JPH02300377A - Cloth for ink-jet dyeing and dyeing method - Google Patents

Abstract

PURPOSE:To obtain the subject cloth having excellent chromophoric properties and sizing properties for ink and giving fine image of deep color by putting specific porous bulky fine particle and water-soluble polymer into cloth. CONSTITUTION:0.5-10wt.% bulky fine particles composed of porous bulky fine particles, preferably porous silica having 0.2-10mu, especially 0.5-5mu average particle diameter, >=40ml/5g, especially >=60ml/5g sedimentation volume and preferably >=1ml/g volume of pores and 0.1-5wt.% water-soluble polymer (natural or synthetic paste adapting to dyeing ink and not impeding to dyeability) are used to pre-treatment of cloth composed of natural or synthetic fiber, especially cellulosic fiber and attached to the cloth to afford cloth for ink-jet dyeing giving highly dignified image having excellent stability of ejected ink, chromophoric properties and sizing properties in ink-jet dyeing.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is an inkjet dyeing method for obtaining high quality images that have excellent ink ejection stability, high color development, and are prevented from bleeding. The present invention relates to a dyeing fabric and a dyeing method using the dyeing fabric.

(Prior Art) Conventionally, methods such as hand printing, roller printing, screen printing, and transfer printing have been used as methods for forming patterns on fabrics, but all of them involve screens with patterns formed in advance,
This method involves preparing an engraving roller and transfer paper.

Furthermore, in recent years, an inkjet printing method has been developed in the field of paper printing and has already been put into practical use.

Pattern formation using the inkjet method can be created without spending time and money by combining it with a pattern reader and computer, so it is also used in the textile field.
It has attracted attention and attempts are being made to apply it directly to fabrics.

When applying this inkjet dyeing to fabrics, it is important to satisfy the following conditions.

(1) Perform bleed prevention treatment to obtain delicate images on fabric.

(2) High color development can be achieved by applying a small amount of ink.

(3) Level dyeing properties can be obtained by applying a small amount of ink.

(4) Ink discharge must be stable.

The present inventors have also already proposed the following method regarding prevention of inkjet bleeding.

(A) A method using special pre-treatment on the fabric.

(B) Method using special ink.

(C) A method using both special pretreatment and special ink.

Regarding (A), water-repellent treatment to prevent ink migration (Japanese Patent Publication No. 60-99081) and water-soluble polymer treatment to improve the water retention of fabrics (Japanese Patent Publication No. 63-315)
Publication No. 92), etc.

Regarding (B), prevention of bleeding by ink with specific viscosity behavior (Japanese Unexamined Patent Publication No. 101669/1983).

Regarding (C), the movement of ink is reduced from both the fabric and the ink.
In addition, in the field of recording materials such as paper, many proposals have been made regarding inorganic materials. For example, JP-A-56-14858
5, Japanese Patent Publication No. 63-56871 to 56876, Japanese Patent Publication No. 63-65033 to 65040, etc. Both have an ink-receiving layer to improve ink absorption.
This is to prevent bleeding and improve color development.

Among these, when the ink requires some kind of additive, even if the effect of preventing bleeding is great, the ejection performance of the ink is often deteriorated. That is, additives increase ink viscosity, increase stickiness, increase insoluble components, etc., resulting in a decrease in ink ejection performance and reliability.

On the other hand, pre-treatment of the fabric alone does not satisfy both a sufficient bleeding prevention effect and high color development. According to studies conducted by the present inventors, in order to obtain a deep color, either the amount of ink applied must be increased or the ink density must be increased.

In other words, increasing the amount of ink applied increases the bleeding,
Furthermore, when the ink concentration increases, the ejection performance decreases.

Therefore, although each factor alone can be satisfied in inkjet bleeding prevention, high dyeing properties, level dyeing properties, and ink ejection performance, it is currently not possible to satisfy all factors.

[Problems to be Solved by the Invention] The present inventors have conducted extensive studies to solve these problems, particularly inkjet bleeding prevention, high color development, level dyeing properties, and ink ejection stability. The present invention was achieved by discovering that by using a fabric pretreated with a combination of specific porous bulky particles and a water-soluble polymer, inkjet printing eliminates the above problems and satisfies all the problems.

