TECHNICAL FIELD

The invention relates to the water-based and completely ecological printing pastes in which 3D effect may be provided by one-mold application, used in 3D printing (three dimensional printing effect) applied on the printed textiles, instead of non-ecological PVC-based printing pastes and acrylic resin-based ecological plastisol printing pastes which do not comprise PVC and phthalate.

STATE OF THE ART

A familiar or similar method has not been found in the market, used by both local and the foreign manufacturers. High density printing applications creates multi-layer printing layers with a number of intermediary drying processes and efforts are made for obtaining 3D effect, which causes additional costs for the company.

Textile printing (printing on textile parts) is the technique of coloring a certain region of the textile surface or abrading the colorant on said region. Specifically, it may be defined as a regional dying.

There are many printing techniques applied on the fabrics in order to obtain patterns with one or more colors. 3D effect printing method has a significant place among these technical applications. In general, when the textile printing types are grouped as follows, 3D printing technique may be considered among the special effect-printings.

Printing Types

1 - Direct printing

2- Discharge printing

3- Reserve printing 4- Transfer printing

5- Ink-jet printing

6- Special effects printing

• Metallic-Shimmer-Reflective printings

• Silvery printings

• High Density (3D) printings

• Puff printings

• Suede printings

• Gel printings

• Printings shining in the dark/under a specific light

• Printings changing color with light and heat

• Scented printings

• Devore printing application

• Cracking effect-printing applications

• Metallic high density printing applications

3D-effect printings have three dimensional appearances on the textile materials. Currently, the printing pastes providing said effect are the pastes consisting of chemical compositions not being water-based. When these pastes are separated into two groups, the first group consists of the resin-based PVC (polyvinyl chloride) being the first products known in the market. In these pastes that are not ecological and that are used less often, the plasticizers are used which plasticize the PVC resin and turning thereof into paste form. These plasticizers are non-ecological alkyl plasticizers such as Dibutyl Phthalate (DBP), Benzylbutyl Phthalate (BBP), Bis-(2-ethylhexyl) Phthalate (DEHP), Diisononyl Phthalate (DINP), Di-n-octyl Phthalate (DNOP), Diisodecyl Phthalate (DIDP), Diisobutyl phthalate (DIBP), and they are harmful to the human health and to the environmental ecology. Thus, they are not preferred for the textile applications any more. Regulations were published limiting and forbidding the use of internationally-accepted ecological PVC resin and plasticizers. REACH REGULATION XVII (RESTRICTIONS ON THE MANUFACTURE, PLACING ON THE MARKET AND USE OF CERTAIN DANGEROUS SUBSTANCES, MIXTURES AND ARTICLES) Article 51 and 52 describes the restrictions concerning the plasticizers mentioned above.

Oeko-Tex® Standard 100 threshold level for treated textiles(product class II) allows for 1000 mg/kg plasticizers mentioned above for the processed textiles. However, some major textile companies leading the sector narrowed all the restricted fields and chose to create standards by determining the rules. For example, a company restricted the use of the phthalates as 50 ppm in the declaration of CHEMICAL RESTRICTIONS 2018 - MANUFACTURING RESTRICTED SUBSTANCES LIST (MRSL) it published. Also, another company stated that it does not prefer PVC use in its MRSL declaration and prefers the total phthalate amount to be below 1000 ppm. Another company entirely prohibited the use of phthalates by its MRSL. Briefly, the PVC-based products of said first group providing 3D effect cause serious risks for both the human health and the environmental ecology in the production phase and during the application of the printing paste.

Other product group providing 3D effect consists of the acrylic resin-based ecological products. This second product group meets the ecological expectations of the sector. However, they also contain some physical challenges during usage. These types of products may have different physical properties in the market. For example, they have diversity from the ones with the harsh feel to the ones with the soft feel. Some of them have sticky touching, which is an undesirable situation. Unevenness (referred to as skull formation in the sector) on the printing lines of some of them is also a negative situation. Another problem is that the oil is expanded by presenting a wet appearance on the printing lines, which is also referred to as oil desorption and that it causes oil formation on the printing surface. All these problems are the physical disadvantages of this ecological product group. In these pastes, acrylic-derived powder resins are used and there are the types of thereof having different TG values. Along with the plasticizer chosen, the physical features of the product such as softness-hardness, clearness- opaqueness, and stickiness are determined. Main plasticizers used in these types of products may include Tri-cresyl phosphate, Acetyl tributyl citrate, Alkyl phenylsulfonate, Isopropylphenyl phosphate.

