KR101387104B1 - Disperse dye for polylactic acid fibers and black dye composition comprising thereof - Google Patents

Disperse dye for polylactic acid fibers and black dye composition comprising thereof Download PDF

Info

Publication number
KR101387104B1
KR101387104B1 KR1020110136747A KR20110136747A KR101387104B1 KR 101387104 B1 KR101387104 B1 KR 101387104B1 KR 1020110136747 A KR1020110136747 A KR 1020110136747A KR 20110136747 A KR20110136747 A KR 20110136747A KR 101387104 B1 KR101387104 B1 KR 101387104B1
Authority
KR
South Korea
Prior art keywords
dye
formula
blue
pla
disperse
Prior art date
Application number
KR1020110136747A
Other languages
Korean (ko)
Other versions
KR20130069162A (en
Inventor
이기승
최민영
이규환
유의상
이현경
서희성
Original Assignee
대영산업 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 대영산업 주식회사 filed Critical 대영산업 주식회사
Priority to KR1020110136747A priority Critical patent/KR101387104B1/en
Publication of KR20130069162A publication Critical patent/KR20130069162A/en
Application granted granted Critical
Publication of KR101387104B1 publication Critical patent/KR101387104B1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C09B67/0051—Mixtures of two or more azo dyes mixture of two or more monoazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
    • C09B29/3608—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered heterocyclic ring with only one nitrogen as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3682—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only sulfur as heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • 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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs

Abstract

본 발명은 폴리락트산(PLA) 섬유의 염색에 이용되는 분산염료에 관한 것으로, 본 발명은 하기 화학식 1의 청색 분산염료, 화학식 2의 적색 분산염료, 화학식 3의 황색 분산염료 화합물 제공하는 한편, 이들을 혼합한 흑색 분산염료 조성물을 제공한다.
[화학식 1]

Figure 112011100441488-pat00030

상기 화학식에서, R1은 -NO2 또는 -COOCH2H3 이고, R2는 -H, -CH3 또는 -NH-CO-CH3 이고, R3는 -H 또는 -OCH3 이고, R4는 -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이고, R5는 -CH2CH3, -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이다.
[화학식 2]
Figure 112011100441488-pat00031

상기 화학식에서, R1은 -CH3 또는 -NH-CO-CH3 이고, R2는 -H 또는 -OCH3 이고, R3 및 R4 는 독립적으로 -CH2CH=CH2, -CH2CH3 또는 -CH2CH2-O-COCH3 이다.
[화학식 3]
Figure 112011100441488-pat00032
The present invention relates to a disperse dye used for dyeing polylactic acid (PLA) fibers, the present invention provides a blue disperse dye of formula (1), a red disperse dye of formula (2), a yellow disperse dye compound of formula (3), It provides a mixed black dispersion dye composition.
[Chemical Formula 1]
Figure 112011100441488-pat00030

In the formula, R 1 is -NO 2 or -COOCH 2 and H 3, R 2 is -H, -CH 3 Or -NH-CO-CH 3 , R 3 is -H or -OCH 3 , R 4 is -CH 2 CH 2 -O-COCH 3 or -CH 2 CH 2 -O-CH 2 CH 2 OH, R 5 is —CH 2 CH 3 , —CH 2 CH 2 —O—COCH 3 or —CH 2 CH 2 —O—CH 2 CH 2 OH.
(2)
Figure 112011100441488-pat00031

In the above formula, R 1 is -CH 3 Or -NH-CO-CH 3 , R 2 is -H or -OCH 3 , and R 3 and R 4 are independently -CH 2 CH = CH 2 , -CH 2 CH 3 or -CH 2 CH 2 -O -COCH 3 .
(3)
Figure 112011100441488-pat00032

Description

폴리락트산(ＰＬＡ) 섬유용 분산염료 및 이를 포함하는 흑색 염료 조성물{Disperse dye for polylactic acid fibers and black dye composition comprising thereof}Disperse dye for polylactic acid fibers and black dye composition comprising thereof