An object of the present invention is to provide a fabric for inkjet dyeing and a dyeing method using the same for obtaining high-quality images that have excellent ink ejection stability, high color development, and are prevented from bleeding. .

[Means for Solving the Problems] In order to achieve the above object, the present invention has the following configuration.

(1) Average particle size is 0.2-10μ, sedimentation volume is 40m
0.5 to 10% by weight of porous bulky fine particles weighing 15g or more
and a fabric for inkjet dyeing, characterized in that 0.1 to 5% by weight of a water-soluble polymer is added.

(2) The fabric for inkjet dyeing according to (1), wherein the porous bulky fine particles have a pore volume of 1 ml/g or more.

(3) The fabric for inkjet dyeing according to (1) or (2), wherein the porous bulky fine particles are hydrophilic porous silica.

(4) A dyeing method characterized by inkjet dyeing using the dyeing fabric according to any one of (1) to (3) above, followed by fixation and soaping treatment.

The present invention will be explained in detail below.

The concept of the present invention is different from the conventional bleeding prevention and coloring properties.

That is, porous inorganic fine particles have conventionally been mainly used in recording paper (Japanese Unexamined Patent Publication No. 148585/1985).

Pretreatment of filler particles (Japanese Patent Publication No. 63-65034) has been proposed (particle size is regulated), but these do not allow for bleeding when porous inorganic fine particles or filler particles are present in the product. Problems include prevention and color development (dot density).

Since paper has no anisotropy, the ink spreads relatively uniformly, but since fabric is made of warp and weft yarns, it spreads relatively easily in the axial direction, and the bleeding and color development behavior of paper and fabric are quite different.

In addition, in inkjet dyeing of fabric, fixation and soaping are performed after inkjet discharge, so unlike paper, the final product fabric does not contain porous inorganic fine particles or filler particles.

Therefore, the final product fabric needs to exhibit good bleeding prevention and coloring properties in this state.

That is, even if the bleeding is small immediately after inkjet, the bleeding may become larger during the fixing (steaming) or soaping process.

Similarly, even if the coloring property is good immediately after inkjet, the coloring property may be significantly reduced because the porous inorganic fine particles or filler particles may interfere with the dyeing property or may not come off properly.

The present inventors have conducted various studies on porous inorganic fine particles and filler particles, and have found that the above-mentioned particle diameters and applicators alone are not sufficient to achieve the goals of inkjet dyeing, such as prevention of bleeding, color development, and level dyeing. However, only the combination of specific porous bulky particles and water-soluble polymers can achieve all of the properties of bleeding prevention, color development, and level dyeing, resulting in delicate images and color development. It has been discovered that it has excellent dyeing properties and level dyeing properties, and can provide a quality with high commercial value.

As a result of various studies on the relationship between the characteristics of porous bulky fine particles and inkjet dyeing characteristics, the present inventors found that the coloring property mainly depends on the sedimentation volume (bulkiness) of the particles, and the bleeding prevention property depends mainly on the pore volume (water absorption amount). ), they found that the level dyeing property of dyed fabrics is correlated with the particle size, and they found an appropriate pretreatment agent that satisfies these requirements at the same time, leading to the invention.

The porous bulky fine particles referred to in the present invention are classified into inorganic porous materials and organic porous materials.

Inorganic porous materials include silica, alumina, alundum,
Examples include porous ceramics, zeolite magnesia, carbon, pearlite shirasu, etc.

Examples of the organic porous material include rubber, resin, fiber, etc., but inorganic porous materials are preferably used, and silica is most preferably used.

Methods for producing these inorganic porous materials include sintering, foaming, hydration, gelation, extrusion, etc., and gelation is preferably used in the case of silica.

The average particle size as used in the present invention refers to the particle size with the highest distribution as measured by a Coulter counter method, centrifugal sedimentation method, or the like.

The average particle size affects the uniformity of dispersion into the pretreated fabric, and the larger the average particle size, the faster the sedimentation will occur in low viscosity treatment liquids.
There are problems in that it is difficult to perform uniform pretreatment and that it is difficult for particles to penetrate into the fabric.

In the present invention, the average particle diameter of the porous bulky particles is 0.2
~10μ, more preferably 0°5~5μ.