In the patent No. EP 1506263A1 , physical and chemical mechanism of the chemical content of this product group is disclosed. In other words, it is mainly disclosed that the plastisol textile paste of said invention does not contain PVC and phthalate in the chemical composition. It is emphasized that core-shell acrylic polymer content is used as the main ingredient of this paste which has an acrylic polymer core with 90-125 °C TG and an acrylic shell with a lower TG value. As the second ingredient, an organic phosphate plasticizer with a viscosity of 60-120 mm2/s, and as the third ingredient, a pigment composition for the colorant combination are disclosed. Physical features of the paste components are described in detail.

Another disadvantage of the 3D-effect pastes disclosed in detail above is that there is a need to clean the templates and other equipment used, after the printing by White spirit and cellulosic thinner, for both types of the application forms of the printing pastes. This results in the need for the protective devices and equipment suitable for the occupational health and safety. It is obvious that this presents additional costs to the company. However, it is one of the advantages of the product of the invention that it requires only water for cleaning the equipment after printing.

The manufacturers and users in the sector have demanded for the water-based types of the 3D-effect printing pastes for 25 years. It is known that some users in the sector, especially the printing professionals from the Far East performs the water-based application of the 3D effect by the method of applying molds of the present water-based elastic pastes one on the top of the other. Also, it is obvious that this will result in the disadvantages for the labor and the cost. DESCRIPTION OF THE INVENTION

Present invention relates to three dimensional printing method developed in order to prevent the disadvantages mentioned above and to supply the technical field with new advantages.

One object of the invention is to provide the ease of use, to meet the present needs, to present usage diversity, to produce Know-How knowledge and skills, and to improve the production process of the user. Also the invention may be utilized in the repeat printing applications and in the home textile products.

The product of the invention is developed upon the intensive demand in the sector and for eliminating the disadvantages of the present products, described in the state of the art. With the use of the product of the invention, the exposure to the chemicals being harmful to the health such as PVC and plasticizers and to the contaminated substances within the fixation steam arising after fixing the print will be avoided. Also, the usage challenges of the management conditions of the ecological acrylic pastes providing 3D effect will be removed; and the deformation problems will be eliminated which occur on the printed textile materials.

The product of the invention provides a significant alternative to the method not being water-based. When the PVC-based product is used among the present products of two different types as stated in the state of the art, the exposure to the chemicals such as PVC and phthalates that are particularly harmful to the human health will be avoided. To eliminate the personal exposure to the phthalates and PVC during the manufacture of these products provides advantages for the product of the invention. This provides advantages because it eliminates the negative situations about handling the dye after production. The invention is advantageous in that it will eliminate the use of petroleum naphtha which is utilized in cleaning the equipment used during the application of the dyes. It will provide economic advantages because the personal protective equipment for the naphtha usages will cause further costs for the company.

Also, the product of the invention provides advantage, compared to another method, ecological oil-based product usage because it utilizes petroleum naphtha in cleaning the equipment.

Considering the situation of the 3D printing pastes in the ready-made garment stage, the product subjected to the plastic printing feels like plastic when one touches the printed area. While washing and friction fastness of the plastic printing is good, dry-cleaning fastness thereof is relatively low. Thus, it is not a printing type suitable for dry-cleaning. However, when one touches the textile which was printed with the product of the invention, it provides a nice and more desirable feeling instead of the feeling of a plastic product. This is a motive to prefer for the user.

Considering the usage areas of the product of the invention, it will be used in the home textile products or in the sectors conducting decorative activities after a while, in addition to the present printed textile sector. Marketing strategies and the activities of the business development departments may constitute a basis for this aim.

Another issue to mention is that some features of the product of the invention is open to development over time. One of them may be the improvement of the fixing duration of the fabric to be treated with printing. In the present situation, fixing process is conducted two times and varies from 4 to 6 minutes in total. The height of the figure to be printed and the surface area of the pattern determines this duration. While the fixing duration is 4-5 min. for the patterns with low levels and small surface areas, it may be 5-6 min. for the patterns with high levels and high surface areas. The fixing durations may be shortened over time, after developing applications and new experiences to be gained. Moreover, there is the possibility to revise the paste based on the variability in the expectations of the users, while said paste becomes more common in the sector.

Drawings

The applications of the present invention summarized briefly above and addressed in more detail below may be understood by referring to the exemplary applications defined in the appended drawings of the invention. However, it has to be mentioned that the appended drawings illustrates the typical applications of this invention only, thus it cannot be assumed that they limit the scope of the invention, because it may allow for equally effective applications.

Figure 1 shows the stages of the method of the invention.

For the ease of understanding, identical reference numbers are used in the possible cases in order to define the identical members common in the figures. The figures have not been drawn to scale and they may be simplified for clarity. It has to be considered that the members and properties of an application may be included in the other applications usefully without any need for further explanation.

Description of the Details in Drawings

The equivalences of the reference numbers shown in the figures are presented below:

1 - Receiving,

2- Stirring in the mixer,

3- Dispersion,

4- Anti-foam-deaerating agent addition,

5- Thickener addition. DETAILED DESCRIPTION OF THE INVENTION

In this detailed description, preferred alternatives of the embodiment of the 3D printing method of the invention are described for better understanding the subject and without any limiting effect.

