, more preferably 0.1% by mass or more, based on the total mass of the binder resin and the colorant. 0.3 mass% or less is contained.

<Printing>
As a method for printing the printing ink of the present invention on a cloth, a conventionally known printing method can be used as a printing method used at the time of producing the printed cloth. After printing the printing ink on the cloth, it is preferable to perform a dry heat treatment. As conditions for the dry heat treatment, conventionally known conditions can be used as conditions for the dry heat treatment performed after printing the printing ink on the cloth.

  As the fabric, a conventionally known fabric can be used as a fabric capable of fixing the colorant. Here, in the present invention, the colorant is fixed to the cloth by the fixing composition of the present invention. For this reason, even when a cloth (eg, a polyester cloth) that is conventionally considered not to have excellent reactivity with the fixing composition, the fixing strength of the colorant to the cloth can be kept high. Therefore, it is possible to effectively prevent deterioration of the printed part due to washing.

[Composition of printed fabric]
The printed fabric of the present invention includes a fabric and a print unit provided on the fabric. The print portion includes a colorant and components derived from the fixing composition of the present invention. Thereby, since the colorant is fixed to the fabric by the fixing composition of the present invention, it is possible to prevent deterioration of the printed part due to washing. In the present specification, the “component derived from the fixing composition of the present invention” refers to the fixing composition after the reaction between the fixing composition of the present invention and at least one of the cloth and the binder resin. Means chemical structure.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.
[Example 1]
First, while stirring 950 g of water, 50 g of PVA (trade name “Kuraray Poval PVA-217E” manufactured by Kuraray Co., Ltd.) was gradually added to water and sufficiently dispersed in water. Further, PVA was completely dissolved in water over 7 hours at 80 ° C. with stirring, and then cooled to room temperature. The aqueous solution thus obtained is hereinafter referred to as “emulsifier aqueous solution”.

  Next, 70 parts by mass of an HDI adduct (trade name “Duranate AE700-100” manufactured by Asahi Kasei Co., Ltd.) and n-undecane (organic solvent, product name “Cactus normal paraffin N— manufactured by JX Nippon Mining & Energy Corporation”) 11 ") 30 parts by mass were mixed. 100 parts by mass of the obtained n-undecane solution (organic solution of polyvalent isocyanate) was added to 100 parts by mass of the aqueous emulsifier solution, and the mixture was vigorously stirred. In this way, a fixing composition was obtained.

  Dispersion liquid containing 100 parts by weight of binder resin (trade name “NK Cooper NR-352HN” manufactured by Shin-Nakamura Chemical Co., Ltd.) and 3 parts by weight of colorant (trade name “WS Blue” manufactured by Toyo Ink Co., Ltd.) 4 parts by weight of the above fixing composition was added. In this way, a printing ink was obtained.

[Example 2]
0.2 parts by mass of oxalic acid dihydrate (manufactured by Kanto Chemical Co., Inc.) is further added to 100 parts by mass of the dispersion containing the binder resin and the colorant (in terms of the total mass of the binder resin and the colorant). A printing ink was produced according to the method described in Example 1 except that.

[Example 3]
The addition of 0.035 parts by mass of an antifoaming agent (trade name “Silicon FZ-5210” manufactured by Toray Dow Corning Co., Ltd.) to 100 parts by mass of the emulsifier aqueous solution and vigorously stirring to produce a fixing composition A printing ink was produced according to the method described in Example 2 except for the above.

[Example 4]
Instead of mixing 70 parts by mass of HDI adduct and 30 parts by mass of n-undecane, 90 parts by mass of HDI isocyanurate (trade name “Duranate TSA-100” manufactured by Asahi Kasei Co., Ltd.) and Isopar L (TonenGeneral) Ink for printing was produced according to the method described in Example 3 except that 10 parts by mass of a trade name (manufactured by Sekiyu Co., Ltd.) was mixed.

[Example 5]
In place of the HDI isocyanurate, a mixture of HDI isocyanurate and HDI oligomer (trade name “Duranate A-201H” manufactured by Asahi Kasei Co., Ltd.) (solid mass ratio of 1: 1) was used. A printing ink was produced according to the method described in Example 4 except for.

[Example 6]
A printing ink was prepared according to the method described in Example 3 except that the HDI oligomer of Example 5 was used instead of the HDI adduct.

[Example 7]
A printing ink was produced according to the method described in Example 3 except that Isopar L of Example 4 was used instead of n-undecane.