The sedimentation volume (ml 15g) as used in the present invention is a factor representing bulkiness. That is, to measure the sedimentation volume, weigh 5 g of porous bulky fine particles, gradually put them into a 200 ml measuring cylinder, let it stand, and measure the volume after 3 minutes (Takushi Revised Japanese Pharmacopoeia Handbook 1981 D26)
1 light silicic anhydride). In other words, it shows how much volume 5g of porous bulky particles has.

The pore volume (ml/g) indicates how many voids a particle (1 g) has, that is, how much water (or ink) the particle has.

The pore volume is measured by the true density (ρt) using the helium replacement method.
The density (ρp) is measured using the mercury displacement method and calculated using the following formula.

Vp= (1/ρp-1/ρt) (1) Hydrophilic porous silica as used in the present invention is one whose surface is covered with hydroxyl groups (-OH), and the hydroxyl groups on the surface are treated with an organic substance. It is preferable that it is not.

Generally, the coloring property of a fabric is determined by the amount of ink applied to the surface of the fabric, if the dyeability is the same and the amount of ink applied is the same. In other words, the greater the amount of ink retained on the surface of the fabric, the better the color development will be; conversely, if the amount of ink retained on the surface of the fabric decreases (the ink will penetrate into the interior of the fabric and be retained), Color development is reduced.

In other words, as the sedimentation volume of fine particles increases, the apparent volume increases, and more particles are present on the surface of the fabric without being covered with water-soluble polymers, and the ink is retained on the surface of the fabric, resulting in color development. This is thought to improve performance.

On the other hand, when the sedimentation volume is small, fewer particles exist on the surface and the ink permeates into the interior of the fabric, resulting in a decrease in color development.

In terms of color development, the sedimentation volume is 115 g or more in 40 m, preferably 15 g or more in 60 ml.

Next, in the present invention, preferably those having a pore volume of 1 ml/g or more are used.

The pore volume referred to in the present invention is important for the amount of ink absorbed, and as the pore volume increases, the voids become larger and the amount of ink absorbed tends to increase, reducing bleeding. From the viewpoint of preventing bleeding, the pore volume is preferably 1 ml/g or more.

In the present invention, these porous bulky fine particles range from 0.5 to
It is necessary to add 10% by weight. If it is less than 0.5% by weight, there is little effect, and if it exceeds 10% by weight, the cost will increase, the viscosity of the processing liquid will increase, it will lack uniformity, and it will not come off easily. This is not preferable because it may become defective and the color development may deteriorate.

The amount applied to the fabric is preferably in the range of 2 to 5% by weight.

Next, in the present invention, it is necessary to use the porous bulky fine particles and a water-soluble polymer together.

The water-soluble polymer referred to in the present invention must be selected from those that allow porous bulky fine particles to adhere to the fabric, further enhance the bleeding prevention effect, and do not inhibit dyeability. For example, in the case of reactive dyes, sodium alginate, carboxymethylcellulose, and poly(meth)acrylate are preferably used.

Water-soluble polymers can be classified into natural thickeners and synthetic thickeners.

Natural thickeners include starch, cellulose such as methylcellulose, hydroxymethylcellulose, and carboxymethylcellulose, gums such as locust bean, gum, and tamarind, and sodium alginate.

Examples of synthetic glues include vinyl-based glues such as polyvinyl alcohol and polyvinyl alcohol ether, acrylic-based glues such as poly(meth)acrylic acid, poly(meth)acrylates, esters, and acrylamide, and maleic acid copolymers such as styrene, Other examples include copolymers with vinyl acetate, polyvinylpyrrolidone, and polyethylene oxide.

Among them, carboxymethylcellulose, sodium alginate, and poly(meth)acrylate are preferably used.

The amount of water-soluble polymer applied is 0.1 to 5% by weight based on the fabric. If it is less than 0.1% by weight, the adhesion with the porous bulky particles will be poor, and if it exceeds 5% by weight, the treatment solution The viscosity of the adhesive increases too much, which limits the application method and results in poor desizing properties. Therefore, a range of 0.5 to 3% by weight is preferably used.

Further, the ratio of the porous bulky fine particles to the water-soluble polymer is 0.05 to 0°8 with respect to 1 part of the porous bulky fine particles, preferably O.
, OS~0.2.

