JPH0747355B2 - Inkjet printing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention provides an ink jet printing method which has an excellent effect of preventing bleeding, obtains a sharp pattern and a color pattern having excellent uniformity, and has excellent dyeing fastness. It is about.

(Prior Art) With the recent development of color ink jet printing technology, it has been attempted to utilize it for textile printing, for example, as shown in JP-A-54-18975. However, when it is applied to a cloth, there arises a problem that the color looks lighter and bleeding is larger than when printing on paper. Further, there are various kinds of cloths to be dyed. Due to these reasons, it is difficult to say that a common bleeding preventive means having a large effect is still being developed.

Many means for preventing bleeding on paper have already been proposed. For example, in JP-A-57-36692, basic latex polymer, JP-A-59-96988, and JP-A-59-106989.
In JP-A-59-95186, a method using a water-soluble polymer such as polyvinylpyrrolidone has been proposed.

Regarding the cloth, for example, USP 4,330,293 proposes to add a synthetic polycarboxylic acid to the ink and an alkaline substance to the cloth.

According to the study of the present inventors, a hydrophobic fiber structure such as a polyester fiber has a particularly large bleeding, and it is difficult to exhibit the bleeding preventing effect, and since a disperse dye ink finely dispersed in water is used as a dye, a polycarboxylic acid is used. It has been found that there is a problem that the dispersion is destroyed when such a substance is added, and the fiber is deteriorated in the pretreatment of the alkaline substance.

Further, in the case of dyeing a fiber structure composed of two or more kinds of fiber materials, it is difficult to use a plurality of dyes due to the difference in dyeability, or it is difficult to uniformly mix the dyes and the process is complicated. As a method for solving this problem and for coloring the hardly dyeable fiber material, there is a method of fixing the pigment to the fiber structure with a binder. As an ink jet ink using such a pigment, there is one using a latex as a binder (Japanese Patent Publication No. 60-32663). It has a high concentration of water resistance and light resistance to paper, but when applied to fabric,
Since the structure is rough compared to paper, bleeding is large, and it is difficult to obtain a sharp pattern that can be compared with conventional printing. Further, when used for clothing, it is required to have high performance in dyeing fastness such as washing resistance, dry cleaning resistance, abrasion resistance, light resistance, and texture, but it is difficult to satisfy these with conventional technology. Is.

(Problems to be Solved by the Invention) An object of the present invention is to solve the problems of the prior art as described above, and particularly in ink jet printing with a pigment, excellent bleeding preventive property, a sharp pattern, and a uniform pattern. An object of the present invention is to provide an ink jet printing method capable of obtaining a color pattern having excellent properties. Further, the object of the present invention is to
An object of the present invention is to provide an ink jet printing method which is excellent in dyeing fastness and durability and has little change in texture.

(Means for Solving Problems) In the ink jet printing method of the present invention, an ink containing a pigment and a water-soluble polyester or a water-dispersible polyester or polyamide component is used as an ink component, and the polyester or polyamide component is used. It is characterized in that a crosslinking agent for crosslinking is blended in the ink or the recording material and crosslinked on the recording material.

The ink jet according to claim (1), wherein the water-soluble or water-dispersible polyester or polyamide is anionic and the recording material is pretreated with a metal salt and / or a cationic compound. How to print.

Acrylic polymers and synthetic rubber latices are usually used as the binder for pigment printing, but in the present invention, water-soluble or water-dispersible polyesters which are usually used as a texture curing agent are used and crosslinked. By cross-linking with an agent, a film having a high degree of durability is formed, and a printed product having excellent dyeing fastness is obtained. Even when using a resin with a hard texture,
It has been found that the texture hardening is extremely small due to the dot-like binder application by the ink jet. Further, by using an anionic binder and pretreating a recording material with a metal salt and / or a cationic compound, it has been found that in addition to the above effects, it is also a method excellent in preventing bleeding. is there.

Hereinafter, the present invention will be described in detail.

The present invention is a paper, a film, a plastic, a fiber structure,
The present invention relates to a method for forming a pattern on a recording material such as metal. As the material to be recorded, since the water-soluble or water-dispersible polyester or polyamide used in the present invention has excellent adhesiveness, its type is not limited as in the past, but especially for a fiber structure. The effect of the present invention is most remarkably exhibited.

