WO2021107253A1 - Natural fiber preprocessing agent for sublimation transfer - Google Patents

Natural fiber preprocessing agent for sublimation transfer Download PDF

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WO2021107253A1
WO2021107253A1 PCT/KR2019/018013 KR2019018013W WO2021107253A1 WO 2021107253 A1 WO2021107253 A1 WO 2021107253A1 KR 2019018013 W KR2019018013 W KR 2019018013W WO 2021107253 A1 WO2021107253 A1 WO 2021107253A1
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parts
weight
natural fiber
fabric
sublimation transfer
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PCT/KR2019/018013
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French (fr)
Korean (ko)
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허경
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(주)라쉬반코리아
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/003—Transfer printing

Definitions

  • the present invention relates to a natural fiber pretreatment agent for sublimation transfer that enables a fabric obtained by dyeing a disperse dye on a natural fiber fabric such as cotton, hemp, or wool by a sublimation transfer method to have excellent washing fastness.
  • Sublimation transfer is a printing method in which a pattern is printed on a transfer paper with transfer ink and then the pattern of the transfer paper is transferred to an object to be transferred. It is a printing method to express
  • This sublimation transfer is based on the sublimability of the disperse dye.
  • the affinity of the disperse dye and the subject is greater than the affinity of the disperse dye and the transfer paper, the dispersed dye is sublimated by heat and pressure and absorbed into the surface of the subject to transfer.
  • the transfer ink in the solid state is vaporized without going through a liquefaction process at a high temperature, and at the same time, micropores are generated on the surface (transfer layer) of the object to be transferred. As a result, the transfer ink in the gaseous state flows into the micropores of the transfer layer. When the surface temperature of the transfer object is lowered, the micropores of the transfer layer are closed again, and the vaporized transfer ink returns to a solid state.
  • the transfer ink is not printed on the surface of the object to be transferred, but the transfer ink is sucked into the transfer layer and integrated. Therefore, it is possible to form clear patterns with excellent fastness by sublimation transfer on synthetic fiber garments, but natural fibers such as cotton fabrics are made of cells, so the degree of expansion and contraction of the fibrous tissue due to heat is low and it is not compatible with disperse dyes.
  • the affinity is weak, so it is difficult to form a pattern by the sublimation transfer method, and the penetrating power into the natural fiber is weak, so the transferred pattern is not clear.
  • Korean Patent Application Laid-Open No. 10-1994-0000260 discloses a transfer paper for cotton fabric using a disperse dye, and a urethane resin layer in which a substrate, a disperse dye printing layer, a transparent organic wax layer, and a phosphorescent powder are mixed sequentially
  • the urethane resin layer is melted by heat transfer under pressure and the molten urethane resin penetrates into the cotton fabric to increase the expansion and contraction action of the cotton fabric like chemical fibers to facilitate penetration of the disperse dye into the transfer paper.
  • the transfer paper for cotton fabric has poor ventilation and stiffness of the cotton fabric, so that the fit and texture are reduced, and the advantages of natural fibers disappear, and by repeated washing There is a problem in that the resin coating film is cracked and the printed pattern is damaged.
  • Korean Patent Publication No. 10-0491408 discloses a transfer paper for cotton fabric comprising a sheet layer, a printing layer and a resin layer, and the resin layer contains ethylene vinyl acetate resin, stearic acid and wax as a lubricant. content is disclosed.
  • the transfer paper when the transfer paper is printed with a disperse dye ink and transferred to a cotton fabric, the dye dispersed in the resin layer is absorbed into the cotton fabric together with the composition constituting the resin layer, so that the surface touch is excellent, and the conventional urethane resin Since it does not create a film that forms on the surface of the cotton fabric, it is possible to obtain the effect of preventing cracking and lowering of the fit.
  • the resin layer composition is dissolved in an organic solvent of toluene, methyl ethyl ketone, or ethyl acetate, but these organic solvents have a problem that is harmful to the human body, and the ethylene vinyl acetate resin has poor adhesion with cotton fibers.
  • organic solvents have a problem that is harmful to the human body, and the ethylene vinyl acetate resin has poor adhesion with cotton fibers.
  • the color fastness of the dispersed dye is not sufficiently supported and the clarity of the transferred pattern is low due to insufficient washing fastness.
  • Korean Patent Publication No. 10-1373928 proposes a coating solution manufacturing technology that satisfies high resolution, texture, and wash fastness, and includes an ethylene vinyl acetate copolymer having a solid content of 60%; Any one or more acids selected from acetic acid, formic acid, citric acid, tartaric acid, and tannic acid; Any one or more resins selected from polyurethane, acrylate copolymer, and polyester copolymer having a solid content of 40%; silane (a homogeneous solution hydrolyzed by stirring an alkoxysilane) or silicone resin (a homogeneous solution emulsified by stirring alone or two or more silicone polyesters and silicone glycol copolymers); air freshener; It is composed of a thermal transfer coating composition comprising an antifoaming agent and an aqueous solution having a pH of 4 to 8.
  • the ethylene vinyl acetate copolymer of the present invention serves as an adhesive to promote the adhesion of the pigment deposited from the transfer paper to the surface of the cotton fabric during transfer, and the acid component maintains the pH of the aqueous solution at 4-8 to disperse the resin component in water. It improves the emulsion stability and dryness and solubility, and the resin component adjusts the curability appropriately to make the pattern printed on cotton fabric clear, and improves the fixability and dryness of ink using anionized dyes to increase durability, silane or Silicone resins are designed to impart flexibility and feel to the fibers due to their inherent resilience and lubricity properties.
  • the present invention was to solve the problems of the prior art by combining the properties of each component of the coating liquid composition, and the combination of these components shows a certain effect in improving the clarity, fastness, flexibility, feel, and ventilation of the printed pattern, but ethylene Vinyl acetate copolymer lacks adhesion to cotton fibers, so it lacks washing fastness.
  • anionized dyes dyed in acid or neutral pH 4-8 are acid dyes or direct dyes, and they dissolve well in water, so It has the disadvantage of low fastness.
  • the sublimation transfer technique it is preferable to use the sublimation transfer technique to express a pattern on an object having a shape and surface that is difficult to print with a general method such as clothing, leather, etc.
  • the dye must have sublimation property, but acid dyes or direct dyes Due to the lack of these properties, there is a limit in vividly expressing the pattern even when printed on a cotton fabric by the sublimation transfer method using the composition of the present invention.
  • the present invention is to solve the above problem, and provides a natural fiber pretreatment agent for sublimation transfer that allows the dyed pattern to be clearly colored and the washing fastness of the fabric is not deteriorated even when the disperse dye is dyed on natural fibers by the sublimation transfer method.
  • the present invention includes 100 parts by weight of water, 25 to 35 parts by weight of an acrylic resin, 5 to 10 parts by weight of a polyester resin, and 3 to 7 parts by weight of a urethane resin, wherein the urethane resin is an acrylic polyol and a silicone-based resin.
  • a natural fiber pretreatment for sublimation transfer prepared by neutralizing a polyol reacted with isocyanate with triethanolamine and then synthesizing with ethylenediamine to prepare an acrylic silicone urethane copolymer, and then adding polycarbodiimide.
  • the acrylic resin is preferably a water-dispersible acrylic resin polymerized from at least one monomer selected from the group consisting of isobutyl acrylate, methyl methacrylate, ethyl acrylate and 2-ethylhexyl methacrylate.
  • the polyester resin is preferably a water-dispersible polyester resin in which hydrogen of a polyester resin synthesized by esterification reaction of ethylene glycol and dimethyl terephthalate is substituted with a sodium sulfonate group.
  • the pretreatment agent is 0.2 to 0.5 parts by weight of a waterproofing enhancer based on 100 parts by weight of water, 0.5 to 2.0 parts by weight of microporous silica, 1-3 parts by weight of a thickener, 0.1 to 0.5 parts by weight of an antifoaming agent, 1 to 2 parts by weight of a coupling agent and at least one additive selected from the group consisting of 0.3 to 1.0 parts by weight of a UV stabilizer.
  • the natural fiber pretreatment agent for sublimation transfer enables the dyeing of vivid patterns on natural fiber fabrics that are difficult to sublimate and transfer disperse dyes, and has excellent washing fastness of the dyed fabrics. Since there is little residual amount, it does not adversely affect the human body.
  • 1 to 5 are test reports obtained by measuring the dyeing characteristics of cotton/wool knitted fabrics dyed by the sublimation transfer method after coating the pretreatment agent of the present invention to the Korea Apparel Testing & Research Institute.
  • sublimation transfer printing of synthetic fiber fabrics such as polyester uses disperse dyes
  • sublimation transfer printing of natural fiber fabrics such as cotton fabrics uses reactive dyes. It is sublimated and comes out of the transfer paper in a molecular state, and this temperature is higher than the softening point of the synthetic fiber polymer, so the polymer of the synthetic fiber becomes flexible and dispersed dye molecules penetrate between them and print. The dye molecules trapped between the polymers have color fastness to washing.
  • the present invention provides a pretreatment agent that can be dyed with a sublimation transfer technique using a disperse dye in natural fiber fabrics that are less harmful to the human body or leather that is difficult to express patterns with a general paper printing method, and the pretreatment agent of the present invention Before sublimation transfer of the disperse dye onto the natural fiber fabric (or leather), it is coated on the fabric in advance so that the disperse dye is firmly bound to the fabric so that the printed pattern has excellent color fastness and vivid color.
  • the natural fiber pretreatment agent for sublimation transfer of the present invention is 25 to 35 parts by weight of acrylic resin, 5 to 10 parts by weight of polyester resin, 3 to 7 parts by weight of urethane resin in 100 parts by weight of water. including parts by weight.