The method for adding porous bulky particles and water-soluble polymers is as follows:
Any method such as pad method, spray method, coating method or printing method may be used, but from the viewpoint of preventing bleeding, it is preferable to impregnate the pretreatment agent into the inside of the fiber structure.In this respect and from the viewpoint of uniformity of treatment, The pad method is the best.

In addition, dyeing aids such as acids, alkalis, and reduction inhibitors may be added to the fabric as required.

The fabric referred to in the present invention is not particularly limited, and may be a woven fabric, a knitted fabric, or a nonwoven fabric, and may be either natural fiber or synthetic fiber, but hydrophilic natural fiber is particularly preferred, and cellulose fiber is more preferably used.

The inkjet dyeing referred to in the present invention is a method in which a liquid such as ink is ejected from a nozzle, and the ejected liquid is turned into droplets and controlled and utilized.The methods include (1) continuous ejection method (deflection type, Divergence type) (2) On-demand type (pressure pulse type, bubble jet type, electrostatic discharge type), and any method may be used.

The optimum amount of ink applied depends on the fabric structure, but if the fabric weight is 60 to 200/%, it is usually 15 to 60 g/rrr.
It is good to give. If the amount of ink applied is small, hot water remains and the coloring properties deteriorate.

On the other hand, when the amount of ink applied is large, the prevention of bleeding becomes greater, so it is necessary to set the optimum amount of applied ink depending on the fabric.

The fabric to which the porous bulky particles and water-soluble polymer of the present invention have been applied is inkjet dyed, then subjected to ink fixation treatment such as steaming, and finally the porous bulky particles and water-soluble polymer are removed. The product is made into a product after undergoing soaping and finishing treatments.

Steaming treatment, soaping treatment and finishing treatment can be carried out using generally known equipment and methods.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The invention is not equally limited to these examples.

(Example) Examples 1 to 3, Comparative Examples 1 to 5 Using bleached and refined cotton fabric (broad double welt weight 81 g/rrr) as cellulose fiber, and using various fine particles shown in Table 1, the following procedure was carried out. Processed and pad (squeezing ratio = 60%) - dried.

(1) Pretreatment of fabric (%) ABC Sodium alginate 1 0 1 Porous bulky fine particles -1010 Sodium carbonate 3 3 3 Next, ink was applied using the ink composition (2) and inkjet conditions (3) shown below.

(2) Ink composition Dye 30% Ethylene glycol 20% Ion exchange water 50% Dyes include a, Remazol Turkis Blue G Liquid (Re
mazol TurquoiseBlue G
Liquid) (manufactured by Hoechst) Cibacron Red 6B Liquid b, (Cibacron Red 6BLiqui
d) (manufactured by Ciba and Geigy) Both were filtered through a 1 micron filter and degassed under reduced pressure before use.

(3) Inkjet conditions Inkjet method: On-demand type Nozzle diameter: 75 microns Applied voltage: 260V Driving frequency: 4000Hz Resolution: 8 dots/mm Inkjet dyeing was performed using the inkjet pretreated cloth obtained in (1) . Next, fixation-soaping was performed for dyeing.

(4) Steam treatment for 15 minutes at 100°C with saturated steam for fixation and soaping. Next, it was washed with water, soaped at 80°C for 5 minutes, and dried.

(5) Measurement The average particle diameter (μ) of the a0 particle diameter was determined by the Coulter counter method.

b. The sedimentation volume is (ml 15g) Weigh 5g of inorganic fine particles, gradually put them into a 200ml measuring cylinder, let it stand,
The volume was measured after 3 minutes.

For the apparent color development of C0 (K/S), all wavelengths were determined using a multi-light source colorimeter, and /S was determined using the following formula.

K/S=(1-R) 2/2R The larger the value of K/S, the higher the color development.

(R measures blue and indicates reflectance at maximum absorption wavelength at 640 nm) d, Uniformity indicates uniformity in fabric pre-treatment.

Uniformity was determined by visual judgment.

e. Bleeding represents the moving distance (mm) of the ink and shows how far the ink spreads on the boundary between blue and red. If it is 0.7 mm or less, a delicate image can be imparted to the fabric.