본 발명은 폴리락트산 섬유(이하, PLA 섬유)의 염색에 이용되는 분산염료에 관한 것으로, 보다 상세하게는 티오펜계 디아조 성분을 함유하는 청색계열 분산염료 화합물과, 프탈이미드계 디아조 성분을 함유하는 적색 및 황색계열 분산염료 화합물에 관한 것이며, 나아가 상기 분산염료 화합물을 포함하여 PLA 섬유 염색시 높은 염착율을 가지고, 심색 및 제반 견뢰도가 우수한 흑색 분산염료 조성물에 관한 것이다.
The present invention relates to a disperse dye used for dyeing polylactic acid fiber (hereinafter referred to as PLA fiber), and more particularly, to a blue-based disperse dye compound containing a thiophene diazo component and a phthalimide diazo component. It relates to a red and yellow series disperse dye compound containing, and furthermore to a black disperse dye composition having a high dyeing rate during dyeing PLA fiber, including the disperse dye compound, excellent in deep color and overall fastness.

폴리락트산(Polylactic acid, 이하 'PLA')는 유산(lactic acid)을 축중합시켜 생성되는 고분자 물질로서 1932년에 최초 개발되었다. 이러한 PLA는 일반 석유계 합성물과 달리 천연원료로부터 생산되므로 높은 생분해성을 가진다. 그러나 이러한 높은 생분해성에도 불구하고, PLA는 높은 제조 비용으로 인해 의료용 봉합사, 이식부품 등과 같은 특수 의료 재료로 한정되어 사용되어 왔다. 근래에 들어서 옥수수 전분을 발효, 글루코스를 거쳐 생산된 유산(latic acid)을 중합하는 새로운 합성 방법이 개발되면서 비용과 생산량 면에서 PLA의 새로운 전환기가 도래하였고, 점차 다양한 산업적 용도로 이용이 증대되고 있다.Polylactic acid (PLA) was first developed in 1932 as a polymer material produced by the polycondensation of lactic acid. Such PLA is produced from natural raw materials, unlike ordinary petroleum compounds, and thus has high biodegradability. However, despite this high biodegradability, PLA has been limited to special medical materials such as medical sutures, implants and the like due to high manufacturing costs. In recent years, new synthetic methods have been developed to ferment corn starch and polymerize latic acid produced by glucose, resulting in a new turnaround time for PLA in terms of cost and yield, and is increasingly being used for various industrial applications. .

PLA 섬유는 외관이 투명하며, 융점, 인장강도, 굴곡강도, 물성조절이 용이할 뿐 아니라, 100%의 직·편직물은 물론, 면·양모·견 등의 천연섬유나 레이온 등의 합성섬유와도 혼용성이 높으며, 종래 섬유에 비해 특유의 경량감이 있고, 새로운 촉감의 소재로 의류 분야에서 각광을 받고 있다. PLA 섬유의 큰 장점은 생분해적 특성으로, 토양에서 30일 이상 방치시 미생물 등에 의해 물과 이산화탄소로 90% 이상 분해되는 것으로 보고된 바 있다.PLA fiber is transparent in appearance, and it is easy to control melting point, tensile strength, flexural strength, and physical properties, as well as 100% of woven and knitted fabrics, as well as natural fibers such as cotton, wool, and dogs, and synthetic fibers such as rayon. It has high compatibility, has a unique lightness compared to the conventional fiber, and has been spotlighted in the field of clothing as a new touch material. The great advantage of PLA fiber is its biodegradable properties, which have been reported to be decomposed more than 90% by water and carbon dioxide by microorganisms when left in the soil for more than 30 days.

근래들어 PLA 섬유는 블라우스, 드레스, 스포츠 웨어 등의 의류로 이용이 확대되면서 효과적인 염색방법이 요구되고 있다. PLA 섬유는 폴리에스테르(PET, polyester) 섬유에서와 같은 에스테르기(-COO-)를 가지므로 분산염료(Disperse dye)와 수소결합에 의한 염착이 가능하다. PET 염색용 분산염료에 대해서는 이미 오래전부터 연구가 진행되어, 충분히 많은 염료들이 상업적으로 시판되고, 염료업계에서는 정형화되어 있다.In recent years, PLA fiber has been increasingly used as a garment such as blouse, dress, sports wear, etc., and an effective dyeing method is required. PLA fiber has the same ester group (-COO-) as in polyester (PET, polyester) fiber, so dyeing by disperse dye and hydrogen bonding is possible. Disperse dyes for PET dyeing have already been studied for a long time, and enough dyes are commercially available and have been formalized in the dye industry.