  • the acrylic resin is a polymer of acrylic acid, methacrylic acid, or its derivatives, and has strong adhesion to the natural fiber fabric, and then micropores are created by heat applied during transfer to introduce the sublimated disperse dye into the fabric. to be fixed on
  • the acrylic resin is flexible, it does not deteriorate the texture of the fabric and does not change color even when exposed to the outdoors, it is colorless and transparent and has high light transmittance, so that the dispersed dye transferred to the fabric can be clearly colored.
  • acrylic resins generally have a softer touch when coated as the glass transition temperature (Tg) is lower, but yellowing occurs during sunlight or hot pressing (180 ⁇ 220 °C).
  • isobutyl acrylate, methyl A water-dispersible acrylic resin polymerized from a monomer of methacrylate, ethyl acrylate, and 2-ethylhexyl methacrylate is used.
  • the acrylic resin is preferably contained in an amount of 25 to 35 parts by weight based on 100 parts by weight of water as a solvent in the pretreatment, and when it is less than 25 parts by weight, the binding power of the acrylic resin for binding the disperse dye to the fabric is insufficient, and the formation of micropores in the polymer is difficult. Insufficient, the color development is not clear, and if it exceeds 35 parts by weight, the flexibility and feel of the fabric are poor.
  • the polyester resin blocks ultraviolet rays to prevent the color from being discolored by sunlight, and thus serves to compensate for the low light fastness, which is a disadvantage of the sublimable disperse dye.
  • polyester resin used in the present invention hydrogen in a polyester-based resin synthesized by esterification reaction of ethylene glycol and dimethyl terephthalate is replaced with a sodium sulfonate group (-SO 3 Na).
  • An acidic polyester resin is used.
  • the sodium sulfonate group which is a functional group of the water-dispersible polyester resin, is dissociated in an aqueous solution to become an SO 3 2- anion, and it is dyed with a cation and an ionic bond in the dye to obtain a vivid color, and indirectly prevents yellowing caused by sunlight This improves the light fastness.
  • the acid radical water-dispersible polyester resin is preferably contained in 5 to 10 parts by weight based on 100 parts by weight of water as a solvent in the pretreatment, and if it is less than 5 parts by weight, the pattern formed on the fabric may be discolored over time, and 10 parts by weight If the amount is exceeded, there is a disadvantage that the color development of the fabric pattern is reduced.
  • the urethane resin is a polymer having a urethane bond (-NH ⁇ CO ⁇ O-) in the center constituting the main chain, and is generally obtained from a reaction between a compound containing a hydroxyl group and a compound having an isocyanate group, and the curability of the pretreatment composition to maintain the elasticity and elasticity of the fabric, excellent abrasion resistance, chemical resistance, solvent resistance, and oxygen stability, form a film on the fiber surface, and further fix the disperse dye bound to the acrylic resin Improves durability and wash fastness.
  • Acrylic polyurethane dispersion is preferable as the urethane resin, and the acrylic urethane resin has excellent weather resistance, gloss and color retention in addition to the properties of the urethane resin, so it improves the light fastness of the sublimated and transferred natural fiber fabric. effective.
  • an acrylic silicone polyurethane resin as the acrylic urethane resin in terms of improving the light fastness of the natural fiber fabric.
  • the acrylic silicone urethane resin is acrylic silicone urethane synthesized with ethylendiamine (EDA) after being neutralized with triethanolamine (TEA) in a prepolymer obtained by reacting acrylic polyol and silicone polyol with isocyanate. It can be prepared by obtaining a copolymer and adding polycarbodiimide as a crosslinking agent thereto to crosslink the acrylic-urethane block copolymer, and sublimation transfer printing is performed by adding a silicone polyol component to the acrylic urethane resin. This softens and increases water resistance, improving washing fastness.
  • EDA ethylendiamine
  • TEA triethanolamine
  • the urethane resin is preferably contained in 3 to 7 parts by weight based on 100 parts by weight of water, which is a solvent, of the pretreatment agent, and if it is less than 3 parts by weight, the wash fastness is low, so that the pattern formed on the fabric is easily discolored by repeated washing and exceeds 7 parts by weight If it does, there is a fear that the surface touch feeling of the fabric may be poor.
  • the natural fiber pretreatment agent for sublimation transfer of the present invention may further contain additives to improve color development, washing fastness, dyeing workability, etc., and as the additives, a water resistance enhancer, microporous silica, and a thickener , an antifoaming agent, a coupling agent, a UV stabilizer, and the like may be used.
  • the water resistance enhancer reacts with the functional group of the disperse dye that may remain on the sublimation transfer-printed fabric to improve the water resistance and washability of the fabric after the sublimation transfer operation, and boric acid is preferred as the water resistance enhancer, and a pretreatment agent It is more preferable to add 0.2 to 0.5 parts by weight based on 100 parts by weight of water.
  • microporous silica is added to improve the hiding power of the fabric to improve color and wash fastness after sublimation transfer, and it is preferable to use 0.5 to 2.0 parts by weight based on 100 parts by weight of water.
  • the thickener improves workability during sublimation transfer printing, and it is preferable to use at least one of an acrylic thickener and a urethane-based thickener, and more preferably use 1-3 parts by weight based on 100 parts by weight of water.
  • the antifoaming agent suppresses the generation of bubbles that may occur in the sublimation transfer printing process or improves workability by removing the bubbles that have already occurred, and it is preferable to use 0.1 to 0.5 parts by weight based on 100 parts by weight of water.
  • the coupling agent promotes the bonding between the pretreatment agent and the fabric and the bonding between the pretreatment agent composition components to prevent the pretreatment agent from being separated from the fabric or from raising the fabric during washing.
  • a coupling agent an epoxysilane-based coupling agent and an aminosilane-based coupling agent are used. It is preferable to use at least one of the coupling agents, and it is more preferable to use 1 to 2 parts by weight based on 100 parts by weight of water.
  • the UV stabilizer is a zinc oxide (ZnO)-based or titanium dioxide (TiO 2 )-based UV stabilizer, which has a different photoinitiation effect than a general UV stabilizer.
  • ZnO zinc oxide
  • TiO 2 titanium dioxide
  • the UV stabilizer When sublimation transfer-printed natural fiber fabric is exposed to sunlight, it promotes light initiation on the surface of the fabric and forms a thin UV-blocking film, thereby improving the transfer or discoloration of disperse dyes in sunlight, 0.3 to 1.0 parts by weight based on 100 parts by weight of water It is preferable to do
  • the natural fiber pretreatment agent for sublimation transfer of the present invention prepared as described above is an acrylic resin that is firmly bound to the natural fiber fabric and fixes the sublimated disperse dye by creating micropores by transfer heat, and is fixed to the acrylic resin by blocking ultraviolet rays.
  • Polyethylene terephthalate was obtained by polymerizing ethylene glycol and dimethyl terephthalate, and then hydrogen of the benzene ring of polyethylene terephthalate was replaced with a sodium sulfonate group to obtain a water-dispersible polyester resin.
  • triethanolamine was added to neutralize it and then reacted with ethylenediamine to prepare an acrylic silicone urethane copolymer, and polycarbodiimide was added thereto to prepare an acrylic silicone urethane resin did.
  • AA-960-60 manufactured by Aekyung Chemical Co., Ltd. was used as the acrylic polyol
  • polydimethylsiloxane (PDMS) was used as the silicone-based polyol.
  • DA-2035 manufactured by Daewon Polymer
  • BYK-012 manufactured by BYK
  • KBM-403 manufactured by Shin-Etsu
  • a zinc oxide UV stabilizer were water-dispersed ZnO.
  • the pretreatment agent-coated knitted fabric is heated and pressed for 15 seconds at a temperature of 200° C. and a pressure of 4 kg f /cm 2 to sublimate. transcription was printed.
  • washing fastness, sweat fastness, and water fastness were all excellent in grades 4 to 5, and the color fastness of the cotton fiber was slightly better than that of the wool fiber. It can be seen that the washing fastness of the transfer-printed natural fiber fabric after being treated with the pretreatment agent of the present invention is very good.
  • washing dimensional change rate was small at -5.0/-2.0 (wale direction/course direction), and it was good as a 4th grade (light surface purging and/or partially formed peel) in the peeling and purging tests, and the content of chemicals remaining in the fabric was also It can be confirmed that it is less than the standard value.
  • natural fibers such as cotton fibers do not transfer disperse dyes well, so washing fastness is poor and safety is a problem due to residual chemicals.
  • natural fiber fabrics treated with the pretreatment agent of the present invention are transferred with disperse dyes. It shows excellent washing fastness and safety even after printing.
  • Pretreatment ingredient ratio (g) dyes Purified water 2-ethylhexyl methacrylate Water-dispersible polyester resin Water-dispersible acrylic silicone urethane resin Additive Note 1)
  • Kinds color Example 2 1000 250 100 70 59 disperse dye black
  • acetate fiber Examples 2 to 5 (grade 3 to 4) / Comparative Example 1 (grade 2)
  • nylon fiber Examples 2 to 5 (grade 3 to 4) / Comparative Example 1 (grade 1 to 2) / Comparative Example 2 (Class 2)/Comparative Example 3 (Class 2-3)
  • Wool Fiber Examples 2-5 (Class 4-5)/Comparative Example 1 (Class 3)/Comparative Example 2 (Class 3-4)
  • Example showed the 4th grade, but Comparative Examples 2 and 3 were measured as 3rd to 4th grade, so it can be seen that the pretreatment of the present invention is effective in improving the light fastness of the cotton fiber.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

The present invention relates to a natural fiber preprocessing agent for sublimation transfer, for enabling a fabric to have excellent wash fastness, the fabric being a natural fiber fabric such as cotton, linen, and wool that has been dyed with a disperse dye via a sublimation transfer method. The natural fiber preprocessing agent for sublimation transfer, according to the present invention, enables dying of a clear and vivid pattern onto the natural fiber fabric difficult to have the disperse dye sublimation transferred thereto, enables the dyed fabric to have excellent wash fastness, and does not have a harmful effect on a human body as almost no chemical residue remains on the fabric after dying via sublimation transfer.