[Comparative Example 1]
Instead of the fixing composition, an aqueous dispersion of blocked isocyanate (trade name “Meikanate SU-268A” manufactured by Meisei Kasei Kogyo Co., Ltd.) is used, and the ratio of the mass of the fixing composition to the mass of the binder resin is shown. A printing ink was produced according to the method described in Example 1 except that the value was changed to the value shown in 1.

[Comparative Example 2]
A self-emulsifying polyisocyanate (trade name “Aquanate 210” manufactured by Nippon Polyurethane Industry Co., Ltd.) is used instead of the fixing composition, and the ratio of the mass of the fixing composition to the mass of the binder resin is shown in Table 1. A printing ink was produced according to the method described in Example 1 except that the values were changed.

[Comparative Example 3]
When an HDI burette body (trade name “Sumijour N-3200” manufactured by Sumitomo Chemical Co., Ltd.) was used instead of the HDI adduct body, the HDI burette body was not dissolved in n-undecane. Therefore, a fixing composition could not be prepared.

[Comparative Example 4]
A printing ink was produced according to the method described in Example 3 except that turpen (trade name “Newsol DX Hisoft” manufactured by Nippon Oil Corporation) was used instead of n-undecane.

In Table 1, “trade name“ Kuraray Poval PVA-217E ” ^{* 11} ” means the trade name “Kuraray Poval PVA-217E” manufactured by Kuraray Co., Ltd., and “trade name“ Silicon FZ-5210 ” ^{* 12} ” -The product name "Silicon FZ-5210" manufactured by Dow Corning Co., Ltd. “Fixing composition (mass%) ^{* 13} ” means the ratio of the mass of the fixing composition to the mass of the binder resin. “Oxalic acid (mass%) ^{* 14} ” means the ratio of the mass of oxalic acid to the total mass of the binder resin and the colorant. “PH ^{* 15} ” indicates the pH measured using a commercially available pH meter.

[Solubility of polyisocyanate]
By visually observing the fixing compositions of Examples 1 to 7 and Comparative Example 4, the solubility of the polyvalent isocyanate in the organic solvent was examined. The results are shown in Table 2. In Table 2, when the polyvalent isocyanate is dissolved in the organic solvent, it is described as “A1”, and when the remaining polyisocyanate is not dissolved, it is described as “C1”.

[Measure flash point]
In Examples 1 to 7, the flash point of an organic solution of polyvalent isocyanate was measured. In Comparative Example 2, the flash point of the self-emulsifying polyisocyanate was measured, and in Comparative Example 4, the flash point of the terpene solution containing the HDI adduct body was measured. The flash point was measured according to the method described above in each case. The results are shown in Table 2.

[Odor determination]
The odor of the fixing composition was qualitatively determined by a sensory method. The results are shown in Table 2. In Table 2, when the odor is equal to or less than that when Isopar L or n-undecane is used, “A2” is indicated. When the odor is stronger than when Isopar L and n-undecane is used, “C2” is indicated. ". If the odor is equal to or less than that when using Isopar L or n-undecane, it can be said that low odor properties during operation can be realized.

[Storage stability of fixing composition]
The fixing composition was stored for 7 hours in a thermostat set at 40 ° C. After taking out the fixing composition from the thermostat, the state of the fixing composition was visually confirmed. Moreover, the storage time in the said thermostat was changed to 1 day, and the same evaluation was performed. The results are shown in Table 2. In Table 2, when the state of the fixing composition is stable even after being stored in the thermostatic bath for 7 hours, it is indicated as “A3”, and the state of the fixing composition is stored even after being stored in the thermostatic bath for one day. Is described as “AA3”. It can be said that the fixing composition is excellent in storage stability if the state of the fixing composition is stable even after being stored in the thermostat for 7 hours.

[Storage stability of printing ink]
When the state of the printing ink immediately after production was visually confirmed, gelation was not confirmed in Examples 1 to 7 and Comparative Examples 1 to 4 (excluding Comparative Example 3) ("A4" in Table 2).

  The printing ink was stored for 7 hours in a thermostat set at 30 ° C. After the printing ink was taken out from the thermostat, the state of the printing ink was visually confirmed. The results are shown in Table 2. In Table 2, when the state of the printing ink is stable even after being stored in the thermostat for 7 hours, it is described as “A5”, and when the printing ink is gelled after being stored in the thermostat for 7 hours. Is marked as “C5”. In Comparative Example 2, the printing ink gelled when stored in the thermostatic bath for 7 hours, so the production of the printed fabric using the printing ink was abandoned.

[Washing resistance (water temperature: 40 ° C.) (when using printing ink immediately after manufacture)]
First, a printing ink immediately after production was printed on a polyester fabric (trade name “2WAY” manufactured by Asahi Kasei Co., Ltd.) using a screen for textile printing. The obtained dough was heat-treated using a dry oven (heat treatment temperature: 120 ° C., heat treatment time: 1 minute). A printed fabric was thus obtained.