그러나, PLA 섬유는 최근들어 의류 재료로 각광받고 있는 만큼, 아직 PLA 섬유에 고유 특성에 맞는 충분한 염료에 대한 연구는 미진한 상태이다. However, PLA fiber has recently been spotlighted as an apparel material, and there is a lack of research on sufficient dyes for PLA fiber.

PLA와 PET가 에스테르기(-COO-)를 가지는 점에서는 유사하나, PET는 벤젠기에 따른 분자 구조가 강직한(rigid) 데 반해, PLA는 유연한(flexible) 분자 구조를 가지고 있다. 또한, PET 섬유는 융점이 260℃ 부근인 반면, PLA 섬유는 160-170℃ 부근이어서 고온염색시 인열강도가 저하되기 때문에 PET 섬유에 비해 저온처리하여야 한다. PET 섬유는 일반적으로 약 130℃ 에서 염색되는 반면, PLA 섬유는 그 보다 낮은 약 110℃ 에서 염색되므로 심색도가 낮아지는 경향이 있다.PLA and PET are similar in that they have an ester group (-COO-). However, PET has a rigid molecular structure, whereas PLA has a rigid molecular structure according to a benzene group. In addition, since the PET fiber has a melting point around 260 ° C., the PLA fiber has a temperature lower than that of the PET fiber because the tear strength is lowered at around 160-170 ° C. when the high temperature dyeing is performed. PET fibers are generally dyed at about 130 ° C., while PLA fibers are dyed at lower about 110 ° C. and therefore tend to have a lower depth.

Figure 112011100441488-pat00001
Figure 112011100441488-pat00001

또한, PLA 섬유는 PET 섬유와는 염착성질이 달라 PET 범용 분산염료로 염색하는 경우 PET 섬유에 비해 단파장으로 이행되어 색상(color shade) 변화가 일어나는 경향이 있다.In addition, PLA fibers have different dyeing properties from PET fibers, and when dyed with PET general-purpose disperse dyes, PLA fibers tend to be shifted to shorter wavelengths, resulting in a change in color shade.

따라서, 종래 PET 섬유용 분산염료가 PLA 섬유에 동일하게 적용되어 목적하는 색상(color shade), 우수한 염착율 및 심색을 가지는 것으로 예측하기는 어렵다.Therefore, it is difficult to predict that conventional dispersion dyes for PET fibers have the same color shade, excellent dyeing ratio, and deep color as applied to PLA fibers.

특히 흑색 염료는 청색계열, 적색계열, 황색계열 등 여러 색채의 염료의 혼합물로 이루어지는 데, 이들 각 염료의 색상, 염착율, 심색도 등이 서로 조화되어야 순수한 흑색으로 발색될 수 있다. 각 염료의 초기 염착율(PLA는 100~110℃에서 초기 염착율)은 흑색 염료에 있어 매우 중요하다. 혼합조성물의 각각의 염료는 서로 경쟁하듯 섬유에 염착되므로, 초기 염착율이 낮으면 섬유의 염착 부위(공간)에서 다른 염료에 밀려 효과적인 염착이 불가능하게 되고, 궁극적으로는 각 색상 조합이 불균형하게 되어 원하는 순수한 흑색을 얻기 힘들다.
In particular, the black dye is composed of a mixture of dyes of various colors, such as blue, red, yellow, etc., the color, dyeing rate, deep color of each of these dyes can be developed in pure black color. The initial dyeing rate of each dye (PLA initial dyeing rate at 100-110 ° C.) is very important for black dyes. Since each dye of the mixed composition is dyed to the fibers as competing with each other, a low initial dyeing rate is pushed by other dyes at the dyeing site (space) of the fiber, making it impossible to effectively dye, and ultimately unbalanced color combinations It's hard to get the pure black you want.

PLA 섬유는 상술한 바와 같이, 최근들어 의류 재료로 주목받는 만큼, PLA 염색에 적합한 분산염료 개발은 아직 미진한 상태이다.As described above, PLA fiber is recently attracting attention as a clothing material, the development of dispersion dyes suitable for PLA dyeing is still insufficient.