Description

승화전사용 천연섬유 전처리제Natural fiber pretreatment agent for sublimation transfer
본 발명은 면, 마, 모와 같은 천연섬유 원단에 분산염료를 승화전사 방식으로 염색한 원단이 우수한 세탁견뢰도를 가지도록 하는 승화전사용 천연섬유 전처리제에 관한 것이다.The present invention relates to a natural fiber pretreatment agent for sublimation transfer that enables a fabric obtained by dyeing a disperse dye on a natural fiber fabric such as cotton, hemp, or wool by a sublimation transfer method to have excellent washing fastness.
승화전사는 전사잉크로 전사지에 무늬를 프린트한 후 피전사체에 전사지의 무늬를 전사하는 방식의 인쇄방법으로서, 의류, 피혁 등과 같이 일반적인 지면 인쇄방법을 적용하기 어려운 형태와 표면을 갖는 피인쇄물에 무늬를 표현하기 위한 인쇄방법이다.Sublimation transfer is a printing method in which a pattern is printed on a transfer paper with transfer ink and then the pattern of the transfer paper is transferred to an object to be transferred. It is a printing method to express
이러한 승화전사는 분산염료의 승화성에 기초한 것으로서, 분산염료와 피전사체의 친화력이 분산염료와 전사지의 친화력보다 큰 경우 분산염료가 열과 압력에 의해 승화되어 피전사체의 표면으로 흡수되어 전사가 이루어진다.This sublimation transfer is based on the sublimability of the disperse dye. When the affinity of the disperse dye and the subject is greater than the affinity of the disperse dye and the transfer paper, the dispersed dye is sublimated by heat and pressure and absorbed into the surface of the subject to transfer.
고체상태의 전사잉크는 고온상태에서 액화과정을 거치지 않고 기화됨과 동시에 피전사체 표면(전사층)에 열에 의한 미세구멍이 발생하고 이에 따라 기체상태의 전사잉크가 전사층의 미세구멍으로 유입되며, 이후 피전사체의 표면온도가 낮아지면 전사층의 미세구멍이 다시 닫히면서 기화된 전사잉크는 다시 고체상태로 되돌아가게 된다.The transfer ink in the solid state is vaporized without going through a liquefaction process at a high temperature, and at the same time, micropores are generated on the surface (transfer layer) of the object to be transferred. As a result, the transfer ink in the gaseous state flows into the micropores of the transfer layer. When the surface temperature of the transfer object is lowered, the micropores of the transfer layer are closed again, and the vaporized transfer ink returns to a solid state.
즉, 피전사체의 표면에 전사잉크가 인쇄되는 것이 아니라 전사잉크가 전사층에 흡입되어 일체화되는 것인데, 합성섬유는 고분자 수지로 이루어져서 열에 의한 섬유조직의 수축팽창도가 크고 분산염료와의 친화력이 뛰어나기 때문에 합성섬유로 된 의류에는 승화전사에 의해 견뢰도가 우수한 무늬를 선명하게 형성할 수 있으나, 면직물과 같은 천연섬유는 세포(cell)로 이루어져서 열에 의한 섬유조직의 팽창수축도가 낮고 분산염료와의 친화력이 약하여 승화전사 방식으로 무늬를 형성하기 곤란하고 천연섬유로의 침투력이 약하여 전사된 무늬가 번지는 등 선명하지 못한 문제점이 있다.That is, the transfer ink is not printed on the surface of the object to be transferred, but the transfer ink is sucked into the transfer layer and integrated. Therefore, it is possible to form clear patterns with excellent fastness by sublimation transfer on synthetic fiber garments, but natural fibers such as cotton fabrics are made of cells, so the degree of expansion and contraction of the fibrous tissue due to heat is low and it is not compatible with disperse dyes. The affinity is weak, so it is difficult to form a pattern by the sublimation transfer method, and the penetrating power into the natural fiber is weak, so the transferred pattern is not clear.
그런데 합성섬유 원단은 천연섬유 원단에 비해 질감이나 흡습성, 통풍성 등이 낮은 단점이 있어서 우수한 질감과 통풍성을 갖는 천연섬유 원단에 분산염료를 이용한 승화전사 인쇄방법의 개발이 꾸준히 요구되어 왔으며, 이러한 방법으로서 천연섬유 원단의 전사부위에 합성섬유와 같은 고분자 수지를 코팅하여 분산염료와의 친화력이 높은 코팅막을 형성한 후 코팅막에 승화전사방법으로 무늬를 전사하는 방법이 제안되었다.However, synthetic fiber fabrics have disadvantages such as lower texture, hygroscopicity, and breathability compared to natural fiber fabrics, so the development of a sublimation transfer printing method using disperse dyes on natural fiber fabrics with excellent texture and breathability has been continuously required. A method of transferring patterns by sublimation transfer to the coating film has been proposed after forming a coating film with high affinity with a disperse dye by coating a polymer resin such as synthetic fiber on the transfer part of the natural fiber fabric.
예를 들어, 한국공개특허공보 제10-1994-0000260호에는 분산염료를 이용한 면직물용 전사지가 제시되어 있는데, 기재, 분산염료 인쇄층, 투명유기질 왁스층 및 축광분말이 혼합된 우레탄수지층이 순차적으로 적층된 전사지를 구성함으로써, 가압 열전사에 의해 우레탄수지층이 용융되고 용융 우레탄수지가 면직물에 침투하여 면직물의 성질을 화학섬유와 같이 팽창수축작용을 증가시켜 분산염료의 침투를 용이하게 함으로 전사지에 전사된 상태 그대로 면직물에 전사시킬 수 있으며, 분산염료인쇄층과 우레탄수지층 사이의 투명유기질 왁스층은 우레탄수지층이 분사염료 인쇄층에 접촉됐을 때 발생하는 염료의 번짐을 막아주어 전사된 무늬의 선명도를 높이도록 설계되었다.For example, Korean Patent Application Laid-Open No. 10-1994-0000260 discloses a transfer paper for cotton fabric using a disperse dye, and a urethane resin layer in which a substrate, a disperse dye printing layer, a transparent organic wax layer, and a phosphorescent powder are mixed sequentially By composing the laminated transfer paper, the urethane resin layer is melted by heat transfer under pressure and the molten urethane resin penetrates into the cotton fabric to increase the expansion and contraction action of the cotton fabric like chemical fibers to facilitate penetration of the disperse dye into the transfer paper. It can be transferred to cotton fabric as it is in the transferred state, and the transparent organic wax layer between the disperse dye printing layer and the urethane resin layer prevents the dye from spreading when the urethane resin layer comes into contact with the spray dye printing layer. designed to increase
그러나 상기 면직물용 전사지는 우레탄수지층이 면직물에 완전히 침투하지 못하고 면직물의 표면에 막을 형성하기 때문에 면직물의 통풍이 불량하고 뻣뻣해져서 착용감과 질감이 저하되어 천연섬유의 장점이 사라지며, 반복 세탁에 의해 수지코팅막이 갈라져서 인쇄된 무늬가 손상되는 등의 문제점이 있다.However, since the urethane resin layer does not completely penetrate into the cotton fabric and forms a film on the surface of the cotton fabric, the transfer paper for cotton fabric has poor ventilation and stiffness of the cotton fabric, so that the fit and texture are reduced, and the advantages of natural fibers disappear, and by repeated washing There is a problem in that the resin coating film is cracked and the printed pattern is damaged.
이러한 문제를 해결하기 위하여, 한국등록특허공보 제10-0491408호에는 시트층, 인쇄층 및 수지층으로 구성되고 상기 수지층이 에틸렌비닐아세테이트 수지, 스테아린산 및 윤활제로서 왁스를 함유하는 면직물용 전사지에 관한 내용이 개시되어 있다.In order to solve this problem, Korean Patent Publication No. 10-0491408 discloses a transfer paper for cotton fabric comprising a sheet layer, a printing layer and a resin layer, and the resin layer contains ethylene vinyl acetate resin, stearic acid and wax as a lubricant. content is disclosed.
상기 공보에 따르면, 상기 전사지에 분산염료 잉크로 인쇄하여 면직물에 전사할 경우 수지층에 분산된 염료가 수지층을 구성하는 조성물과 함께 모두 면직물에 스며들어서 표면 터치감이 우수하고, 종래의 우레탄수지가 면직물 표면에 형성하는 막을 생성하지 않아서 갈라짐 현상과 착용감 저하현상이 방지되는 효과를 얻을 수 있다.According to the publication, when the transfer paper is printed with a disperse dye ink and transferred to a cotton fabric, the dye dispersed in the resin layer is absorbed into the cotton fabric together with the composition constituting the resin layer, so that the surface touch is excellent, and the conventional urethane resin Since it does not create a film that forms on the surface of the cotton fabric, it is possible to obtain the effect of preventing cracking and lowering of the fit.
그러나 상기 전사지에 수지층을 형성하기 위해서 수지층 조성물을 톨루엔, 메틸에틸케톤 또는 에틸아세테이트의 유기용매로 용해하는데 이러한 유기용매는 인체에 유해한 문제점이 있으며, 에틸렌비닐아세테이트 수지는 면 섬유와의 접착력이 부족하여 세탁견뢰도가 충분치 못하고 분산염료의 발색성을 충분히 받쳐주지 못하여 전사된 무늬의 선명도가 낮은 단점이 있다.However, in order to form a resin layer on the transfer paper, the resin layer composition is dissolved in an organic solvent of toluene, methyl ethyl ketone, or ethyl acetate, but these organic solvents have a problem that is harmful to the human body, and the ethylene vinyl acetate resin has poor adhesion with cotton fibers. There is a disadvantage in that the color fastness of the dispersed dye is not sufficiently supported and the clarity of the transferred pattern is low due to insufficient washing fastness.
