KR102518040B1 - Pretreatment composition for high-speed digital printing using polyurethane - Google Patents
Pretreatment composition for high-speed digital printing using polyurethane Download PDFInfo
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- KR102518040B1 KR102518040B1 KR1020210041803A KR20210041803A KR102518040B1 KR 102518040 B1 KR102518040 B1 KR 102518040B1 KR 1020210041803 A KR1020210041803 A KR 1020210041803A KR 20210041803 A KR20210041803 A KR 20210041803A KR 102518040 B1 KR102518040 B1 KR 102518040B1
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 229920005749 polyurethane resin Polymers 0.000 claims description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 21
- 239000004744 fabric Substances 0.000 description 18
- 239000000976 ink Substances 0.000 description 16
- 239000003086 colorant Substances 0.000 description 15
- 238000011161 development Methods 0.000 description 15
- 239000000049 pigment Substances 0.000 description 9
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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Classifications
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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
- D06M15/37—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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
- D06M11/155—Halides of elements of Groups 2 or 12 of the Periodic Table
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Coloring (AREA)
Abstract
본 발명은 우레탄을 이용한 고속 디지털 날염용 전처리제 조성물에 관한 것으로, 본 발명에서는 폴리우레탄계(PU) 바인더 10~30중량부, 염화칼슘(CaCl2) 1~5중량부, 에틸렌글리콜(EG) 5~20중량부, 가교제 1~5중량부 및 물 40~83중량부를 포함하는 것을 특징으로 하는 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물이 개시된다.The present invention relates to a pretreatment composition for high- speed digital printing using urethane. Disclosed is a pretreatment composition for high-speed digital printing using polyurethane, comprising 20 parts by weight, 1 to 5 parts by weight of a crosslinking agent, and 40 to 83 parts by weight of water.
Description
본 발명은 우레탄을 이용한 고속 디지털 날염용 전처리제 조성물에 관한 것으로 보다 상세하게는 폴리우레탄을 양이온수지로 개질함으로써 발색제로 사용되는 염화칼슘과의 반응을 차단하고 분산성을 향상시킴으로써 우수한 습마찰 견뢰도를 가지는 우레탄을 이용한 고속 디지털 날염용 전처리제 조성물에 관한 것이다.The present invention relates to a pretreatment composition for high-speed digital printing using urethane. It relates to a pretreatment composition for high-speed digital printing using urethane.
디지털 날염용 전처리제는 섬유를 디지털 프린터로 날염하기 전에 잉크가 원단에 번지지 않고 선명한 무늬가 형성되도록 하는 용도로 사용된다. 이러한 전처리 조제와 전처리 기술은 섬유의 종류와 사용하는 잉크에 따라 달라지기 때문에, 다양한 섬유소재에 따른 전처리 조제 및 처리기술의 개발이 필요하다.A pretreatment agent for digital printing is used to ensure that ink does not bleed through the fabric and forms a clear pattern before printing the fabric with a digital printer. Since these pretreatment preparations and pretreatment techniques vary depending on the type of fiber and the ink used, it is necessary to develop pretreatment preparations and treatment techniques according to various textile materials.
한편, 디지털 날염의 고부가 아이템 적용을 위해서는 폴리에스테르/면 또는 나일론/면과 같은 복합소재의 디지털 날염을 위한 전처리 기술이 필요한데, 디지털 날염용 원단의 전처리기술은 아직까지는 실크, 면 등의 일부 범용 소재에 국한되어 있으며, 상술한 복합소재용 디지털 날염을 위한 전처리 기술에 대한 개발은 미미한 실정이다.On the other hand, in order to apply high value-added items of digital printing, pre-processing technology for digital printing of composite materials such as polyester/cotton or nylon/cotton is required. It is limited to, and the development of pretreatment technology for digital printing for composite materials described above is insignificant.