따라서, 본 발명은 PLA 섬유에 대해 염착율이 높고, 색도 및 견뢰도가 우수한 청색계열, 적색계열, 황색계열의 신규한 분산염료를 제공하며, 나아가 상기 분산염료를 포함하는 흑색 염료 조성물을 제공하는 데 그 목적이 있다.
Accordingly, the present invention provides a novel dyes of blue, red and yellow dyes having high dyeing rate and excellent color and fastness to PLA fibers, and furthermore, to provide a black dye composition comprising the dispersion dyes. The purpose is.

상술한 제반 문제를 해결하기 위하여,In order to solve the above-mentioned problems,

본 발명은 하기 화학식 1의 구조를 가지는 청색계열의 분산염료 화합물를 제공한다.The present invention provides a blue-based dispersed dye compound having a structure of Formula 1 below.

[화학식 1][Chemical Formula 1]

Figure 112011100441488-pat00002
Figure 112011100441488-pat00002

상기 화학식에서, R1은 -NO2 또는 -COOCH2H3 이고, R2는 -H, -CH3 또는 -NH-CO-CH3 이고, R3는 -H 또는 -OCH3 이고, R4는 -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이고, R5는 -CH2CH3, -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이다.In the formula, R 1 is -NO 2 or -COOCH 2 and H 3, R 2 is -H, -CH 3 Or -NH-CO-CH 3 , R 3 is -H or -OCH 3 , R 4 is -CH 2 CH 2 -O-COCH 3 or -CH 2 CH 2 -O-CH 2 CH 2 OH, R 5 is —CH 2 CH 3 , —CH 2 CH 2 —O—COCH 3 or —CH 2 CH 2 —O—CH 2 CH 2 OH.

상기 청색계열 분산염료는 PLA 섬유의 염색특성이 우수하다. 특히, 하기 화학식 1-1의 분산염료는 염색공정의 초기 염착율이 매우 우수할 뿐 아니라, 색상도 순수 청색으로 발색되며, 심색도 매우 우수한 것으로 확인되었다.The blue-based dispersion dyes have excellent dyeing properties of PLA fibers. In particular, the disperse dye of the following Chemical Formula 1-1 is not only very excellent in the initial dyeing rate of the dyeing process, the color is also pure blue color, it was confirmed that the deep color is also very excellent.

[화학식 1-1][Formula 1-1]

Figure 112011100441488-pat00003
Figure 112011100441488-pat00003

한편, 본 발명은 하기 화학식 2의 구조를 가지는 적색계열의 분산염료 화합물을 제공한다.On the other hand, the present invention provides a red-based dispersion dye compound having a structure of formula (2).

[화학식 2](2)

Figure 112011100441488-pat00004
Figure 112011100441488-pat00004

상기 화학식에서, R1은 -CH3 또는 -NH-CO-CH3 이고, R2는 -H 또는 -OCH3 이고, R3 및 R4 는 독립적으로 -CH2CH=CH2, -CH2CH3 또는 -CH2CH2-O-COCH3 이다.In the above formula, R 1 is -CH 3 Or -NH-CO-CH 3 , R 2 is -H or -OCH 3 , and R 3 and R 4 are independently -CH 2 CH = CH 2 , -CH 2 CH 3 or -CH 2 CH 2 -O -COCH 3 .

상기 적색계열의 분산염료는 하기 화학식 2-1인 것인 가장 바람직하다.The red series of the disperse dye is most preferably the formula 2-1.

[화학식 2-1][Formula 2-1]

Figure 112011100441488-pat00005
Figure 112011100441488-pat00005

또 한편, 본 발명은 하기 화학식 3의 구조를 가지는 황색계열의 분산염료 화합물을 제공한다.On the other hand, the present invention provides a yellow-based dispersion dye compound having a structure of the formula (3).

[화학식 3](3)

Figure 112011100441488-pat00006
Figure 112011100441488-pat00006

상기 분산염료는 폴리락트산(PLA) 섬유의 염색에 바람직하게 사용될 수 있다.The disperse dye may be preferably used for dyeing polylactic acid (PLA) fibers.