The fibrous structure is an arbitrary structure composed of fibers, and includes knitted fabric, woven fabric, non-woven fabric, and yarn. The material of the fiber structure is not particularly limited, and any of natural fiber, regenerated fiber, synthetic fiber can be used alone or a composite product, but a composite material or a non-staining fiber material that is difficult to dye with a single dye The method of the present invention is more effective for a fiber structure composed of

The pigment used in the present invention is an inorganic pigment or an organic pigment, and an appropriate pigment used as an ink component can be used. For example, it can be appropriately used from the pigments described in the color index. Among these pigments, one or a plurality of these pigments are dispersed in a liquid medium and used depending on the purpose of use. Excess dispersant for commercial pigment liquids,
There are some that contain activators, etc.
Since the discharge stability is often adversely affected in many cases, it is preferable that the content of these additives is as small as possible. In addition to pigments, dye components can also be included.

The water-soluble or water-dispersible polyester used in the present invention is well known to those skilled in the art, and a polyester containing a hydrophilic group is usually used. Examples are JP-B 47-40873 and JP-B 5
No. 0-121336, etc., a dicarboxylic acid is usually used as an acid component, a diol is used as an alcohol component, and a bifunctional monomer containing —SO ₃ M is used as a third component in combination for polycondensation. It is synthesized by this. Also,
A polyfunctional monomer component having a carboxyl group or a hydroxyl group may be introduced into the molecule to impart hydrophilicity. The functional group of the —SO ₃ M-containing bifunctional monomer is preferably an ester-forming functional group, that is, a carboxyl group (or its derivative) or a hydroxyl group. Preferred -SO ₃ M-containing difunctional monomer is sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or 4-sulfo-2,7
Examples thereof include sodium salt of dicarboxylic acid. A particularly preferred monomer is 5-sodium sulfoisophthalic acid or a derivative thereof, such as rhidium sulfodimethylisophthalate. The amount of the -SO ₃ M-containing bifunctional monomer as the third component in the above is contained in such a proportion that it is 2 to 25 mol%, particularly 3 to 15 mol% of the total monomer components. Is desirable.
It should be noted that an excessive --SO ₃ M group is not preferable because it may be water-soluble even after crosslinking.

The carboxyl residue of the water-soluble or water-dispersible polyester is preferably in the range of 0.01 to 0.5 mol per 1 kg of the resin.
This has a significant meaning when the water-soluble or water-dispersible polyester is crosslinked with a crosslinking agent, and the range of 0.02 to 0.2 mol is particularly preferable.

Water-soluble or water-dispersible polyamides used in the present invention are also well known. For example, a normal polyamide such as polyhexamethylene adipamide, which is appropriately copolymerized with a hydrophilic monomer component such as 5-sodium sulfoisophthalate,
It is a polyamide obtained by copolymerizing a monomer component such as α-dimethylamino-ε-caprolactam.

The cross-linking agent in the present invention is a compound having two or more functional groups capable of reacting with a water-soluble or water-dispersible polyester or polyamide. Specific examples of these functional groups include an epoxy group, an alkoxy group, an alkoxymethyl group, an aziridine group, an isocyanate group, and an amide group. Of these, epoxy compounds, aziridine compounds, isocyanate compounds, blocked isocyanate compounds and aminoplast resins are preferred. The epoxy compound is a compound containing at least two epoxy groups represented by a glycidyl group in its molecule, and specifically, ethylene glycol diglycidyl ethers (ethylene glycol chains 1 to 30), propylene glycol di- Glycidyl ethers (propylene glycol chains 1 to 15), glycerol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, succinic acid, adipic acid diglycidyl ester, glycidyldimethylhydantoin, furfurylglycidyl Examples include ether.
Particularly preferred epoxy compounds are sorbitol polyglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, polyethylene glycol diglycidyl ether.

The aziridine compound contains at least two derivatives of ethyleneimine in the molecule, and specific examples thereof include the following, but are not limited thereto.

In the present invention, it is preferable to use a water-soluble aziridine compound.

The isocyanate compound has at least two isocyanate groups in the molecule, and specific examples thereof include tolylene diisocyanate, xylene diisocyanate, and hexamethylene diisocyanate. The blocked isocyanate compound is an isocyanate compound in which the isocyanate group is stabilized with phenol, alcohol, oxime, lactam, sodium acid sulfite, active methylene compound or the like in order to reduce the reactivity of the isocyanate group.

The aminoplast resin is a condensate of a compound containing an amino group and an aldehyde, and formaldehyde adducts such as melamine, urea and aniline are preferably used. Further, a methylol compound, an alkoxy compound, an alkoxymethyl compound, an amidated compound of these compounds, and an initial condensation product thereof are also included. Particularly preferred is a melamine derivative represented by the following general formula.