또한, 디지털 날염에 있어서 셀룰로오스/나일론 복합소재와 같이 친화성이 있는 염료의 종류가 서로 다른 복합소재를 각각의 섬유소재에 적합한 두 가지 이상의 염료를 사용하여 한꺼번에 원스텝(one step)으로 프린팅하거나 또는 투스텝(two step)으로 프린팅하는 것에 많은 문제점이 있다. 원스텝으로 진행할 경우, 각 잉크에 적합하지 않은 직물상의 전처리로 인해 염료(잉크)의 발색 안정성이 크게 낮아질 우려가 있으며, 만약 투스텝으로 디지털 프린팅하여 날염을 실시하면 서로 다른 염료의 고착시에 원하는 디자인 무늬를 맞추기가 어려울 뿐더러 반복적 프린팅으로 인해 형태안정성이 낮아질 수가 있다.In addition, in digital printing, composite materials with different types of dyes with affinity, such as cellulose/nylon composites, can be printed in one step at once using two or more dyes suitable for each fiber material, or two-step There are many problems with printing in two steps. In the case of one-step processing, there is a risk that the color development stability of the dye (ink) will be significantly lowered due to pretreatment on the fabric that is not suitable for each ink. It is difficult to match the shape, and shape stability may be lowered due to repetitive printing.
이러한 문제점 때문에, 현재 각 제조사에서는 소재종류에 상관없고, 전처리공정이 필요없는 안료형 잉크를 개발하여 복합소재 또는 디지털 날염 적용이 어려운 소재에 적용하기도 한다. 그러나 안료형 잉크는 채도나 선명성이 염료형 잉크를 사용할 때보다 현저히 낮아 고발색을 요구하는 디지털 날염용 제품에 적합하지 않다는 단점이 있다.Because of these problems, currently, each manufacturer develops a pigment-type ink that does not require a pretreatment process regardless of the type of material and applies it to composite materials or materials that are difficult to apply digital printing. However, the pigment-type ink has a disadvantage in that it is not suitable for products for digital printing requiring high color development because the saturation or sharpness is significantly lower than that of the dye-type ink.
이러한 단점을 개선하기 위한 것으로 EVA 바인더를 사용한 안료잉크용 DTP전처리제가 개발되었으며, 상기 EVA바인더를 사용한 안료잉크용 DTP전처리제는 발색성능은 매우 뛰어나나 일부 색상의 마찰 견뢰도를 좀 더 향상시키기 위한 개선 연구가 필요하다.In order to improve these disadvantages, a DTP pretreatment agent for pigment ink using an EVA binder was developed, and the DTP pretreatment agent for pigment ink using the EVA binder has excellent color development performance, but is improved to further improve the friction fastness of some colors. Research is needed.
안료 잉크에 기본적으로 사용되는 폴리우레탄계(PU) 바인더를 사용하여 전처리제를 배합(formulation)할 경우 발색제로 사용되는 염화칼슘(CaCl2)와 반응하여 젤화 현상이 발생하므로 분산 및 분무가 어려워 전처리제로서 사용할 수 없는 것임을 확인하였다. When formulating a pretreatment using a polyurethane (PU) binder, which is basically used in pigment ink, it reacts with calcium chloride (CaCl 2 ) used as a coloring agent to cause gelation, making it difficult to disperse and spray. Confirmed that it is not usable.
본 발명의 발명자들은 염과 반응하지 않는 PU계 바인더를 사용하면 견뢰도가 증진시킬 수 있을 것으로 판단하여, 폴리우레탄을 양이온수지로 개질함으로써 발색제로 사용되는 염화칼슘과의 반응을 차단하고 분산성을 향상시킴으로써 우수한 습마찰 견뢰도를 가지는 우레탄을 이용한 고속 디지털 날염용 전처리제 조성물을 제공하는 것을 그 해결과제로 한다. The inventors of the present invention determined that the use of a PU-based binder that does not react with salt can improve fastness, and by modifying polyurethane with a cationic resin to block the reaction with calcium chloride used as a coloring agent and improve dispersibility, To solve the problem is to provide a pretreatment composition for high-speed digital printing using urethane having excellent wet rub fastness.