또 한편, 본 발명은 상기 청색계열, 적색계열 및 황색계열의 분산염료 화합물 중 1종 이상, 바람직하게는 이들 모두를 포함하는 흑색계열 분산염료 조성물을 제공한다. 상기 흑색계열 분산염료 화합물 전체 100 중량%를 기준으로 상기 청색계열의 분산염료 화합물은 40 ~ 90 중량%이고, 상기 적색계열의 분산염료 화합물은 5 ~ 40 중량%이고, 상기 황색계열의 분산염료 화합물은 5 ~ 30 중량%을 포함하는 것이 바람직하다.
On the other hand, the present invention provides a black-based dispersed dye composition comprising at least one, preferably all of the above-mentioned blue-based, red-based and yellow-based dispersed dye compounds. The blue-based dispersed dye compound is 40 to 90% by weight, the red-based dispersed dye compound is 5 to 40% by weight, and the yellow-based dispersed dye compound based on 100% by weight of the total black-based dispersed dye compound. It is preferable to include 5 to 30% by weight of silver.

본 발명에 따라 제조된 청색 염료, 적색 염료, 황색 염료는 PLA 섬유 염색시 초기 염착율이 매우 우수할 뿐 아니라, 염료별 색상(color shade) 및 견뢰도가 우수하며, 이들 각 염료를 혼합하여 제조된 흑색 염료의 경우 PLA 섬유에 대한 염착율 및 견뢰도가 매우 우수하여 PLA 염색에 유용하게 이용될 수 있다.
The blue dyes, red dyes, and yellow dyes prepared according to the present invention not only have excellent initial dyeing rate when dyeing PLA fibers, but also have excellent color shade and color fastness for each dye, and are prepared by mixing each of these dyes. In the case of a black dye, the dyeing rate and color fastness to the PLA fiber is very excellent, and thus may be usefully used for PLA dyeing.

도 1은 공지 염료인 분산염료 청색 148의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 2는 공지 염료인 분산염료 청색 106의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 3은 공지 염료인 분산염료 청색 79의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 4는 공지 염료인 분산염료 청색 60의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 5는 공지 염료인 분산염료 청색 56의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 6은 분산염료 청색 148의 변형 화합물(화학식 D1)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 7은 분산염료 청색 148의 또 다른 변형 화합물(화학식 D2)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 8은 분산염료 청색 148의 또 다른 변형 화합물(화학식 D3)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 9는 분산염료 청색 148의 또 다른 변형 화합물(화학식 D4)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 10은 분산염료 청색 106의 변형 화합물(화학식 D5)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 11은 본 발명의 일 실시예에 따른 청색계열 분산염료(화학식 1-1)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 12는 본 발명의 일 실시예에 따른 청색계열 분산염료(화학식 1-9)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 13은 본 발명의 일 실시예에 따른 적색계열 분산염료(화학식 2-1)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 14는 본 발명의 일 실시예에 따른 황색계열 분산염료(화학식 3)의 PLA 섬유에 대한 시간별 염착율 및 색상 변화를 나타낸 도이다.
도 15a는 본 발명에 따른 흑색 분산염료(시료명: ② "A")와 종래 상업용 PET용 흑색 염료(시료명: ① "Black")로 염색한 PLA 섬유에 대하여 표준시험 방식에 따른 세탁견뢰도, 마찰견뢰도, 일광견뢰도, 땀견뢰도 및 승화견뢰도를 테스트 결과이다.
도 15b는 종래 상업용 PET용 흑색 염료(시료명: ① "Black")의 PLA 견뢰도 테스트 사진이다.
도 15c는 본 발명에 따른 흑색 분산염료(시료명: ② "A")의 PLA 테스트 사진이다.1 is a diagram showing the time-dependent dyeing rate and color change of the PLA fiber of the known dye dye dispersion blue 148.
Figure 2 is a diagram showing the time-dependent dyeing rate and color change for PLA fiber of the dye dye blue 106, a known dye.
Figure 3 is a diagram showing the time-dependent dyeing rate and color change of PLA fiber of the dispersion dye blue 79, a known dye.
Figure 4 is a diagram showing the time-dependent dyeing rate and color change for PLA fiber of the dispersion dye blue 60, a known dye.
5 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the disperse dye blue 56, a known dye.
FIG. 6 is a view showing the time-dependent dyeing rate and color change of PLA fiber of the modified compound of the disperse dye blue 148 (Formula D1).
FIG. 7 is a view showing the time-dependent dyeing rate and color change of PLA fiber of another modified compound of the disperse dye blue 148 (Formula D2).
FIG. 8 is a graph showing the time-dependent dyeing rate and color change of PLA fiber of another modified compound of the disperse dye blue 148 (Formula D3).
FIG. 9 is a view showing the time-dependent dyeing rate and color change of PLA fiber of another modified compound of the disperse dye blue 148 (Formula D4).
10 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the modified compound of the disperse dye blue 106 (Formula D5).
Figure 11 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the blue-based dispersion dye (Formula 1-1) according to an embodiment of the present invention.
12 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the blue-based dispersion dye (Formula 1-9) according to an embodiment of the present invention.
13 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the red-based dispersion dye (Formula 2-1) according to an embodiment of the present invention.
14 is a view showing the time-dependent dyeing rate and color change of the PLA fiber of the yellow-based dispersion dye (Formula 3) according to an embodiment of the present invention.
Figure 15a is a fastness to wash, friction fastness according to the standard test method for the PLA fiber dyed with a black dispersion dye (sample name: ② "A") and a conventional black dye for commercial PET (sample name: ① "Black") according to the present invention The results of the test were tested for daylight fastness, sweat fastness and sublimation fastness.
15B is a PLA fastness test photograph of a conventional black dye for commercial PET (sample name: ① "Black").
Figure 15c is a PLA test picture of the black dispersion dye (sample name: ② "A") according to the present invention.