The results of Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 1.

As shown in Table 1, Comparative Example 1 was untreated and had the largest amount of bleeding. Comparative Example 2 is a treatment with a water-soluble polymer alone, Comparative Example 3 is a treatment with an inorganic particle alone, and in both cases the bleeding is slightly smaller, but it is insufficient.Comparative Example 4.5 is a treatment with an inorganic particle and a water-soluble polymer. However, the target for preventing bleeding, which is 0.7 mm or less, has not been achieved.

Therefore, as shown in Examples 1 to 3, the combined treatment of a water-soluble polymer and specific particles provides good bleeding prevention properties.

Furthermore, even if the particle size is the same, if the sedimentation volume differs, the coloring property (K/S) will change. Color development has a correlation with (K/S) sedimentation volume, and color development tends to improve as the sedimentation volume increases. Therefore, from the viewpoint of color development, porous bulky fine particles with a sedimentation volume of 40 ml/5 g or more are required.

The uniformity of pretreatment has a correlation with the particle size of the particles, and when the particle size exceeds 10μ, it appears non-uniform to the naked eye (Comparative Example 5)
.

In other words, a treatment liquid with low viscosity causes rapid sedimentation and cannot be uniformly pretreated.

On the other hand, when the particle size was 10 μm or less, a pretreated fabric with very good uniformity was obtained.

As mentioned above, the color development is correlated with the sedimentation volume and the uniformity of pretreatment is correlated with the particle size, and the present invention has a comprehensive improvement in color development, bleeding, and uniformity of pretreatment compared to Comparative Examples 1 to 5. Excellent.

Examples 4 to 7, Comparative Example 6 Various inorganic fine particles having different particle characteristics such as sedimentation volume and pore volume were treated in the same manner as in Example 1(C).

f. The pore volume was determined from equation (1) described in the text. The pore volume (ml/1g) is how many ml is 1g of inorganic fine particles
In other words, it represents how much ink it can absorb.

The results of Examples 4 to 7 and Comparative Example 6 are shown in Table 2.

As shown in Table 2, the bleeding correlates with the pore volume, and as the pore volume increases, the bleeding tends to decrease.

This is thought to be due to the fact that as the pore volume increases, ink absorption improves. Comparative Example 6 has a small pore volume and large bleeding, but the present invention (Examples 4 to 7) has a large pore volume and small bleeding. In terms of bleeding, the pore volume is 1ml/
Examples 8 to 11 and Comparative Examples 7 to 8, in which the weight ratio is more preferable, are as follows.The same treatments as in Example 1 were performed except for the pretreatment (1) shown below.

(1) Pretreatment of fabric (%) Water-soluble Porous bulk Sodium carbonate polymer High fine particles Lithium Example 8 1 1.0 3 Example 9 1 3.0 3 Example 10 1 5.0 3 Example 11 1 7.0 3 Comparative Example 7.10.33 Comparative Example 8 1 0.6 3 Water-soluble polymer: Sodium alginate Porous bulky fine particles: 5YLOID 244 In addition, Examples 8 to 11,
The results of Comparative Examples 7 and 8 are shown in Table 3.As shown in Table 3, in terms of color development and bleeding prevention,
The more the porous bulky fine particles increase, the better. , Comparative Examples 7 and 8, which have a small amount of porous bulky particles, do not have sufficient color development and bleeding prevention effects.

Therefore, in terms of color development and bleeding prevention, the present invention (Example 8)
- 11), the solid content of the porous bulky fine particles on the fabric is required to be 0.5% or more, preferably 2% or more.

Examples 12 to 14, Comparative Examples 9 to 10 The same treatments as in Example 1 were performed except for the pretreatment (1) shown below.

(1) Fabric pretreatment (%) Water-soluble Porous bulk Sodium carbonate polymer High fine particles Lithium Example 12 0.2 7.5 3 Example 13 0.5 7.5 3 Example 14 1.0 7. 5 3 Comparative Example 9-7.53 Comparative Example 10 0.1 7.5 3 Water-soluble polymer: Sodium alginate Porous bulky fine particles: 5YLOID 244 Examples 12-1
4. Table 4 shows the color development and bleeding prevention results of Comparative Examples 9 and 10.