이에, 한국등록특허공보 제10-1373928호에서는 고해상도와 질감 및 세탁견뢰도를 만족하는 코팅액 제조기술을 제시하고 있으며, 고형분 함량이 60 %인 에틸렌비닐아세테이트 공중합체; 아세트산, 개미산, 구연산, 주석산, 탄닌산 중에서 선택되는 어느 1종 이상의 산; 고형분 함량이 40 %인 폴리우레탄, 아크릴레이트 공중합체, 폴리에스테르 공중합체 중에서 선택되는 어느 1종 이상의 수지; 실란(알콕시실란을 교반하여 가수분해된 균일계 용액) 또는 실리콘 수지(실리콘 폴리에스테르, 실리콘 글리콜 공중합체를 단독 또는 2종 이상 교반하여 유화된 균일계 용액); 방향제; 소포제;를 포함하고 pH 4~8의 수용액으로 이루어진 열전사 코팅액 조성물로 구성된다.Accordingly, Korean Patent Publication No. 10-1373928 proposes a coating solution manufacturing technology that satisfies high resolution, texture, and wash fastness, and includes an ethylene vinyl acetate copolymer having a solid content of 60%; Any one or more acids selected from acetic acid, formic acid, citric acid, tartaric acid, and tannic acid; Any one or more resins selected from polyurethane, acrylate copolymer, and polyester copolymer having a solid content of 40%; silane (a homogeneous solution hydrolyzed by stirring an alkoxysilane) or silicone resin (a homogeneous solution emulsified by stirring alone or two or more silicone polyesters and silicone glycol copolymers); air freshener; It is composed of a thermal transfer coating composition comprising an antifoaming agent and an aqueous solution having a pH of 4 to 8.
상기 발명의 에틸렌비닐아세테이트 공중합체는 전사시 면직물 등의 표면에 전사지로부터 침착되는 색소의 부착을 도모하기 위한 접착제 역할을 하고, 산 성분은 수용액의 pH를 4~8로 유지시켜 수지성분의 수분산성과 유화안정성 및 건조성과 용해성을 향상시키며, 수지 성분은 경화성을 적절하게 조정하여 면직물에 인쇄되는 무늬를 선명하게 하고 음이온화된 염료를 사용한 잉크의 정착성과 건조성을 향상시켜 내구성을 증가시키며, 실란 또는 실리콘 수지는 실리콘오일 고유의 반발성, 윤활성과 같은 특성으로 인하여 섬유에 유연성과 촉감을 부여하도록 하였다.The ethylene vinyl acetate copolymer of the present invention serves as an adhesive to promote the adhesion of the pigment deposited from the transfer paper to the surface of the cotton fabric during transfer, and the acid component maintains the pH of the aqueous solution at 4-8 to disperse the resin component in water. It improves the emulsion stability and dryness and solubility, and the resin component adjusts the curability appropriately to make the pattern printed on cotton fabric clear, and improves the fixability and dryness of ink using anionized dyes to increase durability, silane or Silicone resins are designed to impart flexibility and feel to the fibers due to their inherent resilience and lubricity properties.
상기 발명은 코팅액 조성물의 각 성분이 가진 특성을 조합하여 종래의 문제들을 해소하고자 하였고 이들 성분조합으로 인해 인쇄된 무늬의 선명성, 견뢰도, 유연성, 촉감, 통풍성 향상에 어느 정도 효과를 나타내기는 하나, 에틸렌비닐아세테이트 공중합체는 면 섬유와의 접착력이 부족하여 세탁견뢰도가 부족하고 상기와 같이 pH 4~8의 산성이나 중성에서 염색되는 음이온화된 염료는 산성염료나 직접염료인데 이들은 물에 잘 용해되므로 습윤견뢰도가 낮은 단점이 있다.The present invention was to solve the problems of the prior art by combining the properties of each component of the coating liquid composition, and the combination of these components shows a certain effect in improving the clarity, fastness, flexibility, feel, and ventilation of the printed pattern, but ethylene Vinyl acetate copolymer lacks adhesion to cotton fibers, so it lacks washing fastness. As described above, anionized dyes dyed in acid or neutral pH 4-8 are acid dyes or direct dyes, and they dissolve well in water, so It has the disadvantage of low fastness.
또한, 의류, 피혁 등과 같이 일반적인 방법을 인쇄하기 어려운 형태와 표면을 갖는 피인쇄물에 무늬를 표현하기 위해서는 승화전사 기법을 이용하는 것이 바람직하고 이를 위해서 염료가 승화성을 가져야 하나, 산성염료나 직접염료는 이러한 특성이 부족하여 상기 발명의 조성물을 이용하여 면직물에 승화전사 방법으로 인쇄하여도 무늬를 선명하게 표현하는 데에는 한계가 있다.In addition, it is preferable to use the sublimation transfer technique to express a pattern on an object having a shape and surface that is difficult to print with a general method such as clothing, leather, etc. For this purpose, the dye must have sublimation property, but acid dyes or direct dyes Due to the lack of these properties, there is a limit in vividly expressing the pattern even when printed on a cotton fabric by the sublimation transfer method using the composition of the present invention.
본 발명은 상기의 문제를 해결하기 위한 것으로서, 천연섬유에 분산염료를 승화전사 방식으로 염색하여도 염색된 무늬가 선명히 발색되고 원단의 세탁견뢰도가 저하되지 않도록 하는 승화전사용 천연섬유 전처리제를 제공하는 것이다.The present invention is to solve the above problem, and provides a natural fiber pretreatment agent for sublimation transfer that allows the dyed pattern to be clearly colored and the washing fastness of the fabric is not deteriorated even when the disperse dye is dyed on natural fibers by the sublimation transfer method. will do
상기 과제를 해결하기 위하여, 본 발명은 물 100 중량부, 아크릴 수지 25~35 중량부, 폴리에스테르 수지 5~10 중량부 및 우레탄 수지 3~7 중량부를 포함하며, 상기 우레탄 수지는 아크릴계 폴리올 및 실리콘계 폴리올을 이소시아네이트와 반응시킨 프리폴리머에 트리에탄올아민으로 중화시킨 후 에틸렌디아민과 합성하여 아크릴 실리콘 우레탄 공중합체를 제조한 후 폴리카르보디이미드를 첨가하여 제조되는 승화전사용 천연섬유 전처리제를 제공한다.In order to solve the above problems, the present invention includes 100 parts by weight of water, 25 to 35 parts by weight of an acrylic resin, 5 to 10 parts by weight of a polyester resin, and 3 to 7 parts by weight of a urethane resin, wherein the urethane resin is an acrylic polyol and a silicone-based resin. Provided is a natural fiber pretreatment for sublimation transfer prepared by neutralizing a polyol reacted with isocyanate with triethanolamine and then synthesizing with ethylenediamine to prepare an acrylic silicone urethane copolymer, and then adding polycarbodiimide.
이때, 상기 아크릴 수지는 이소부틸아크릴레이트, 메틸 메타크릴레이트, 에틸아크릴레이트 및 2-에틸헥실메타크릴레이트로 이루어진 군 중에서 선택되는 적어도 어느 하나의 모노머로부터 중합된 수분산성 아크릴 수지인 것이 바람직하다.In this case, the acrylic resin is preferably a water-dispersible acrylic resin polymerized from at least one monomer selected from the group consisting of isobutyl acrylate, methyl methacrylate, ethyl acrylate and 2-ethylhexyl methacrylate.
또한, 상기 폴리에스테르 수지는 에틸렌글리콜과 디메틸테레프탈레이트를 에스테르화 반응시켜 합성된 폴리에스테르 수지의 수소를 술폰산나트륨기로 치환한 수분산성 폴리에스테르 수지인 이 바람직하다.In addition, the polyester resin is preferably a water-dispersible polyester resin in which hydrogen of a polyester resin synthesized by esterification reaction of ethylene glycol and dimethyl terephthalate is substituted with a sodium sulfonate group.
또한, 상기 전처리제는 물 100 중량부 기준 내수화 증진제 0.2~0.5 중량부, 미세다공성 실리카 0.5~2.0 중량부, 증점제 1-3 중량부, 소포제 0.1~0.5 중량부, 커플링제 1~2 중량부 및 자외선 안정제 0.3~1.0 중량부로 이루어진 군 중에서 선택되는 적어도 어느 하나의 첨가제를 더 포함하는 이 바람직하다.In addition, the pretreatment agent is 0.2 to 0.5 parts by weight of a waterproofing enhancer based on 100 parts by weight of water, 0.5 to 2.0 parts by weight of microporous silica, 1-3 parts by weight of a thickener, 0.1 to 0.5 parts by weight of an antifoaming agent, 1 to 2 parts by weight of a coupling agent and at least one additive selected from the group consisting of 0.3 to 1.0 parts by weight of a UV stabilizer.
본 발명에 따른 승화전사용 천연섬유 전처리제는 분산염료의 승화전사가 어려운 천연섬유 원단에 선명한 무늬의 염색을 가능하게 하고 염색된 원단의 세탁견뢰도가 우수하며, 승화전사 염색 후 원단에 남는 약품의 잔류량이 거의 없어서 인체에 악영향을 끼치지 않는다.The natural fiber pretreatment agent for sublimation transfer according to the present invention enables the dyeing of vivid patterns on natural fiber fabrics that are difficult to sublimate and transfer disperse dyes, and has excellent washing fastness of the dyed fabrics. Since there is little residual amount, it does not adversely affect the human body.