상기한 과제를 해결한 본 발명에 따른 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물은 폴리우레탄계(PU) 바인더 10~30중량부, 염화칼슘(CaCl2) 1~5중량부, 에틸렌글리콜(EG) 5~20중량부, 가교제 1~5중량부 및 물 40~83중량부를 포함하는 것을 특징으로 한다. The pretreatment composition for high-speed digital printing using polyurethane according to the present invention, which solves the above problems, contains 10 to 30 parts by weight of a polyurethane-based (PU) binder, 1 to 5 parts by weight of calcium chloride (CaCl 2 ), ethylene glycol (EG) It is characterized by comprising 5 to 20 parts by weight, 1 to 5 parts by weight of a crosslinking agent and 40 to 83 parts by weight of water.
여기서, 상기 폴리우레탄계 (PU) 바인더는 폴리우레탄수지를 준비하고, 상기 폴리우레탄수지를 양이온수지액으로 처리하여 개질시킨 개질폴리우레탄인 것을 특징으로 한다. Here, the polyurethane-based (PU) binder is characterized in that it is a modified polyurethane prepared by preparing a polyurethane resin and modifying the polyurethane resin by treating the polyurethane resin with a cationic resin solution.
여기서, 상기 폴리우레탄은 수평균분자량이 2,000~5,000인 폴리에테르계 폴리올 30~55 중량%와 수평균분자량이 1,000~3,000인 폴리에스테르계 폴리올 45~70 중량%의 혼합물로 이루어진 것을 특징으로 한다. Here, the polyurethane is characterized in that it consists of a mixture of 30 to 55% by weight of a polyether polyol having a number average molecular weight of 2,000 to 5,000 and 45 to 70% by weight of a polyester polyol having a number average molecular weight of 1,000 to 3,000.
여기서, 상기 양이온수지는 SAC(Strongly Acidic Cation exchange resin)과 WAC(Weakly Acidic Cation exchange resin)로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 한다. Here, the cation resin is characterized in that any one selected from the group consisting of Strongly Acidic Cation exchange resin (SAC) and Weakly Acidic Cation exchange resin (WAC).
여기서, 상기 가교제는 디에탄올아민, 모노에틸렌글리콜, 디에틸렌글리콜, 1,6-헥산디올 디아실레이트, 트리메틸올프로판, 트리아크릴레이트로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 한다.Here, the crosslinking agent is characterized in that any one selected from the group consisting of diethanolamine, monoethylene glycol, diethylene glycol, 1,6-hexanediol diacylate, trimethylolpropane, and triacrylate.
본 발명에 따라 제공되는 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물은 사용되는 폴리우레탄을 양이온성 수지로 개질시킴으로써 수분상성을 향상시키고, 조성되는 염화칼슘과의 반응성을 억제하여 최종 배합되는 전처리제 조성물이 젤화되지 않아 전처리제로서 적합한 물성을 확보할 수 있고, 또한 염과 반응하지 않는 PU계 바인더를 사용함으로써 우수한 습마찰 견뢰도를 가지는 전처리제 조성물을 제공할 수 있다.The pretreatment composition for high-speed digital printing using polyurethane provided according to the present invention improves moisture resistance by modifying polyurethane used with a cationic resin and suppresses the reactivity with calcium chloride to be finally formulated as a pretreatment composition. A pretreatment composition having excellent wet rub fastness can be provided by using a PU-based binder that does not gel and thus has properties suitable as a pretreatment agent and does not react with salt.
도 1 은 본 발명에 따른 전처리제를 사용것과 사용하지 않은 것의 발색성능을 비교한 사진이다.
도 2 는 본 발명에 따른 전처리제를 사용것과 사용하지 않은 것의 발색성능을 비교한 그래프이다.
도 3 은 본 발명에 따른 전처리제를 사용하여 전처리한 원단과 종래의 전처리제를 사용하여 전처리한 원단의 인쇄 상태를 비교한 사진이다.