However, in the formula, R _{1 to} R ₆ : -H (however, all H are excluded) -OC _n H _{2n + 1} (n = _{1 to} 16) -CH ₂ OC _n H _{2n + 1} (n = 1 To 16) —CH ₂ OH —CH ₂ CH ₂ OH —CONH ₂ —CONHCH ₂ OH The crosslinking reaction in the present invention means a binder component composed of a water-soluble or water-dispersible polyester or polyamide and two or more functional groups. That is, the compound has a three-dimensional network structure. The properties of the binder component change due to the crosslinking reaction, but in the present invention, it is necessary to perform sufficient crosslinking so that the water-soluble or water-dispersible binder becomes water-insoluble. However, since excessive crosslinking leads to a texture effect, the amount of crosslinking agent used should be determined to satisfy these conditions. In addition, if the water solubility of the binder is too large or the number of reactive groups is too small, the binder may be dissolved in water even if it is cross-linked, so care must be taken when selecting the binder.

The concentration of each component is preferably in the following range with water as the main medium.

The pigment component is contained in an amount of 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the total amount of the ink.

The binder component consisting of water-soluble or water-dispersible polyester or polyamide is in the range of 1 to 40 wt%, more preferably 5 to 20 wt%.

When the cross-linking agent component is added to the ink, the amount is preferably 0.1 to 40 wt%, preferably 0.5 to 20 wt% with respect to the binder amount. When it is applied on the recording material, the amount is preferably 0.1 to 50% by weight, and more preferably 0.5 to 25% by weight, based on the amount of binder applied. The method of applying the cross-linking agent is not particularly limited, and it may be applied by a dipping method, a pad method, a coating method, a spray method, an ink jet method, or the like.

Further, a catalyst that accelerates the crosslinking reaction may be provided in the ink or on the recording material. It is preferably applied onto the recording material from the viewpoint of ink stability. Pretreatment with a metal salt type catalyst is preferable also from the viewpoint of preventing bleeding.

In addition, wetting agents (mainly polyhydric alcohols, glycol ethers, etc.), physical property modifiers (viscosity, pH, surface tension, conductivity, etc.), preservatives, bactericides, chelation in order to obtain good ink properties. It is also preferable to add an agent or the like.

The cross-linking reaction occurs even after air-drying after the ink jet dye, but it is preferable to react by a heat treatment. More preferably, by baking at 130 to 170 ° C. for 1 to 5 minutes or by treating in saturated steam at 100 ° C. for 1 to 10 minutes, a tough crosslinked binder film with little change in texture is formed. Further, after the ink jet dye, by steaming in the presence of water without being dried, or by crosslinking with microwave or electron beam irradiation, a crosslinked binder film having toughness and very little change in texture can be formed.

It is preferable to pretreat the recording material with a metal salt and / or a cationic compound in order to obtain a sharp pattern with excellent bleeding prevention effect. These compounds form a complex with an anionic water-soluble or water-dispersible polyester or polyamide to prevent ink bleeding. The metal salt is not particularly limited, but a water-soluble metal salt having a valence of 2 or more is preferable, and specific examples thereof include halosaponified compounds such as Zn, Mg, Ca, Ba and Al, nitrates, acetates, carbonates and the like. There is. Particularly preferred are Ba and Ca halides. The cationic compound is selected from amine salts, quaternary ammonium salts, polymers thereof. In particular,
Examples of amine salts include higher alkyl amine salts, amide-type amine salts obtained from fatty acids and lower amines, and quaternary ammonium salts include those obtained by quaternization reaction of amines. Examples of those contained in the polymer include those contained in the main chain and those pendant to the side chain. Preferred cationic compound pretreatment agents are polyamines and polyammonium salts. The pretreatment agent is preferably water-soluble, and may be used alone or in combination of two or more. The applied amount is determined by the degree of ink bleeding on the recording material, but is usually in the range of 0.1 to 10% with respect to the weight of the recording material. Type of pretreatment agent,
Bleeding can be controlled arbitrarily by the applied amount. The applying method is not particularly limited, and a crosslinking agent, a catalyst and the like can be applied by a dipping method, a coating method, a spray method, an ink jet method or the like.

(Examples) The effects of the present invention will be described in more detail with reference to Examples.

Example 1 Dyeing was performed under the following fabric (1), ink composition (2), and ink jet condition (3).

(1) Fabric A mixed-spun fabric (textile poplin) composed of polyester 65 / cotton 35 was pretreated with the following chemicals.