도 1 내지 도 5는 본 발명의 전처리제를 코팅한 후 승화전사 방법으로 염색한 면/모 편물을 한국의류시험연구원에 의뢰하여 염색특성을 측정한 시험성적서이다.1 to 5 are test reports obtained by measuring the dyeing characteristics of cotton/wool knitted fabrics dyed by the sublimation transfer method after coating the pretreatment agent of the present invention to the Korea Apparel Testing & Research Institute.
통상, 폴리에스테르와 같은 합성섬유 원단의 승화전사 날염은 분산염료를 이용하고 면직물과 같은 천연섬유 원단의 승화전사 날염은 반응성 염료를 이용하여 왔는데, 이는 승화형 분산염료는 전사과정의 160 ℃ 이상의 열에 의해 승화되어 분자상태로 전사지로부터 나오고 이 온도는 합성섬유 고분자의 연화점 이상의 온도이므로 합성섬유의 고분자가 유연해져 그 사이로 분산염료 분자가 침투하여 날염되며, 전사가 완료된 후 열을 제거하여 온도가 낮아지면 고분자 사이에 갇힌 염료분자들이 세탁견뢰도를 가지면서 색상을 구현하게 된다.In general, sublimation transfer printing of synthetic fiber fabrics such as polyester uses disperse dyes, and sublimation transfer printing of natural fiber fabrics such as cotton fabrics uses reactive dyes. It is sublimated and comes out of the transfer paper in a molecular state, and this temperature is higher than the softening point of the synthetic fiber polymer, so the polymer of the synthetic fiber becomes flexible and dispersed dye molecules penetrate between them and print. The dye molecules trapped between the polymers have color fastness to washing.
그러나 면섬유와 같은 천연섬유는 고온의 상태에서도 분산염료 분자가 침투할 수 있는 공간이 형성되지 않아서 승화된 분산염료의 전사가 잘 이루어지지 않으며, 이에 따라 천연섬유 원단에 승화전사 날염하기 위해서는 천연섬유와 공유결합하여 결착되는 반응성 염료를 사용하는 것이 일반적이나 분산염료와 같은 다양한 색상을 표현하는데 제약이 있고 분산염료에 비하여 가격이 고가이다.However, natural fibers such as cotton fibers do not form a space for dispersed dye molecules to penetrate even at high temperatures, so the transfer of sublimated disperse dyes is difficult. It is common to use reactive dyes that are bound by covalent bonding, but there is a limitation in expressing various colors such as dispersed dyes, and the price is higher than that of dispersed dyes.
이에, 본 발명에서는 인체에 해가 적은 천연섬유 원단이나 일반적인 지면 인쇄방법으로 무늬를 표현하기 어려운 피혁에 분산염료를 사용하여 승화전사 기법으로 염색할 수 있는 전처리제를 제공하며, 본 발명의 전처리제는 천연섬유 원단(또는 피혁)에 분산염료를 승화전사하기 전에 미리 원단에 코팅처리됨으로써 분산염료가 원단에 견고하게 결착되도록 하여 인쇄된 무늬의 견뢰도가 우수하면서 선명하게 발색되도록 한다.Accordingly, the present invention provides a pretreatment agent that can be dyed with a sublimation transfer technique using a disperse dye in natural fiber fabrics that are less harmful to the human body or leather that is difficult to express patterns with a general paper printing method, and the pretreatment agent of the present invention Before sublimation transfer of the disperse dye onto the natural fiber fabric (or leather), it is coated on the fabric in advance so that the disperse dye is firmly bound to the fabric so that the printed pattern has excellent color fastness and vivid color.
본 발명의 승화전사용 천연섬유 전처리제는 물 100 중량부에 아크릴 수지(acrylic resin) 25~35 중량부, 폴리에스테르 수지(polyester resin) 5~10 중량부, 우레탄 수지(urethane resin) 3~7 중량부를 포함한다.The natural fiber pretreatment agent for sublimation transfer of the present invention is 25 to 35 parts by weight of acrylic resin, 5 to 10 parts by weight of polyester resin, 3 to 7 parts by weight of urethane resin in 100 parts by weight of water. including parts by weight.
상기 아크릴 수지는 아크릴산이나 메타크릴산 또는 그 유도체의 중합체로서, 부착성이 강하여 천연섬유 원단에 견고히 결착된 후 전사시 가해지는 열에 의해 미세구멍이 생성되어 승화된 분산염료를 유입함으로써 분산염료가 원단에 고정되도록 한다.The acrylic resin is a polymer of acrylic acid, methacrylic acid, or its derivatives, and has strong adhesion to the natural fiber fabric, and then micropores are created by heat applied during transfer to introduce the sublimated disperse dye into the fabric. to be fixed on
또한, 아크릴 수지는 유연하여 원단의 질감을 저하시키지 않고 옥외에 노출되어도 변색되지 않으며, 무색·투명하고 광선의 투과율이 높아서 원단에 전사된 분산염료가 선명하게 발색될 수 있다.In addition, since the acrylic resin is flexible, it does not deteriorate the texture of the fabric and does not change color even when exposed to the outdoors, it is colorless and transparent and has high light transmittance, so that the dispersed dye transferred to the fabric can be clearly colored.
그런데 아크릴 수지는 일반적으로 유리전이온도(glass transition temperature, Tg)가 낮을수록 코팅시 촉감이 부드러우나 일광이나 열프레스 작업(180~220 ℃)시 황변현상이 발생한다.However, acrylic resins generally have a softer touch when coated as the glass transition temperature (Tg) is lower, but yellowing occurs during sunlight or hot pressing (180~220 ℃).
따라서 전사 대상물인 천연섬유 원단의 부드러운 촉감과 더불어 일광견뢰도를 향상시키기 위하여 유리전이온도가 낮으면서 황변현상의 발생을 억제할 필요가 있으며, 이를 위하여 본 발명에서는 이소부틸아크릴레이트(isobutyl acrylate), 메틸 메타크릴레이트(methyl methacrylate), 에틸아크릴레이트(ethyl acrylate), 2-에틸헥실메타크릴레이트(2-ethylhexyl methacrylate)의 모노머(monomer)로부터 중합된 수분산성 아크릴 수지를 사용한다.Therefore, it is necessary to suppress the occurrence of yellowing while having a low glass transition temperature in order to improve the light fastness as well as the soft feel of the natural fiber fabric, which is the transfer object. To this end, in the present invention, isobutyl acrylate, methyl A water-dispersible acrylic resin polymerized from a monomer of methacrylate, ethyl acrylate, and 2-ethylhexyl methacrylate is used.
상기 아크릴 수지는 전처리제 중 용매인 물 100 중량부 기준 25~35 중량부 함유되는 것이 바람직하며, 25 중량부 미만이면 분산염료를 원단에 결착시키는 아크릴 수지의 결착력이 부족하고 고분자의 미세구멍 생성이 부족하여 발색이 선명하지 못하며, 35 중량부를 초과하면 원단의 유연성과 촉감이 불량해진다.The acrylic resin is preferably contained in an amount of 25 to 35 parts by weight based on 100 parts by weight of water as a solvent in the pretreatment, and when it is less than 25 parts by weight, the binding power of the acrylic resin for binding the disperse dye to the fabric is insufficient, and the formation of micropores in the polymer is difficult. Insufficient, the color development is not clear, and if it exceeds 35 parts by weight, the flexibility and feel of the fabric are poor.
상기 폴리에스테르 수지는 자외선을 차단하여 발색된 색상이 일광에 의해 탈색되는 현상을 방지하므로 승화성 분산염료의 단점인 낮은 일광견뢰도를 보완하는 역할을 수행한다.The polyester resin blocks ultraviolet rays to prevent the color from being discolored by sunlight, and thus serves to compensate for the low light fastness, which is a disadvantage of the sublimable disperse dye.
본 발명에서 사용되는 폴리에스테르 수지로서 에틸렌글리콜(ethylene glycol)과 디메틸테레프탈레이트(dimethyl terephthalate)를 에스테르화 반응시켜 합성된 폴리에스테르계 수지의 수소를 술폰산나트륨기(-SO3Na)로 치환한 수분산성 폴리에스테르 수지를 사용한다.As a polyester resin used in the present invention, hydrogen in a polyester-based resin synthesized by esterification reaction of ethylene glycol and dimethyl terephthalate is replaced with a sodium sulfonate group (-SO 3 Na). An acidic polyester resin is used.
상기 수분산성 폴리에스테르 수지의 작용기인 술폰산나트륨기는 수용액 내에서 해리되어 SO3 2- 음이온으로 되며, 염료 중의 양이온과 이온결합으로 염착되어 선명한 색상을 얻을 수 있으며, 일광에 의한 황변현상을 간접적으로 방지하여 일광견뢰도를 향상시킨다.The sodium sulfonate group, which is a functional group of the water-dispersible polyester resin, is dissociated in an aqueous solution to become an SO 3 2- anion, and it is dyed with a cation and an ionic bond in the dye to obtain a vivid color, and indirectly prevents yellowing caused by sunlight This improves the light fastness.
산기 수분산성 폴리에스테르 수지는 전처리제 중 용매인 물 100 중량부 기준 5~10 중량부 함유되는 것이 바람직하며, 5 중량부 미만이면 원단에 형성된 무늬가 시간이 지남에 따라 변색될 우려가 있고 10 중량부를 초과하면 원단 무늬의 발색도가 저하되는 단점이 있다.The acid radical water-dispersible polyester resin is preferably contained in 5 to 10 parts by weight based on 100 parts by weight of water as a solvent in the pretreatment, and if it is less than 5 parts by weight, the pattern formed on the fabric may be discolored over time, and 10 parts by weight If the amount is exceeded, there is a disadvantage that the color development of the fabric pattern is reduced.