도 4 는 본 발명에 따른 전처리제를 사용하여 전처리된 원단의 10곳을 채취하여 CMYK 4색을 인쇄 후 색차를 측정하기 위한 시료를 도시한 것이다.1 is a photograph comparing the color development performance of those using and not using a pretreatment agent according to the present invention.
Figure 2 is a graph comparing the color development performance of those using and not using a pretreatment agent according to the present invention.
3 is a photograph comparing the printing conditions of a fabric pretreated using a pretreatment agent according to the present invention and a fabric pretreated using a conventional pretreatment agent.
4 shows a sample for measuring color difference after printing 4 colors of CMYK by taking 10 places of fabric pretreated using a pretreatment agent according to the present invention.
이하, 본 발명을 보다 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명의 발명자들은 종래의 EVA계 바인더를 사용한 안료잉크용 DTP 전처리제의 문제점으로 지적되는 낮은 습마찰 견뢰도를 개선하고자 안출한 것으로, 안료 잉크에 기본적으로 사용되는 폴리우레탄계(PU) 바인더를 사용하여 전처리제를 배합(formulation)할 경우 견뢰도를 증진시킬 수 있을 판단하고 상기 폴리우레탄을 사용하여 고속 디지털 날염용 전처리제를 배합하여 보았으나, 발색제로 사용되는 염화칼슘(CaCl2)와 반응하여 젤화 현상이 발생하여 분산 및 분무가 어려워 전처리제로서 사용할 수 없는 것임을 확인하였다. The inventors of the present invention have devised to improve the low wet friction fastness, which is pointed out as a problem of the DTP pretreatment agent for pigment ink using a conventional EVA-based binder, by using a polyurethane-based (PU) binder that is basically used for pigment ink. When formulating a pretreatment agent, it was determined that the fastness could be improved, and a pretreatment agent for high-speed digital printing was formulated using the polyurethane, but gelation occurred due to reaction with calcium chloride (CaCl 2 ) used as a coloring agent It was confirmed that it could not be used as a pretreatment agent because it was difficult to disperse and spray.
이를 해결하기 위하여 본 발명의 발명자들은 염과 반응하지 않는 PU계 바인더를 양이온성 수지로 개질시키고, 그 개질된 폴리우레탄을 사용하여 전처리제를 배합하였을 경우 염화칼슘과의 반응을 억제시켜 젤화현상 문제를 개선할 수 있음을 확인하고 본 발명을 완성하였다. In order to solve this problem, the inventors of the present invention modified a PU-based binder that does not react with salt into a cationic resin, and when a pretreatment agent was mixed using the modified polyurethane, the gelation problem was solved by suppressing the reaction with calcium chloride. It was confirmed that it could be improved and the present invention was completed.
이를 보다 구체적으로 설명하면,To explain this more specifically,
본 발명에 따른 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물은 폴리우레탄계(PU) 바인더 10~30중량부, 염화칼슘(CaCl2) 1~5중량부, 에틸렌글리콜(EG) 5~20중량부, 가교제 1~5중량부 및 물 40~83중량부를 포함하는 것에 그 기술적 특징이 있다. The pretreatment composition for high-speed digital printing using polyurethane according to the present invention includes 10 to 30 parts by weight of a polyurethane-based (PU) binder, 1 to 5 parts by weight of calcium chloride (CaCl 2 ), 5 to 20 parts by weight of ethylene glycol (EG), Its technical feature is that it contains 1 to 5 parts by weight of a crosslinking agent and 40 to 83 parts by weight of water.
바람직하게 상기 조성물을 구성하는 상기 폴리우레탄계 바인더는 양이온성 수지로 개질시킨 개질 폴리우레탄 바인더를 사용하는 것이다. Preferably, the polyurethane-based binder constituting the composition is to use a modified polyurethane binder modified with a cationic resin.