  The washing resistance (water temperature: 40 ° C.) of the printed fabric was evaluated according to the method described in JIS L 0804 (Dye Fastness Test (Gray Scale for Discoloration)). The results are shown in Table 2. In Table 2, when the gray scale is 4 or more, “A6” is indicated, and when the gray scale is 3 or more and less than 4, “B6” is indicated. If the gray scale is 3 or more, it can be said that the printed fabric has excellent washing resistance.

[Washing resistance (water temperature: 60 ° C.) (when using printing ink immediately after manufacture)]
Except for changing the water temperature from 40 ° C. to 60 ° C., according to the method described in [Washing resistance (water temperature: 40 ° C.) (when using printing ink immediately after production)], the washing resistance of the printed fabric (Water temperature: 60 ° C.) was evaluated. The results are shown in Table 2. In Table 2, when the gray scale is 4 or more, “A7” is indicated, and when the gray scale is less than 3, “C7” is indicated. If the gray scale is 3 or more, it can be said that the printed fabric has excellent washing resistance.

[Washing resistance (water temperature: 40 ° C) (when using printing ink after storage for 7 hours at 30 ° C)]
First, printing ink stored for 7 hours in a thermostat set at 30 ° C. was printed on a polyester fabric (trade name “2WAY” manufactured by Asahi Kasei Co., Ltd.) using a screen for textile printing. The obtained dough was heat-treated using a dry oven (heat treatment temperature: 120 ° C., heat treatment time: 1 minute). A printed fabric was thus obtained.

  The washing resistance (water temperature: 40 ° C.) of the printed fabric was evaluated according to the method described in JIS L 0804 (Dye Fastness Test (Gray Scale for Discoloration)). The results are shown in Table 2. In Table 2, when the gray scale is 4 or more, it is described as “A8”, when the gray scale is 3 or more and less than 4, it is described as “B8”, and when the gray scale is less than 3 Is denoted as “C8”. If the gray scale is 3 or more, it can be said that the printed fabric has excellent washing resistance.

[Washing resistance (water temperature: 60 ° C.) (when using printing ink after storage for 7 hours at 30 ° C.)]
Except for changing the water temperature from 40 ° C. to 60 ° C., according to the method described above [washing resistance (water temperature: 40 ° C.) (when using printing ink after storage at 30 ° C. for 7 hours)], The washing resistance (water temperature: 60 ° C.) of the printed fabric was evaluated. The results are shown in Table 2. In Table 2, when the gray scale is 4 or more, “A9” is indicated. When the gray scale is 3 or more and less than 4, “B9” is indicated. When the gray scale is less than 3, Is written as “C9”. If the gray scale is 3 or more, it can be said that the printed fabric has excellent washing resistance.

In Table 2, “after storage” of “storage stability (after storage) ^{* 21} ” means that the printing ink was stored in a thermostat set at 30 ° C. for 7 hours. “Immediately after production ^{* 22} ” describes the evaluation result of the washing resistance of the printed fabric when the printed fabric is produced using the printing ink immediately after production. “After storage ^{* 23} ” describes the evaluation results of the washing resistance of the printed fabric when the printed fabric was produced using the printing ink stored in a thermostatic bath set at 30 ° C. for 7 hours.

[Discussion]
In Examples 1 to 7, the solubility of polyisocyanate in an organic solvent is excellent, the flash point of the organic solution of polyisocyanate is higher than 60 ° C., the odor of the fixing composition is lowered, and the fixing composition Has excellent storage stability. Furthermore, even when the printing ink stored at 30 ° C. for 7 hours was used, the washing resistance of the printed fabric (water temperature: 40 ° C.) and the washing resistance of the printed fabric (water temperature: 60 ° C.) were excellent.

  In Examples 3 to 7, the fixing composition was superior in storage stability compared to Examples 1 and 2, and was stable even when stored at 40 ° C. for 1 day. In Examples 3 to 7, the fixing composition further contains an antifoaming agent. Therefore, it is considered that such a result was obtained.

  In Examples 2 to 7, compared to Example 1, even when the printing ink was used after storage at 30 ° C. for 7 hours, the printed fabric was excellent in washing resistance. In Examples 2 to 7, since the printing ink further contains oxalic acid, it is considered that the activity of the polyvalent isocyanate in the printing ink is maintained. Therefore, it is considered that such a result was obtained.