상기 우레탄 수지는 주사슬을 구성하는 중심부에 우레탄 결합(-NH·CO·O-)을 가지는 중합체로서 일반적으로 수산기를 함유하는 화합물과 이소시아네이트기를 가지는 화합물과의 반응 등에서 얻고 있으며, 전처리제 조성물의 경화성을 조정하여 원단의 신축성과 탄력성을 유지하고 내마모성, 내약품성, 내용제성, 산소에 대한 안정성이 우수하며, 섬유표면에 피막을 형성하고 상기 아크릴 수지와 결착된 분산염료를 더욱 고정하여 전사된 무늬의 내구성과 세탁견뢰도를 향상시킨다.The urethane resin is a polymer having a urethane bond (-NH · CO · O-) in the center constituting the main chain, and is generally obtained from a reaction between a compound containing a hydroxyl group and a compound having an isocyanate group, and the curability of the pretreatment composition to maintain the elasticity and elasticity of the fabric, excellent abrasion resistance, chemical resistance, solvent resistance, and oxygen stability, form a film on the fiber surface, and further fix the disperse dye bound to the acrylic resin Improves durability and wash fastness.
상기 우레탄 수지로서 아크릴 우레탄 수지(acrylic polyurethane dispersion, AUD)가 바람직하며, 아크릴 우레탄 수지는 상기 우레탄 수지의 특성에 더하여 내후성, 광택 및 색상 유지율이 우수하므로 승화전사된 천연섬유 원단의 일광견뢰도를 향상시키는데 효과적이다.Acrylic polyurethane dispersion (AUD) is preferable as the urethane resin, and the acrylic urethane resin has excellent weather resistance, gloss and color retention in addition to the properties of the urethane resin, so it improves the light fastness of the sublimated and transferred natural fiber fabric. effective.
더욱더, 상기 아크릴 우레탄 수지로서 아크릴 실리콘 우레탄 수지(acrylic silicone polyurethane resin)를 사용하는 것이 천연섬유 원단의 일광견뢰도를 향상시키는 점에서 좀 더 바람직하다.Furthermore, it is more preferable to use an acrylic silicone polyurethane resin as the acrylic urethane resin in terms of improving the light fastness of the natural fiber fabric.
상기 아크릴 실리콘 우레탄 수지는 아크릴계 폴리올 및 실리콘계 폴리올을 이소시아네이트(isocyanate)와 반응시킨 프리폴리머(prepolymer)에 트리에탄올아민(triethanolamine, TEA)으로 중화공정을 거친 후 에틸렌디아민(ethylendiamine, EDA)과 합성한 아크릴 실리콘 우레탄 공중합체를 얻고 여기에 가교제로서 폴리카르보디이미드(polycarbodiimide)를 첨가하여 아크릴-우레탄 블록공중합체를 가교시키는 방법으로 제조될 수 있으며, 아크릴 우레탄 수지에 실리콘 폴리올 성분이 첨가됨으로 인하여 승화전사 날염된 원단이 부드러워지고 내수성이 증가하여 세탁견뢰도가 향상된다.The acrylic silicone urethane resin is acrylic silicone urethane synthesized with ethylendiamine (EDA) after being neutralized with triethanolamine (TEA) in a prepolymer obtained by reacting acrylic polyol and silicone polyol with isocyanate. It can be prepared by obtaining a copolymer and adding polycarbodiimide as a crosslinking agent thereto to crosslink the acrylic-urethane block copolymer, and sublimation transfer printing is performed by adding a silicone polyol component to the acrylic urethane resin. This softens and increases water resistance, improving washing fastness.
상기 우레탄 수지는 전처리제 중 용매인 물 100 중량부 기준 3~7 중량부 함유되는 것이 바람직하며, 3 중량부 미만이면 세탁견뢰도가 낮아서 원단에 형성된 무늬가 반복세탁에 의해 탈색되기 쉽고 7 중량부를 초과하면 원단의 표면 터치감이 불량해질 우려가 있다.The urethane resin is preferably contained in 3 to 7 parts by weight based on 100 parts by weight of water, which is a solvent, of the pretreatment agent, and if it is less than 3 parts by weight, the wash fastness is low, so that the pattern formed on the fabric is easily discolored by repeated washing and exceeds 7 parts by weight If it does, there is a fear that the surface touch feeling of the fabric may be poor.
또한, 본 발명의 승화전사용 천연섬유 전처리제는 발색, 세탁견뢰도, 염색작업성 등을 향상시키기 위하여 첨가제를 더 혼합할 수 있으며, 상기 첨가제로서 내수화 증진제, 미세다공성 실리카(microporous silica), 증점제, 소포제, 커플링제, 자외선 안정제 등이 사용될 수 있다.In addition, the natural fiber pretreatment agent for sublimation transfer of the present invention may further contain additives to improve color development, washing fastness, dyeing workability, etc., and as the additives, a water resistance enhancer, microporous silica, and a thickener , an antifoaming agent, a coupling agent, a UV stabilizer, and the like may be used.
상기 내수화 증진제는 승화전사 날염된 원단에 잔류할 수 있는 분산염료의 관능기와 반응하여 승화전사 작업 후 원단의 내수성 및 세탁성을 개선하며, 내수화 증진제로서 붕산(boric acid)이 바람직하고 전처리제의 물 100 중량부 기준 0.2~0.5 중량부 첨가되는 것이 더욱 바람직하다.The water resistance enhancer reacts with the functional group of the disperse dye that may remain on the sublimation transfer-printed fabric to improve the water resistance and washability of the fabric after the sublimation transfer operation, and boric acid is preferred as the water resistance enhancer, and a pretreatment agent It is more preferable to add 0.2 to 0.5 parts by weight based on 100 parts by weight of water.
상기 미세다공성 실리카는 원단의 은폐력을 향상시켜 승화전사 작업 후 색감과 세탁견뢰도를 향상시키기 위하여 첨가되며, 물 100 중량부 기준 0.5~2.0 중량부를 사용하는 것이 바람직하다.The microporous silica is added to improve the hiding power of the fabric to improve color and wash fastness after sublimation transfer, and it is preferable to use 0.5 to 2.0 parts by weight based on 100 parts by weight of water.
상기 증점제는 승화전사 날염시 작업성을 향상시키며, 아크릴계 증점제와 우레탄계 증점제 중 하나 이상을 사용하는 것이 바람직하고 물 100 중량부 기준 1-3 중량부를 사용하는 것이 더욱 바람직하다.The thickener improves workability during sublimation transfer printing, and it is preferable to use at least one of an acrylic thickener and a urethane-based thickener, and more preferably use 1-3 parts by weight based on 100 parts by weight of water.
상기 소포제는 승화전사 날염 공정에서 발생할 수 있는 기포의 생성을 억제하거나 이미 발생한 기포를 제거하여 작업성을 향상시키며, 물 100 중량부 기준 0.1~0.5 중량부를 사용하는 것이 바람직하다.The antifoaming agent suppresses the generation of bubbles that may occur in the sublimation transfer printing process or improves workability by removing the bubbles that have already occurred, and it is preferable to use 0.1 to 0.5 parts by weight based on 100 parts by weight of water.
상기 커플링제는 전처리제와 원단의 결합 및 전처리제 조성성분 간의 결합을 촉진하여 세탁시 원단으로부터 전처리제가 이탈되거나 원단에 기모가 발생하는 것을 방지하며, 커플링제로서 에폭시실란계 커플링제와 아미노실란계 커플링제 중 하나 이상을 사용하는 것이 바람직하고 물 100 중량부 기준 1~2 중량부를 사용하는 것이 더욱 바람직하다.The coupling agent promotes the bonding between the pretreatment agent and the fabric and the bonding between the pretreatment agent composition components to prevent the pretreatment agent from being separated from the fabric or from raising the fabric during washing. As a coupling agent, an epoxysilane-based coupling agent and an aminosilane-based coupling agent are used. It is preferable to use at least one of the coupling agents, and it is more preferable to use 1 to 2 parts by weight based on 100 parts by weight of water.
상기 자외선 안정제는 일반적인 자외선 안정제와는 다른 광 개시 효과가 있는 산화아연(ZnO) 계열이나 이산화티타늄(TiO2) 계열의 자외선 안정제를 사용하여. 승화전사 날염된 천연섬유 원단이 일광에 노출시 원단표면의 광 개시를 촉진하여 얇은 자외선 차단 피막을 형성함으로써 일광에서 분산염료의 이행이나 탈색을 개선하며, 물 100 중량부 기준 0.3~1.0 중량부를 사용하는 것이 바람직하다.The UV stabilizer is a zinc oxide (ZnO)-based or titanium dioxide (TiO 2 )-based UV stabilizer, which has a different photoinitiation effect than a general UV stabilizer. When sublimation transfer-printed natural fiber fabric is exposed to sunlight, it promotes light initiation on the surface of the fabric and forms a thin UV-blocking film, thereby improving the transfer or discoloration of disperse dyes in sunlight, 0.3 to 1.0 parts by weight based on 100 parts by weight of water It is preferable to do
상기와 같이 제조되는 본 발명의 승화전사용 천연섬유 전처리제는 천연섬유 원단에 견고히 결착되고 전사 열에 의해 미세구멍을 생성하여 승화된 분산염료를 고정하는 아크릴 수지, 자외선을 차단하여 아크릴 수지에 고정된 분산염료의 탈색을 방지하는 폴리에스테르 수지 및 피막을 형성하여 아크릴 수지와 결착된 분산염료를 더욱 고정하여 전사된 무늬의 내구성과 세탁견뢰도를 향상시키는 우레탄 수지가 조합되어, 천연섬유 원단에 분산염료를 승화전사 방식으로 염색하여도 원단이 선명한 무늬를 나타내면서 세탁견뢰도가 우수한 장점을 갖는다.The natural fiber pretreatment agent for sublimation transfer of the present invention prepared as described above is an acrylic resin that is firmly bound to the natural fiber fabric and fixes the sublimated disperse dye by creating micropores by transfer heat, and is fixed to the acrylic resin by blocking ultraviolet rays. Polyester resin to prevent discoloration of dispersed dye and urethane resin to improve the durability and wash fastness of the transferred pattern by further fixing the dispersed dye bound to the acrylic resin by forming a film. Even when dyed by sublimation transfer, the fabric shows a clear pattern and has the advantage of excellent washing fastness.