1-a: untreated 1-b: CaCl ₂ · 2H ₂ O 20 g / + catalyst ⁽¹⁾ 1 g / pretreatment 1-c: CaCl ₂ · 2H ₂ O 50 g / + catalyst 1 g / pretreatment 1-d: BaCl ₂ · 2H ₂ O 50g / + catalyst 1 g / pretreatment 1-e: cationic compound ⁽²⁾ 50 g / + catalyst 1 g / pretreatment (1) Sumitex acclerafor ACX from Sumitomo chemical Co. (2) Kemisutatsuto 6300H from Sanyo chemical Industries (Co. ) Pad (pickup 70%)-dried (100 ° C, 2 minutes).

(2) Ink composition (1) Dexcel Blue H2R Dainippon Ink Co., Ltd. (2) Terephthalic acid 50mol% Isophthalic acid 30mol% 5-Sodium isophthalate 20mol% Polyester from ylene glycol 100mol% (3) Sumitex Resin M-3 (Sumitomo Chemical ( (Methylated trimethylol melamine) (4) Denacol Ex313 (Nagase Sangyo Co., Ltd. (glycerol-luge and tri-glycidyl ether) The ink was used after degassing under reduced pressure after passing through a 5μ filter. .

(3) Ink jet condition Ink jet method: On-demand type Nozzle diameter 75 (μ) Nozzle-fabric distance: 1 (mm) Printing voltage: 50 (V) Resolution: 8 dots / mm After applying ink under the above conditions, at 150 ° C Crosslinking was performed by baking for 3 minutes. The bleeding was measured by measuring the dot diameter with a microscope and determining the major axis. The results are shown in Table 1. First
As is clear from the table, when the pre-treated fabric of the present invention is used as a recording material, it has an excellent effect of preventing bleeding and is soft with little change in texture.

In particular, the texture is markedly different from the comparative example, and the dot diameter is large (large bleeding) as in the comparative example.
Then, the entire surface of the fiber is covered with resin, and the texture is significantly hardened. On the other hand, when the dot diameter is small and the bleeding is small as in the method of the present invention, it adheres to the fiber surface in the form of dots, so that there is no need to fix the entire tissue, there is a degree of freedom as a woven fabric, and the texture becomes extremely flexible. .

Example 2 The same ink composition (Ink B) as in Example 1 was used, except that the fabric was a polyester filament woven fabric (texture palace) and cotton broad were different, and the fabric pretreatment (1-d) was performed, and the same method was used. Ink jet dyeing was performed.

Dyeing fastness, dot diameter, and color developability were measured, and the results are shown in Table 2.

All the fabrics using the ink of the method of the present invention have good dyeing fastness and can form a durable coating film. A cloth pretreated with a metal salt is excellent in color developability and bleeding prevention, and has a soft texture, which is a particularly preferable method.

Example 3 Ink jet dyeing was carried out in the same manner as in Example 1 using the cloth and ink composition shown below.

(1) Cloth (broad woven fabric of 65 polyester / 35 cotton) 2-a Untreated (no pretreatment) 2-b Pretreatment 2-c Pretreatment 2-d pretreatment (2) Ink composition Ink C Ink D Pigment (Example 1) 10 10 Water-dispersible polyester ⁽¹⁾ 40 40 Melamine resin-1.5 1,3 Butanediol 20 20 Ion-exchanged water 30 28.5 Total 100 100 (1) Eastman WD size (solid content: 25%) manufactured by Eastman Co., Ltd. The dyeing fastness, color developability, dot diameter, and texture were measured in the same manner, and the results are shown in Table 3.

The cloth of the present invention was pretreated with a crosslinking agent (2-c, 2
It is recognized that -d and that the ink has a cross-linking agent added (Ink D) have excellent fastness and good film durability as compared to the ink having no cross-linking agent added (Ink C). Further, when the cloth was a mixture of both the cross-linking agent and the metal salt, the dot diameter was small, and a fiber pattern in which bleeding was prevented was obtained.

(Effects of the Invention) The present invention improves the durability of the film, which is a drawback of conventional pigment printing, and at the same time, improves bleeding, which is a problem of ink jet dyeing. Since it can be added, its industrial value is very large.

Claims (2)

[Claims] 1. An ink containing a pigment and a water-soluble or water-dispersible polyester or polyamide component as an ink component is used, and a crosslinking agent for crosslinking the polyester or polyamide component is blended in the ink or a recording material. And an inkjet printing method characterized by crosslinking on a recording material. 2. An ink containing a pigment and a water-soluble or water-dispersible anionic polyester or polyamide component as an ink component, and a crosslinking agent for crosslinking the polyester or polyamide component in the ink or a metal salt or / And an ink-jet printing method, which comprises blending in a recording material pretreated with a cationic compound and crosslinking on the recording material.