본 발명자들은 PLA 섬유에 대하여 색상, 색도 및 견뢰도 등 염색성이 우수한 신규 분산염료 화합물을 개발하는 한편, 나아가 이들을 혼합한 흑색 분산염료 조성물을 개발하기 위해 다음과 같이 일련의 연구를 진행하였다.
The present inventors have developed a series of new disperse dye compounds having excellent dyeing properties such as color, chromaticity and color fastness of PLA fibers, and further develop a black disperse dye composition containing these as follows.

상업용 Commercial PETPET 염색용 분산염료의  Of disperse dyes for dyeing PLAPLA 섬유 염색성 검토 Fiber dyeability review

PLA 섬유용 청색계열 분산염료를 개발하기 위하여, 상용적으로 시판되는 하기 표 1의 PET용 청색계열 분산염료를 가지고, 110℃에서 PLA 섬유를, 130℃에서 PET(Polyester) 섬유를 염색하여 각각의 염색 특성을 확인하였다.In order to develop a blue-based dispersion dye for PLA fiber, with a commercially available blue-based dispersion dye for PET in Table 1, PLA fiber at 110 ℃, dyeing PET (Polyester) fiber at 130 ℃ each The staining characteristics were confirmed.

PLA 섬유용 청색계열 분산염료는 다른 염료(적색계열, 옐루우계열)와의 염착 균형을 맞추기 위하여 염색공정의 100~110℃ 초기 시점에서 염착율이 높아야 한다. 또한 색상(color shade)이 선명한 청색를 띠어야 하고, 색도도 우수하여 한다.In order to balance dyeing with other dyes (red, yellow), PLA-based blue dyes should have high dyeing rates at the beginning of the dyeing process. Also, the color shade should be vivid blue and the chromaticity is also excellent.

PLA 섬유를 각 염료가 용해된 염액에 함침시키고, 2℃/분의 속도로 110℃까지 승온시킨 다음, 온도를 유지하면서 40분간 염색시켰다. 이후 2℃/분의 속도로 서서히 냉각시킨 다음, 가성소다 및 차아황산나트륨이 용해된 후처리액에 넣어 15분간 침지한 다음, 수세한 후 건조시켰다. PET 섬유는 동일하게 실시하되 130℃까지 승온시켜 염색시켰다.PLA fibers were impregnated in the salt solution in which each dye was dissolved, and the temperature was raised to 110 ° C. at a rate of 2 ° C./min, and then dyed for 40 minutes while maintaining the temperature. Thereafter, the mixture was slowly cooled at a rate of 2 ° C./minute, and then immersed in a post-treatment solution in which caustic soda and sodium hyposulfate were dissolved, soaked for 15 minutes, washed with water, and dried. PET fibers were subjected to the same but dyed by raising the temperature to 130 ℃.