상기 개질 폴리우레탄 바인더는 일예로 폴리우레탄수지를 준비하고, 상기 폴리우레탄수지를 양이온성 수지액으로 처리하여 개질시킨 개질폴리우레탄을 사용하는 것이다. For example, the modified polyurethane binder is prepared by preparing a polyurethane resin and using a modified polyurethane modified by treating the polyurethane resin with a cationic resin solution.
이때, 바람직하게 상기 폴리우레탄은 수평균분자량이 2,000~5,000인 폴리에테르계 폴리올 30~55 중량%와 수평균분자량이 1,000~3,000인 폴리에스테르계 폴리올 45~70 중량%의 혼합물로 이루어진 것을 사용하는 것이고, 상기 양이온수지는 SAC(Strongly Acidic Cation exchange resin)과 WAC(Weakly Acidic Cation exchange resin)로 이루어진 군에서 선택되는 어느 하나를 사용하는 것이다. At this time, preferably, the polyurethane uses a mixture of 30 to 55% by weight of a polyether polyol having a number average molecular weight of 2,000 to 5,000 and 45 to 70% by weight of a polyester polyol having a number average molecular weight of 1,000 to 3,000 And, the cation resin is to use any one selected from the group consisting of SAC (Strongly Acidic Cation exchange resin) and WAC (Weakly Acidic Cation exchange resin).
상기 폴리우레탄을 개질시 상기 폴리우레탄과 양이온성 수지는 바람직하게 6:4 내지 7:3의 범위내의 중량비로 혼합하여 개질시키는 것이다. 만일 상기 중량비 범위의 임계치를 벗어날 경우에는 폴리우레탄이 무기엽과 반응하여 전처리제가 겔화되어 사용할 수 없는 문제가 있을 수 있다. When modifying the polyurethane, the polyurethane and the cationic resin are preferably mixed and modified in a weight ratio within the range of 6:4 to 7:3. If it is out of the critical value of the above weight ratio range, polyurethane reacts with the inorganic leaf and there may be a problem in that the pretreatment agent is gelled and cannot be used.
본 발명에 따르면, 바람직하게 상기 가교제는 디에탄올아민, 모노에틸렌글리콜, 디에틸렌글리콜, 1,6-헥산디올 디아실레이트, 트리메틸올프로판 트리아크릴레이트로 이루어진 군에서 선택되는 어느 하나를 사용하는 것이다. According to the present invention, preferably, the crosslinking agent is to use any one selected from the group consisting of diethanolamine, monoethylene glycol, diethylene glycol, 1,6-hexanediol diacylate, and trimethylolpropane triacrylate. .
본 발명에 따르면, 상기 폴리우레탄 바인더는 습마찰 견뢰도를 향상시키고 발색성을 향상시키기 위하여 사용되는 것으로 그 배합량이 10중량부 미만일 경우에는 견뢰도가 저하되는 문제가 있고, 30중량부를 초과할 경우에는 최종 인쇄물의 열처리 시 원단의 터치가 좋지 못한 문제가 있다. According to the present invention, the polyurethane binder is used to improve wet rub fastness and color development, and when the blending amount is less than 10 parts by weight, there is a problem in that fastness is lowered, and when it exceeds 30 parts by weight, the final printed product There is a problem that the touch of the fabric is not good during heat treatment.
본 발명에 따르면, 상기 염화칼슘(CaCl2)은 발색제로 사용되는 것으로, 그 사용량이 1중량부 미만일 경우에는 발색 성능이 현저하게 저하되는 문제가 있고, 5중량부를 초과하는 경우에는 발색성능이 더 이상 크게 증가하지 않는다.According to the present invention, the calcium chloride (CaCl2) is used as a coloring agent, and when the amount thereof is less than 1 part by weight, there is a problem in that the color development performance is significantly lowered, and when it exceeds 5 parts by weight, the color development performance is no longer greatly increased. does not increase
본 발명에 따르면, 상기 에틸렌글리콜(EG)은 발색성을 향상시키기 위해 사용되는 것으로, 그 사용량이 5중량부 미만일 경우에는 염화칼슘과 같이 발색 성능이 낮은 한 문제가 있고, 20중량부를 초과 할 경우 발색성능은 더 이상 크게 증가하지 않아 제조비용이 상승하는 단점이 있다.According to the present invention, the ethylene glycol (EG) is used to improve color development, and when the amount thereof is less than 5 parts by weight, there is a problem in that color development performance is low, such as calcium chloride, and when it exceeds 20 parts by weight, color development performance There is a disadvantage that the manufacturing cost increases because it does not increase significantly anymore.