이하, 본 발명을 하기의 실시예 및 비교예에 의거하여 좀 더 상세하게 설명한다.Hereinafter, the present invention will be described in more detail based on the following Examples and Comparative Examples.
단, 하기의 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 치환 및 균등한 타 실시예로 변경할 수 있음은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다.However, the following examples are only for illustrating the present invention, and the present invention is not limited by the following examples, and can be substituted and changed to other equivalent examples without departing from the technical spirit of the present invention. It will be apparent to those of ordinary skill in the art to which the present invention pertains.
<실시예 1><Example 1>
에틸렌글리콜과 디메틸테레프탈레이트를 중합반응시켜 폴리에틸렌테레프탈레이트(polyethyleneterephthalate)를 얻은 다음 상기 폴리에틸렌테레프탈레이트의 벤젠고리의 수소를 술폰산나트륨기로 치환하여 수분산성 폴리에스테르 수지를 얻었다. 또한, 아크릴계 폴리올과 실리콘계 폴리올을 이소시아네이트와 반응시킨 후 트리에탄올아민을 첨가하여 중화시킨 후 에틸렌디아민과 반응시켜 아크릴 실리콘 우레탄 공중합체를 제조하였으며, 여기에 폴리카르보디이미드를 첨가하여 아크릴 실리콘 우레탄 수지를 제조하였다. 아크릴계 폴리올로는 애경화학 주식회사의 AA-960-60을, 실리콘계 폴리올로는 PDMS(Polydimethylsiloxane)을 이용하였다. Polyethylene terephthalate was obtained by polymerizing ethylene glycol and dimethyl terephthalate, and then hydrogen of the benzene ring of polyethylene terephthalate was replaced with a sodium sulfonate group to obtain a water-dispersible polyester resin. In addition, after reacting the acrylic polyol and the silicone polyol with isocyanate, triethanolamine was added to neutralize it and then reacted with ethylenediamine to prepare an acrylic silicone urethane copolymer, and polycarbodiimide was added thereto to prepare an acrylic silicone urethane resin did. AA-960-60 manufactured by Aekyung Chemical Co., Ltd. was used as the acrylic polyol, and polydimethylsiloxane (PDMS) was used as the silicone-based polyol.
물 1 ㎏에 2-에틸헥실메타크릴레이트 300 g, 상기 수분산성 폴리에스테르 수지 70 g, 상기 수분산성 아크릴 실리콘 우레탄 수지 55 g, 붕산(내수화 증진제) 4 g, 미세다공성 실리카 10 g, 아크릴계 증점제 20 g, 소포제 3 g, 에폭시실란계 커플링제 15 g, 산화아연계 자외선 안정제 7 g을 혼합하여 승화전사용 천연섬유 전처리제를 제조하였으며, 이를 면/모 소재 편물에 0.2 ㎜ 두께로 코팅되도록 스프레이 코팅하고 건조 및 냉각하였다. 아크릴계 증점제는 ㈜대원포리머사 제품 DA-2035, 소포제는 BYK사 제품 BYK-012, 에폭시실란계 커플링제는 신에츠사제품 KBM-403, 산화아연계 자외선 안정제는 수분산 나노화 시킨 ZnO를 이용하였다. 300 g of 2-ethylhexyl methacrylate in 1 kg of water, 70 g of the water-dispersible polyester resin, 55 g of the water-dispersible acrylic silicone urethane resin, 4 g of boric acid (water resistance enhancer), 10 g of microporous silica, acrylic thickener A natural fiber pretreatment for sublimation transfer was prepared by mixing 20 g, 3 g of an antifoaming agent, 15 g of an epoxysilane-based coupling agent, and 7 g of a zinc oxide-based UV stabilizer. Coated, dried and cooled. As an acrylic thickener, DA-2035 manufactured by Daewon Polymer, an antifoaming agent, BYK-012 manufactured by BYK, an epoxy silane coupling agent, KBM-403 manufactured by Shin-Etsu, and a zinc oxide UV stabilizer were water-dispersed ZnO.
종이를 기재로 하는 전사지에 분산염료를 이용하여 무늬를 프린팅한 후 전사프린트(transfer printing)를 이용하여 상기 전처리제가 코팅된 편물에 온도 200 ℃, 압력 4 ㎏f/㎠로 15 초간 가열가압하여 승화전사 날염하였다.After printing a pattern using a disperse dye on a transfer paper based on paper, using transfer printing, the pretreatment agent-coated knitted fabric is heated and pressed for 15 seconds at a temperature of 200° C. and a pressure of 4 kg f /cm 2 to sublimate. transcription was printed.
상기에서 전사 날염된 편물 원단을 한국의류시험연구원에 의뢰하여 염색특성을 측정하고 그 결과를 도 1 내지 도 5에 도시하였다.The above-mentioned transfer-printed knitted fabric was requested to the Korea Apparel Testing & Research Institute to measure the dyeing characteristics, and the results are shown in FIGS. 1 to 5 .
도 1~5의 결과를 보면, 세탁견뢰도, 땀견뢰도, 물견뢰도 모두 4~5급으로 우수하고 모섬유에 비하여 면섬유의 견뢰도가 조금 더 우수하였으며 마찰견뢰도와 일광견뢰도는 모두 4급으로 분석되어, 본 발명의 전처리제로 처리된 후 전사날염된 천연섬유 원단의 세탁견뢰도가 매우 우수함을 알 수 있다.1 to 5, washing fastness, sweat fastness, and water fastness were all excellent in grades 4 to 5, and the color fastness of the cotton fiber was slightly better than that of the wool fiber. It can be seen that the washing fastness of the transfer-printed natural fiber fabric after being treated with the pretreatment agent of the present invention is very good.
더불어 세탁치수변화율이 -5.0/-2.0(웨일방향/코스방향)으로 작고 필링과 퍼징 시험에서도 4급(경미한 표면 퍼징 및/또는 부분적으로 형성된 필)으로 양호하였으며, 원단에 잔류하는 약품의 함량 또한 기준치 미만임을 확인할 수 있다.In addition, the washing dimensional change rate was small at -5.0/-2.0 (wale direction/course direction), and it was good as a 4th grade (light surface purging and/or partially formed peel) in the peeling and purging tests, and the content of chemicals remaining in the fabric was also It can be confirmed that it is less than the standard value.
일반적으로 면섬유와 같은 천연섬유에는 분산염료의 전사가 잘 이루어지지 않아서 세탁견뢰도가 불량하고 잔류약품으로 인해 안전성이 문제시되나, 상기 결과와 같이 본 발명의 전처리제로 처리된 천연섬유 원단은 분산염료로 전사날염하여도 우수한 세탁견뢰도 및 안전성을 나타낸다.In general, natural fibers such as cotton fibers do not transfer disperse dyes well, so washing fastness is poor and safety is a problem due to residual chemicals. As a result, natural fiber fabrics treated with the pretreatment agent of the present invention are transferred with disperse dyes. It shows excellent washing fastness and safety even after printing.
<실시예 2~5> 및 <비교예 1~3><Examples 2 to 5> and <Comparative Examples 1 to 3>
하기 표 1의 조성비로 승화전사용 천연섬유 전처리제를 제조한 후 이를 각각 면직물에 0.2 ㎜ 두께로 코팅되도록 스프레이 코팅하고 건조 및 냉각하였으며, 종이를 기재로 하는 전사지에 표 1의 염료 및 색상으로 프린팅한 후 상기 실시예 1과 같은 방법으로 승화전사 날염하였다.After preparing a natural fiber pretreatment agent for sublimation transfer with the composition ratio of Table 1 below, it was spray-coated to be coated on a cotton fabric to a thickness of 0.2 mm, dried and cooled, and printed with the dye and color of Table 1 on a paper-based transfer paper. After that, sublimation transfer printing was performed in the same manner as in Example 1.
전처리제 성분비(g)Pretreatment ingredient ratio (g) 염료dyes
정제수Purified water 2-에틸헥실메타크릴레이 2-ethylhexyl methacrylate 수분산성 폴리에스테르 수지Water-dispersible polyester resin 수분산성 아크릴 실리콘 우레탄 수지Water-dispersible acrylic silicone urethane resin 첨가제주1) Additive Note 1) 종류Kinds 색상color
실시예 2Example 2 10001000 250250 100100 7070 5959 분산염료disperse dye blackblack
실시예 3Example 3 10001000 350350 5050 3030 5959 분산염료disperse dye graygray
실시예 4Example 4 10001000 250250 5050 3030 5959 분산염료disperse dye redred
실시예 5Example 5 10001000 350350 100100 7070 5959 분산염료disperse dye orangeorange
비교예 1Comparative Example 1 10001000 300300 7070 5050 5959 유성염료oil dye blackblack
비교예 2Comparative Example 2 10001000 250250 5050 3030 5959 유성염료oil dye redred
비교예 3Comparative Example 3 10001000 350350 100100 7070 5959 유성염료oil dye orangeorange
주1) 붕산(4 g)+미세다공성 실리카(10 g)+아크릴계 증점제(20 g)+소포제(3 g)+에폭시실란계 커플링제(15 g)+산화아연계 자외선 안정제(7 g)Note 1) Boric acid (4 g) + microporous silica (10 g) + acrylic thickener (20 g) + defoamer (3 g) + epoxy silane coupling agent (15 g) + zinc oxide UV stabilizer (7 g)
상기 실시예 2~5 및 비교예 1~3에서 전사날염된 면섬유 원단의 염색특성을 측정하고 그 결과를 하기 표 2에 나타내었다. The dyeing characteristics of the transfer-printed cotton fiber fabrics in Examples 2 to 5 and Comparative Examples 1 to 3 were measured, and the results are shown in Table 2 below.