성분 계열Component series 분산염료명Disperse Dye Name 구조식constitutional formula Benzisothiazole계
Azo계Benzisothiazole series
Azo series Disperse Blue 148Disperse Blue 148

Figure 112011100441488-pat00007
Figure 112011100441488-pat00007
Thiazole계
Azo계Thiazole
Azo series Disperse Blue 106Disperse Blue 106
Figure 112011100441488-pat00008
Figure 112011100441488-pat00008
 Benzene계
Azo계Benzene series
Azo series Disperse Blue 79Disperse Blue 79
Figure 112011100441488-pat00009
Figure 112011100441488-pat00009
 anthraquinone계anthraquinone series Disperse Blue 60Disperse Blue 60
Figure 112011100441488-pat00010
Figure 112011100441488-pat00010
 anthraquinone계anthraquinone series Disperse Blue 56Disperse Blue 56
Figure 112011100441488-pat00011
Figure 112011100441488-pat00011

도 1 내지 도 5는 상기 표 1의 각 염료의 염색시간별 염착율(dye adsorption rate)의 변화 및 색상(color shade)을 나타낸다.1 to 5 show the change and color shade of dye adsorption rate for each dye of Table 1 above.

이들 분산염료는 PET 섬유에 대해서는 비교적 양호하였으나, PLA 섬유에 대해서는 안트라퀴논(anthraquinone)계 분산염료 청색 60 및 청색 56은 초기 염착률(the initial adsorption rate)이 낮을 뿐 아니라 색도도 낮아 본 발명에서 요구되는 염색성(dyeability)을 충족하지 못하였고(도 4 및 도 5 참조), 아조(azo)계 분산염료 중에서 벤젠(benzene)계의 경우 초기 염착률이 낮고, 진보라색(dark violet)으로 발색되어 역시 본 발명에 요구되는 염색성을 충족하지 못하였다(도 3 참조).These disperse dyes are relatively good for PET fibers, but for an PLA fiber, anthraquinone-based disperse dyes blue 60 and blue 56 not only have low initial adsorption rate but also low color, which are required by the present invention. It did not meet the dyeability (dyeability) (see Figs. 4 and 5), and in the azo (azo) disperse dyes in the case of the benzene (benzene) low initial dyeing rate, it is also developed as a dark violet (violet violet) It did not meet the dyeability required for the present invention (see Figure 3).

벤즈이소티아졸계 아조염료인 분산염료 청색 148과, 티아졸계 아조염료인 분산염료 청색 106의 경우 100 ~ 110℃에서 초기 염착률은 양호하였으나, PLA 섬유에서 분산염료 청색 148은 적보라색(reddish violet)으로, 분산염료 청색 106은 진보라색으로 발색되어 본 발명에서 이루고자 하는 선명한 청색 분산염료는 아니었다(도 1 및 2 참조).
The disperse dye blue 148, which is a benzisothiazole azo dye, and the disperse dye blue 106, which is a thiazole azo dye, have a good initial dyeing rate at 100 to 110 ° C., but the disperse dye blue 148 is reddish violet in PLA fiber. As a result, the disperse dye blue 106 was not a vivid blue disperse dye to be achieved in the present invention by developing a progressive color (see FIGS. 1 and 2).

신규 분산염료 유도체 합성Synthesis of New Disperse Dye Derivatives

이에 본 발명자들은 초기 염착율이 우수한 상기 분산염료 청색 148와 청색 106의 구조로부터 하기 표 2에 표시된 신규 유도체를 설계·합성하는 한편, 신규 티오펜계 유도체를 합성하였다.The present inventors designed and synthesized the novel derivatives shown in Table 2 from the structures of the disperse dyes blue 148 and blue 106 having excellent initial dyeing rates, and synthesized new thiophene derivatives.

염료 계열Dye series 구조식constitutional formula 화학식 D1Formula D1 Benzisothiazole계Benzisothiazole series

Figure 112011100441488-pat00012
Figure 112011100441488-pat00012
화학식 D2Formula D2 Benzisothiazole계Benzisothiazole series
Figure 112011100441488-pat00013
Figure 112011100441488-pat00013
 화학식 D3Formula D3 Benzisothiazole계Benzisothiazole series
Figure 112011100441488-pat00014
Figure 112011100441488-pat00014
 화학식 D4Chemical Formula D4 Benzisothiazole계Benzisothiazole series
Figure 112011100441488-pat00015
Figure 112011100441488-pat00015
 화학식 D5Formula D5 Thiazole계Thiazole
Figure 112011100441488-pat00016
Figure 112011100441488-pat00016
 화학식 1-1(1-1) Thiophene계Thiophene
Figure 112011100441488-pat00017
Figure 112011100441488-pat00017
 화학식 1-91-9 Thiophene계Thiophene
Figure 112011100441488-pat00018
Figure 112011100441488-pat00018