본 발명에 따르면, 상기 가교제는 그 사용량이 1중량부 미만일 경우에는 견뢰도가 현저하게 저하되는 문제가 있고, 5중량부를 초과할 경우에는 오히려 견뢰도가 저하되는 문제가 있다. According to the present invention, when the amount of the crosslinking agent is less than 1 part by weight, fastness is significantly reduced, and when it exceeds 5 parts by weight, fastness is rather deteriorated.
이하, 본 발명을 바람직한 실험예와 첨부된 도면을 참조하여 보다 상세히 설명하기로 한다. 단, 하기에 서술되는 실험예와 첨부도면은 본 발명을 설명하기 위한 일예시 및 시험결과로서 하기에 서술되는 실험예로 본 발명을 한정하는 것은 아니며, 본 발명의 특허청구범위의 기재된 발명의 범위를 벗어나지 않는 범위 내에서 당업계의 통상의 기술자가 얼마 든지 변형 가능한 것이다. Hereinafter, the present invention will be described in more detail with reference to preferred experimental examples and accompanying drawings. However, the experimental examples and accompanying drawings described below do not limit the present invention to the experimental examples described below as examples and test results for explaining the present invention, and the scope of the invention described in the claims of the present invention Within the range that does not deviate from, a person skilled in the art can make any modifications.
[PU계 바인더 기반 DTP 전처리제 배합][Formulation of PU binder-based DTP pretreatment agent]
하기 표 1에 실험에 사용된 전처리제 배합비율을 나타내었다. Table 1 below shows the blending ratio of the pretreatment used in the experiment.
(중량부)blending amount
(parts by weight)
상기 표 1의 PU계 바인더는 양이온성 수지인 SAC타입의 CMP08로 개질시킨 개질폴리우레탄 바인더를 사용하였다. 그 개질방법은 상기 본 발명의 설명에 개시된 방법에 따라 개질하였다. The PU-based binder in Table 1 used a modified polyurethane binder modified with SAC-type CMP08, which is a cationic resin. The modification method was modified according to the method disclosed in the description of the present invention above.
[전처리제 성능 시험][Pretreatment performance test]
1) 일광견뢰도: 상기 표 1의 전처리제로 처리한 원단과 미처리한 원단을 DTP용 안료잉크인 CMYK 4색상을 사용하여 DTP인쇄 후 일광 견뢰도를 측정하여 보았으며 그 결과는 하기 표 2에 나타내었다. 일광 견뢰도 측정 결과 4색상에 대해 4급 이상으로 매우 좋은 성능을 나타내는 것을 알 수 있었다. 1) Daylight fastness: Daylight fastness was measured after DTP printing of fabrics treated with the pretreatment and untreated fabrics in Table 1 using 4 colors of CMYK, which are pigment inks for DTP, and the results are shown in Table 2 below. As a result of daylight fastness measurement, it was found that it showed very good performance of 4th grade or higher for 4 colors.
2) 세탁견뢰도: 상기 표 1의 전처리제로 처리한 원단과 미처리한 원단을 DTP용 안료잉크인 CMYK 4색상을 사용하여 DTP인쇄 후 세탁 견뢰도를 측정하여 보았으며 그 결과는 하기 표 3에 나타내었다. 세탁 견뢰도 측정 결과 4색상에 대해 406바인더는 4급, 그 외의 조건은 모든 색상에 대해 4-5급으로 매우 우수한 성능을 나타내는 것을 알 수 있었다. 2) Washing fastness: Washing fastness was measured after DTP printing of fabrics treated with the pretreatment and untreated fabrics in Table 1 using 4 colors of CMYK, which are pigment inks for DTP, and the results are shown in Table 3 below. As a result of the measurement of washing fastness, it was found that the 406 binder showed very excellent performance, with 4 grades for 4 colors and 4-5 grades for all other conditions.