The product of the invention presents an alternative to the PVC-based ecological acrylic pastes that have been used in the 3D-effect method. It is an important factor that the paste combination of the invention has intensive solid substance content. The product of the invention requires water-based polyetheric polyurethane dispersion which has 60% solid substance among the main polymer materials, in order to have a good 3D effect. Also, in order to have an effective 3D effect on the fabric, the product of the invention requires polyethylene glycol with 1500 molecular weight among the main polymer materials. The product of the invention requires micro globules with acrylic copolymer structure expandable by heating, in order to support the solid substances. Also, the product of the invention requires the use of surfactants, anti-foam agent, and thickeners, in order to improve the working conditions of this main material. In this case, it comprises following chemicals:

Polyetheric-based polyurethane dispersion

Polyethylene glycol with 1500 molecular weight

Micro globules with an acrylic structure

Surfactant

Anti-foam-deaerating agents

Thickener with a polyacrylic ester structure

The paste of the invention requires the use of titanium dioxide as the filling powder, in order to obtain a 3D effect on the white patterns on the fabric. Thus, the invention comprises following chemicals:

Polyetheric-based polyurethane dispersion Polyethylene glycol with 1500 molecular weight

Micro globules with an acrylic structure

Surfactant

Anti-foam-deaerating agents

Titanium dioxide filling powder

Thickener with a polyacrylic ester structure

The product of the invention is water based, contrary to the conventional pastes and it presents the 3D effect on the fabric due to its intense solid substance.

Water-based 3D-effect paste of the invention consists of polyetheric-based polyurethane dispersion, polyethylene glycol with 1500 molecular weight, micro globules with an acrylic structure, surfactant, anti-foam-deaerating agents, titanium dioxide (in the case of white color application), and polyacrylic ester materials as the thickener.

The type with high solid substance of the polyurethane dispersion and the other polymeric substances of the formulation synergistically polymerized by being cured in a certain temperature. Thus, it enables 3D-effect formation by creating film layers on the fabric surface. Polyetheric based polyurethane dispersion is comprised in the proportion of 75-80% in the formulation of the invention.

Polyethylene glycol with 1500 molecular weight which is used in the water- based 3D-effect paste of the invention is a substance supporting the solid substance in the formulation and promoting the 3D effect due to its long polymer chain and it is between 5 to 10% g in the formulation of the invention.

Micro globules with a polyacrylic structure used in the water-based 3D-effect paste of the invention supports the solid substance within the formulation and prevents the 3D level reduction to occur due to the loss of the volatile component, by expanding during the printing fixation. It is used in the proportion of 2-3% in the formulation of the invention. Surfactants used in the water-based 3D-effect paste of the invention enables the homogeneous distribution of all raw materials used in the formulation and facilitates the use of the dye in the working environment. It is used in the proportion of 3-5% in the formulation of the invention.

Anti-foam - deaerating agent used in the water-based 3D-effect paste of the invention enables the elimination of the air bubbles created during the paste production phase and during usage. It is used in the proportion of 0.5-1 % in the formulation of the invention.

Titanium dioxide used in the water-based 3D-effect paste of the invention is utilized in the paste production phase in order to obtain printings with white 3D effects and it is contained 5-10% in the formulation of the invention.

Thickener with a polyacrylic ester structure used in the water-based 3D-effect paste of the invention enables the paste to be maintained in an appropriate viscosity, and it is contained 2% in the formulation of the invention.

The operation of preparing 3D-effect paste consists of the following steps:

• Firstly, polyurethane is introduced into the dispersion mixer. Then, other substances are added. Thus, receiving (1 ) step is completed.

• Stirring in the mixer (2) is maintained in order to obtain a homogeneous appearance.

• If the paste is produced in white color, the dispersion (3) of the titanium dioxide is carried out within the polyurethane dispersion, then other substances are added.

• Anti-foam - deaerating agent addition (4) step is carried out by introducing anti-foam - deaerating agent in a certain proportion.

• Thickener is added until an appropriate viscosity is obtained. Another issue to mention is that some features of the product of the invention is open to development over time. One of them may be the improvement of the fixing duration of the fabric to be treated with printing. In the present situation, fixing process is conducted two times and varies from 4 to 6 minutes in total. The height of the figure to be printed and the surface area of the pattern determines this duration. While the fixing duration is 4-5 min. for the patterns with low levels and small surface areas, it may be 5-6 min. for the patterns with high levels and high surface areas. The fixing durations may be shortened over time, after developing applications and new experiences to be gained. Moreover, there is the possibility to revise the paste based on the variability in the expectations of the users, while said paste becomes more common in the sector.