As shown in Table 4, those with no sodium alginate added (Comparative Example 9) and those with a small amount (Comparative Example 1)
0) The product has a slightly large amount of bleeding.

On the other hand, those to which porous bulky fine particles have been added have improved color development, but the bleeding is somewhat large.

That is, it can be seen that the amount of water-soluble polymer on the fabric is required to be 0.1% or more in terms of color development and prevention of bleeding.

Table 3 Concentration, color development, and bleeding of inorganic fine particles The values in parentheses () are based on the solid amount of inorganic fine particles on the fabric (o, w, f
) is shown.

Table 4 Concentration and coloring property of water-soluble polymer () The values in () are the solid amount of water-soluble polymer (o, w) on the fabric.
, f).

Example 16, Comparative Example 12 Woven fabric from polyester fiber (120g/bonzie with second stitch)
Comparative Example 12 using rd) and not adding inorganic fine particles,
Pretreatment (1) was carried out under the conditions shown below to impart inorganic fine particles.

(1) Pretreatment of fabric (%) Comparative example 12 Example 16 C, M, C11 SYLOID 150-7 malic acid
22 Pad (265% reduction) - Dry. Next, an ink was applied using the ink composition (2) and inkjet conditions (3) shown below.

(2) Ink composition Dye 10% 1.4 Butanediol 20% Ion-exchanged water 70% Dye a, CI Desperse Yellow 42 (CI D
ISPER9E YELLOW 42) b, CI DISPERS BLUE 56 (CI DISPER
8E BLUR56) After filtration with a 1 micron filter, deaeration was performed under reduced pressure before use.

(3) Inkjet conditions Same as Example 1 (4) Fixation - Soaping Steaming treatment at 170°C for 7 minutes with superheated steam, then washing with water, and normal RC at 80°C.

The results of Example 16 and Comparative Example 12 are shown in Table 5.

(Note: Comparative Example 11 was untreated.) As shown in Table 5, the present invention is excellent in color development and bleeding even in polyester fibers.

Example 17 Comparative Example 13, which does not contain inorganic fine particles, and Example 17, which contains inorganic fine particles, were pretreated (1) using a fabric made of silk (habutae double stitch weight: 62 g/%) by the following method.

(1) Pretreatment of fabric (%) Comparative Example 13 Example 17 C, M, C11 Nipsil E220-10 Trisodium Phosphate 22 Pad (squeezing ratio 260%) - Dry. Next, an ink composition (2) shown below was prepared.

(2) Ink composition Dye 10% Ethylene glycol 20% Ion-exchanged water 70% Dyes include a, Cibacron Yellow 6G Liquid (Ciba
cron Yellow 6G Liquid) (manufactured by Ciba Geigy) b, Cibacron Turquoise GR Liquid (Ciba Geigy)
cron Turquoise GRLiquid) (
(manufactured by Civer Geigy) (3) Inkjet conditions Same as Example 1 (4) Fixation - Soaping Same as Example 1 The results of Example 17 and Comparative Examples 13 to 14 are shown in Table 6.

(Note: Comparative Example 13 was untreated) As shown in Table 6, the present invention is superior in color development and bleeding even on silk.

(Effects of the Invention) The inkjet fabric of the present invention has excellent coloring properties and good ink bleeding prevention properties, so that dark and delicate images can be obtained.

Furthermore, since the dyeing method of the present invention does not require any special additives in the ink components, it can be used for a wide range of natural fibers and synthetic fibers without impairing ejection performance.

Claims (4)

[Claims] (1) Average particle size is 0.2-10μ, sedimentation volume is 40m
0.5 to 10% by weight of porous bulky fine particles of l/5g or more
and a fabric for inkjet dyeing, characterized in that 0.1 to 5% by weight of a water-soluble polymer is added. (2) The fabric for inkjet dyeing according to claim (1), wherein the porous bulky fine particles have a pore volume of 1 ml/g or more. (3) The fabric for inkjet dyeing according to claim (1) or (2), wherein the porous bulky fine particles are hydrophilic porous silica. (4) inkjet dyeing using the dyeing fabric according to any one of claims (1) to (3), and then fixing;
A dyeing method characterized by soaping treatment.