3) 마찰견뢰도: 상기 표 1의 전처리제로 처리한 원단과 미처리한 원단을 DTP용 안료잉크인 CMYK 4색상을 사용하여 DTP인쇄 후 마찰견뢰도를 측정하여 보았으며 그 결과는 하기 표 4에 나타내었다. 마찰견뢰도 측정 결과 4색상에 대해 건마찰은 미처리보다 향상되는 것을 알 수 있었고, 항상 문제가 되었던 습마찰 견뢰도도 개선되는 효과가 있는 것을 알 수 있었다. 3) Friction fastness: Friction fastness was measured after DTP printing of the fabric treated with the pretreatment agent in Table 1 and the untreated fabric using 4 colors of CMYK, which is a DTP pigment ink, and the results are shown in Table 4 below. As a result of measuring the color fastness to rubbing, it was found that dry rubbing was improved compared to untreated for the four colors, and it was found that the wet rubbing fastness, which was always a problem, was also improved.
견뢰도dry friction
fastness
견뢰도wet friction
4) 발색성: 상기 표 1의 전처리제로 처리한 원단과 미처리한 원단을 DTP용 안료잉크인 CMYK 4색상을 사용하여 DTP인쇄 후, 인쇄색상을 비교하여 발색성능을 비교하여 보았으며, 그 결과는 도 1 및 2에 나타내었다. 그 결과 미처리 원단에 비해 아주 높은 발색 성능을 나타내는 것을 알 수 있었다. 4) Color development: After DTP printing of fabrics treated with the pretreatment agent in Table 1 and untreated
5) 인쇄면의 선예도: 인쇄면의 선예도를 (주)선진의 전처리제를 사용한 것과 대비하여 보았으며, 그 결과 도 3에 도시된 바와 같이, (주)선진제품과 인쇄 상태가 다르지 않은 상태인 것을 확인 할 수 있었다. 5) Sharpness of the printed surface: The sharpness of the printed surface was compared with the use of Sunjin's pretreatment agent, and as a result, as shown in Figure 3, the state of printing is not different from Sunjin's product was able to confirm that
특히, 위사 방향의 경우 본 발명의 전처리제제품이 적용된 제품이 그 인쇄경계가 더욱 깨끗한 것을 확인 할 수 있었으며, (주)선진제품 대비 100% 유사한 첨예성을 보이는 것을 확인 할 수 있었다. In particular, in the case of the weft direction, it was confirmed that the printed border of the product to which the pretreatment product of the present invention was applied was cleaner, and it was confirmed that the sharpness was 100% similar to that of the Sunjin product.
6) 색차측정: 표 1의 전처리제로 전처리된 원단의 10곳을 채취하여 CMYK 4색을 인쇄 후 색차를 측정한 결과 색상에 차이가 없음을 알 수 있었다.(도 4 및 표 5 참조) 6) Color difference measurement: As a result of measuring the color difference after taking 10 places of the fabric pretreated with the pretreatment agent in Table 1 and
- 원단 10yd를 준비하고 시작점 5 point(A~E) 및 종료점 5point(F~J)에서 각각 시료를 채취 - Prepare 10 yards of fabric and take samples from 5 starting points (A~E) and 5 ending points (F~J)
- 시작점 중앙인 A를 기준으로 하여 각 색상의 색차(△E)를 측정하였으며, 그 결과 최대 색차는 0.4를 넘지 않았다.(표 5 참조) - The color difference (ΔE) of each color was measured based on A, the center of the starting point, and as a result, the maximum color difference did not exceed 0.4 (see Table 5).