  In Comparative Example 1, the washing resistance (water temperature: 60 ° C.) of the printed fabric was lowered even when the printing ink immediately after production was used. In addition, when the printing ink stored at 30 ° C. for 7 hours was used, not only the washing resistance (water temperature: 60 ° C.) of the printed fabric but also the washing resistance (water temperature: 40 ° C.) of the printed fabric decreased. In Comparative Example 2, the storage stability of the printing ink was lowered. In Comparative Example 3, the undissolved residue of the HDI burette body with respect to n-undecane was confirmed. From these facts, it was found that it is preferable to use an HDI adduct, an HDI isocyanurate, or an HDI oligomer as the polyvalent isocyanate.

  In Comparative Example 4, the flash point of the terpene solution containing the HDI adduct was 45 ° C. (60 ° C. or less). Therefore, according to the provisions of the International Maritime Dangerous Goods Regulation, the fixing composition of Comparative Example 4 cannot be transported by ship as normal cargo, resulting in high transportation costs. In addition, the use of terpenes is not preferable in terms of the working environment because the odor is stronger than when n-undecane or Isopar L is used. Therefore, it was found that n-undecane or Isopar L is preferably used as the organic solvent.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

<Organic solvent>
The organic solvent of the present invention dissolves the polyvalent isocyanate of the present invention. Therefore, examples of the organic solvent of the present invention include a solvent having a boiling point of 180 ° C. or higher, or a solvent having a flash point higher than 60 ° C. (more preferably, a solvent having a flash point of 70 ° C. or higher). For example, as the organic solvent of the present invention, n- undecane, n- dodecane, n- tridecane, Tonen trade name of General Sekiyu KK "ISOPAR (Registered R) L 'and its trade name" Isopar (registered trademark ) it is preferred to use at least one of M '.

[Example 4]
Instead of mixing 70 parts by weight of HDI adduct and 30 parts by weight of n-undecane, 90 parts by weight of HDI isocyanurate (trade name “Duranate TSA-100” manufactured by Asahi Kasei Corporation) and Isopar (registered trademark) A printing ink was produced according to the method described in Example 3 except that 10 parts by mass of L (trade name, manufactured by TonenGeneral Sekiyu KK) was mixed.

[Example 7]
A printing ink was produced according to the method described in Example 3 except that Isopar (registered trademark) L of Example 4 was used instead of n-undecane.

[Odor determination]
The odor of the fixing composition was qualitatively determined by a sensory method. The results are shown in Table 2. In Table 2, when the odor is equal to or less than that when using Isopar (registered trademark) L or n-undecane, “A2” is indicated, and the odor is determined from when using Isopar (registered trademark) L and n-undecane. If it is too strong, write “C2”. If the odor is equal to or less than that when using Isopar (registered trademark) L or n-undecane, it can be said that low odor properties during operation can be realized.

In Comparative Example 4, the flash point of the terpene solution containing the HDI adduct was 45 ° C. (60 ° C. or less). Therefore, according to the provisions of the International Maritime Dangerous Goods Regulation, the fixing composition of Comparative Example 4 cannot be transported by ship as normal cargo, resulting in high transportation costs. In addition, the use of terpenes is not preferable in terms of the working environment because the odor is stronger than when n-undecane or Isopar (registered trademark) L is used. Therefore, it turned out that it is preferable to use n-undecane or Isopar (trademark) L as an organic solvent.

Claims (6)

A fixing composition for fixing a colorant to a cloth,
An organic solution containing an organic solvent and a polyisocyanate dissolved in the organic solvent, and an emulsifier are dispersed in a water-soluble solvent,
The polyvalent isocyanate is at least one of an adduct of hexamethylene diisocyanate, an isocyanurate of hexamethylene diisocyanate, and an oligomer of hexamethylene diisocyanate,
A fixing composition having a flash point of the organic solution higher than 60 ° C. The ratio of the mass of the polyvalent isocyanate to the total mass of the organic solvent and the polyvalent isocyanate is 50% by mass to 95% by mass,
The fixing composition according to claim 1, wherein the emulsifier is contained in an amount of 2% by mass to 12% by mass with respect to a total mass of the organic solvent and the polyvalent isocyanate.   The fixing composition according to claim 1, further comprising an antifoaming agent. Preparing the fixing composition according to any one of claims 1 to 3,
Preparing a printing ink containing at least the fixing composition, a binder resin, and a colorant;
And a step of printing the printing ink on the cloth and fixing the colorant on the cloth.   The method for producing a print fabric according to claim 4, wherein the printing ink further comprising at least one of an organic acid and an inorganic acid is prepared. Dough,
A printing unit provided on the fabric,
The printed portion includes a colorant and a component derived from the fixing composition according to any one of claims 1 to 3.