세탁견뢰도주1) Washing fastness Note 1) 일광견뢰도주2) Fastness to sunlight Note 2)
변퇴색discoloration 이염otitis 오염pollution
아세테이트acetate 면if 나일론nylon 폴리에스테르Polyester 아크릴acryl 울fence
실시예 2Example 2 44 4-54-5 44 4-54-5 33 4545 4-54-5 4-54-5 44
실시예 3Example 3 44 4-54-5 44 4-54-5 3-43-4 4-54-5 4-54-5 4-54-5 44
실시예 4Example 4 4-54-5 4-54-5 3-43-4 4-54-5 33 44 4-54-5 44 4- 4 -
실시예 5Example 5 4-54-5 4-54-5 3-43-4 4-54-5 33 4-54-5 4-54-5 44 4- 4 -
비교예 1Comparative Example 1 44 3-43-4 22 44 1-21-2 4-54-5 4-54-5 33 44
비교예 2Comparative Example 2 44 3-43-4 3-43-4 4-54-5 22 4-54-5 4-54-5 3-43-4 33
비교예 3Comparative Example 3 4-54-5 4-54-5 3-43-4 4-54-5 2-32-3 4-54-5 4-54-5 44 3-43-4
주1) KS K ISO 105-C06:2014(텍스타일-염색 견뢰도 시험-제C06부:가정용 및 상업용 세탁에 대한 견뢰도) 시험법; (시험조건) 시험온도 40 ℃, 시험시간 30 분, 0.4 % 세제, 구슬 수 10 개주2) KS K ISO 105-B02:2010(텍스타일―염색 견뢰도 시험―제B02부:인공광 견뢰도:크세논 아크법) 시험법; (시험조건) 표준퇴색시간 20 h, 4급 이상Note 1) Test method of KS K ISO 105-C06:2014 (Textile-Dyeing fastness test-Part C06: Fastness to household and commercial laundry); (Test conditions) Test temperature 40 ℃, test time 30 minutes, 0.4% detergent, number of beads 10 pcs Note 2) KS K ISO 105-B02:2010 (Textile - Color fastness test - Part B02: Artificial light fastness: xenon arc method) test method; (Test conditions) Standard fading time 20 h, Grade 4 or higher
상기 표 2를 보면, 변퇴색은 실시예와 비교예 간에 유의적인 차이를 나타내지 않았으나, 이염도는 본 발명에 따른 실시예가 4~5급이나 비교예 1, 2에서 3~4급으로 약간 저하되었다.Referring to Table 2, the discoloration did not show a significant difference between the Example and the comparative example, but the degree of dye transfer was slightly lowered to the 3rd to 4th grade in Comparative Examples 1 and 2, but in Examples 4-5 in the present invention. .
오염도에서는 아세테이트 섬유:실시예 2~5(3~4급)/비교예 1(2급), 나일론 섬유:실시예 2~5(3~4급)/비교예 1(1~2급)/비교예 2(2급)/비교예 3(2~3급), 울 섬유:실시예 2~5(4~5급)/비교예 1(3급)/비교예 2(3~4급)으로 측정되어, 본 발명의 승화전사용 천연섬유 전처리제를 면섬유에 코팅한 후 승화전사 날염하는 것이 세탁견뢰도를 향상시킴을 알 수 있다.In the degree of contamination, acetate fiber: Examples 2 to 5 (grade 3 to 4) / Comparative Example 1 (grade 2), nylon fiber: Examples 2 to 5 (grade 3 to 4) / Comparative Example 1 (grade 1 to 2) / Comparative Example 2 (Class 2)/Comparative Example 3 (Class 2-3), Wool Fiber: Examples 2-5 (Class 4-5)/Comparative Example 1 (Class 3)/Comparative Example 2 (Class 3-4) It can be seen that, after coating the natural fiber pretreatment agent for sublimation transfer of the present invention on cotton fiber, the sublimation transfer printing improves the washing fastness.
일광견뢰도를 보면, 실시예는 4급을 나타내었으나 비교예 2, 3은 3~4급으로 측정되어, 본 발명의 전처리제가 면섬유의 일광견뢰도 향상에 효과적임을 알 수 있다.Looking at the light fastness, the Example showed the 4th grade, but Comparative Examples 2 and 3 were measured as 3rd to 4th grade, so it can be seen that the pretreatment of the present invention is effective in improving the light fastness of the cotton fiber.

Claims (4)

  1. 물 100 중량부, 아크릴 수지 25~35 중량부, 폴리에스테르 수지 5~10 중량부 및 우레탄 수지 3~7 중량부를 포함하고,100 parts by weight of water, 25 to 35 parts by weight of an acrylic resin, 5 to 10 parts by weight of a polyester resin, and 3 to 7 parts by weight of a urethane resin,
    상기 우레탄 수지는 아크릴계 폴리올 및 실리콘계 폴리올을 이소시아네이트와 반응시킨 프리폴리머에 트리에탄올아민으로 중화시킨 후 에틸렌디아민과 합성하여 아크릴 실리콘 우레탄 공중합체를 제조한 후 폴리카르보디이미드를 첨가하여 제조되는 승화전사용 천연섬유 전처리제.The urethane resin is a natural fiber for sublimation transfer prepared by neutralizing an acrylic polyol and a silicone polyol in a prepolymer reacted with isocyanate with triethanolamine, then synthesizing with ethylenediamine to prepare an acrylic silicone urethane copolymer, and then adding polycarbodiimide pretreatment.
  2. 청구항 1에 있어서,The method according to claim 1,
    상기 아크릴 수지는 이소부틸아크릴레이트, 메틸 메타크릴레이트, 에틸아크릴레이트 및 2-에틸헥실메타크릴레이트로 이루어진 군 중에서 선택되는 적어도 어느 하나의 모노머로부터 중합된 수분산성 아크릴 수지인 것을 특징으로 하는 승화전사용 천연섬유 전처리제.The acrylic resin is a water-dispersible acrylic resin polymerized from at least one monomer selected from the group consisting of isobutyl acrylate, methyl methacrylate, ethyl acrylate and 2-ethylhexyl methacrylate. Use natural fiber pretreatment.
  3. 청구항 1에 있어서,The method according to claim 1,
    상기 폴리에스테르 수지는 에틸렌글리콜과 디메틸테레프탈레이트를 에스테르화 반응시켜 합성된 폴리에스테르 수지의 수소를 술폰산나트륨기로 치환한 수분산성 폴리에스테르 수지인 것을 특징으로 하는 승화전사용 천연섬유 전처리제.The polyester resin is a natural fiber pretreatment for sublimation transfer, characterized in that it is a water-dispersible polyester resin in which hydrogen of a polyester resin synthesized by esterification reaction of ethylene glycol and dimethyl terephthalate is substituted with a sodium sulfonate group.
  4. 청구항 1에 있어서,The method according to claim 1,
    상기 전처리제는 물 100 중량부 기준 내수화 증진제 0.2~0.5 중량부, 미세다공성 실리카 0.5~2.0 중량부, 증점제 1-3 중량부, 소포제 0.1~0.5 중량부, 커플링제 1~2 중량부 및 자외선 안정제 0.3~1.0 중량부로 이루어진 군 중에서 선택되는 적어도 어느 하나의 첨가제를 더 포함하는 것을 특징으로 하는 승화전사용 천연섬유 전처리제.The pretreatment agent is 0.2 to 0.5 parts by weight of a waterproofing enhancer based on 100 parts by weight of water, 0.5 to 2.0 parts by weight of microporous silica, 1-3 parts by weight of a thickener, 0.1 to 0.5 parts by weight of an antifoaming agent, 1-2 parts by weight of a coupling agent and ultraviolet rays Natural fiber pretreatment agent for sublimation transfer, characterized in that it further comprises at least one additive selected from the group consisting of 0.3 to 1.0 parts by weight of a stabilizer.
PCT/KR2019/018013 2019-11-29 2019-12-18 Natural fiber preprocessing agent for sublimation transfer WO2021107253A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000027779A (en) * 1998-10-29 2000-05-15 장용균 Resin composition for decorative polyester film and preparation method thereof
JP2009197228A (en) * 2001-04-03 2009-09-03 Clariant Internatl Ltd Azo compound
KR101373928B1 (en) * 2013-05-24 2014-03-12 김계수 Heat transfer coating solution composition and digital sublimation transfer textile using thereof
KR20150058198A (en) * 2012-09-21 2015-05-28 가부시키가이샤 아데카 Aqueous dispersion of polyurethane resin, fire-resistant polyester-based fiber using same, and method for producing said fiber
KR20170093148A (en) * 2014-12-12 2017-08-14 이관병 Binder composition for natural fiber sublimation transfer printing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000027779A (en) * 1998-10-29 2000-05-15 장용균 Resin composition for decorative polyester film and preparation method thereof
JP2009197228A (en) * 2001-04-03 2009-09-03 Clariant Internatl Ltd Azo compound
KR20150058198A (en) * 2012-09-21 2015-05-28 가부시키가이샤 아데카 Aqueous dispersion of polyurethane resin, fire-resistant polyester-based fiber using same, and method for producing said fiber
KR101373928B1 (en) * 2013-05-24 2014-03-12 김계수 Heat transfer coating solution composition and digital sublimation transfer textile using thereof
KR20170093148A (en) * 2014-12-12 2017-08-14 이관병 Binder composition for natural fiber sublimation transfer printing

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