이와 같은 본 발명은 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물은 사용되는 폴리우레탄을 양이온성 수지로 개질시킴으로써 수분상성을 향상시키고, 조성되는 염화칼슘과의 반응성을 억제하여 최종 배합되는 전처리제 조성물이 젤화되지 않아 전처리제로서 적합한 물성을 확보할 수 있고, 또한 염과 반응하지 않는 PU계 바인더를 사용함으로써 우수한 습마찰 견뢰도를 가지는 등의 효과가 있는 매우 유용한 발명이다.In the present invention, the pretreatment composition for high-speed digital printing using polyurethane improves moisture resistance by modifying the polyurethane used with a cationic resin and suppresses the reactivity with calcium chloride to form a pretreatment composition finally formulated. It is a very useful invention that does not gel and can secure physical properties suitable as a pretreatment agent, and also has effects such as having excellent wet rub fastness by using a PU-based binder that does not react with salt.
Claims (5)
폴리우레탄계(PU) 바인더 10~30중량부, 염화칼슘(CaCl2) 1~5중량부, 에틸렌글리콜(EG) 5~20중량부, 가교제 1~5중량부 및 물 40~83중량부를 포함하는 것으로,
상기 폴리우레탄계 (PU) 바인더는 폴리우레탄수지를 준비하고, 상기 폴리우레탄수지를 SAC(Strongly Acidic Cation exchange resin)과 WAC(Weakly Acidic Cation exchange resin)로 이루어진 군에서 선택되는 어느 하나의 양이온수지액을 준비하고, 상기 폴리우레탄수지와 양이온성수지액을 6:4 내지 7:3의 범위내의 중량비로 혼합하여 개질시킨 개질폴리우레탄을 사용하고,
상기 가교제는 디에탄올아민, 모노에틸렌글리콜, 디에틸렌글리콜, 1,6-헥산디올 디아실레이트, 트리메틸올프로판, 트리아크릴레이트로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 하는 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물.
In the pretreatment composition for high-speed digital printing
10 to 30 parts by weight of a polyurethane-based (PU) binder, 1 to 5 parts by weight of calcium chloride (CaCl 2 ), 5 to 20 parts by weight of ethylene glycol (EG), 1 to 5 parts by weight of a crosslinking agent, and 40 to 83 parts by weight of water. ,
The polyurethane-based (PU) binder prepares a polyurethane resin, and uses any one cationic resin solution selected from the group consisting of SAC (Strongly Acidic Cation exchange resin) and WAC (Weakly Acidic Cation exchange resin) for the polyurethane resin. prepared, and using a modified polyurethane modified by mixing the polyurethane resin and the cationic resin liquid at a weight ratio within the range of 6:4 to 7:3,
The crosslinking agent is one selected from the group consisting of diethanolamine, monoethylene glycol, diethylene glycol, 1,6-hexanediol diacylate, trimethylolpropane, and triacrylate. A pretreatment composition for digital printing.
상기 폴리우레탄은 수평균분자량이 2,000~5,000인 폴리에테르계 폴리올 30~55 중량%와 수평균분자량이 1,000~3,000인 폴리에스테르계 폴리올 45~70 중량%의 혼합물로 이루어진 것을 특징으로 하는 폴리우레탄을 이용한 고속 디지털 날염용 전처리제 조성물.According to claim 1,
The polyurethane is composed of a mixture of 30 to 55% by weight of a polyether polyol having a number average molecular weight of 2,000 to 5,000 and 45 to 70% by weight of a polyester polyol having a number average molecular weight of 1,000 to 3,000. Pretreatment composition for high-speed digital printing using
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| WO2019216279A1 (en) | 2018-05-11 | 2019-11-14 | 株式会社クラレ | Method for modifying polyurethane, polyurethane, polishing pad, and method for modifying polishing pad |
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| JP2009046780A (en) | 2007-08-21 | 2009-03-05 | Dic Corp | Ink jet receiving agent for fiber substrate and ink jet recording medium using the same |
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