염료 합성 방법은 2-아미노-5-니트로벤즈이소티아졸(2-amino-5-nitrobenzisothiazole), 2-아미노-5-니트로티아졸(2-amino-5-nitrothiazole), 2-아미노-3,5-디니트로티오펜(2-amino-3,5-dinitrothiophene) 각각을 디아조체(diazo agent)로 하여 아미노기를 디아조화시킨 다음, 상기 각각의 커플러(coupler)와 커플링 반응시켜 염료를 합성하였다. 커플러체의 -N(CH2CH2OCOCH3)기는 -N(CH2CH2OH)기를 아세틸화(acetylation)반응시켜 치환시켰다.
Dye synthesis methods include 2-amino-5-nitrobenzisothiazole, 2-amino-5-nitrothiazole, 2-amino-3, Each of 5-dinitrothiophene (2-amino-3,5-dinitrothiophene) was used as a diazo agent to diazotize an amino group, and then coupled with each of the couplers to synthesize a dye. . The -N (CH 2 CH 2 OCOCH 3 ) group of the coupler was substituted by acetylation reaction of the -N (CH 2 CH 2 OH) group.

실시예Example 1: 청색 분산염료의 제조(화학식 1-1) 1: Preparation of Blue Disperse Dyes (Formula 1-1)

진한 황산(농도 98%) 120중량부에 아질산나트륨 6.2중량부를 실온에서 천천히 가입하고, 60~70℃를 유지하면서 1시간 동안 교반하였다. 반응물을 10℃ 이하로 냉각시킨 후, 같은 온도에서 2-아미노-3,5-디니트로티오펜(2-amino-3,5-dinitrothiophene) 14.9중량부를 약 30분 동안 천천히 가하였다. 5~10℃에서 1시간 교반하여 디아조화시켰다.6.2 parts by weight of sodium nitrite was slowly added to 120 parts by weight of concentrated sulfuric acid (concentration 98%) at room temperature, and stirred for 1 hour while maintaining 60 to 70 ° C. After the reaction was cooled to 10 ° C. or lower, 14.9 parts by weight of 2-amino-3,5-dinitrothiophene was slowly added at about the same temperature for about 30 minutes. It diazotized by stirring at 5-10 degreeC for 1 hour.

물 400중량부, 얼음 200중량부, 아세트산 20중량부의 혼합액을 만든 후 커플러체인 N,N-디아세톡시에틸-m-톨루이딘(N,N-diacethoxyethyl-m-toluidine) 22.1중량부를 완전히 용해시킨 다음 10℃ 미만으로 냉각시켰다. 디아조 화합물을 0~10℃에서 약 1시간 동안 가하고, 같은 온도에서 1시간 동안 교반하였다. 10% 희석시킨 소듐 하이드록시드를 pH 3~4가 될때까지 첨가하였다. 그 후 감압여과 및 물로 수세하여 청색 염료를 수득하였다(수율:75.06%).400 parts by weight of water, 200 parts by weight of ice and 20 parts by weight of acetic acid were prepared, and 22.1 parts by weight of the coupler chain N, N-diacethoxyethyl-m-toluidine was completely dissolved. Cool to below 10 ° C. The diazo compound was added at 0-10 ° C. for about 1 hour and stirred at the same temperature for 1 hour. 10% diluted sodium hydroxide was added until pH 3-4. Then, the resultant was filtered under reduced pressure and washed with water to give a blue dye (yield: 75.06%).

상기 순수 청색 염료 100중량부를 나프탈렌 설포산 포름알데히드 축합형 분산제 50중량부와 리그닌 설폰산계 분산제 50중량부 및 물 80중량부에 가입하여 염료입자의 90% 이상의 0.5㎛미만이 되도록 분쇄하여 액상의 염료 분산액을 제조하였다.
100 parts by weight of the pure blue dye is added to 50 parts by weight of naphthalene sulfoic acid formaldehyde condensation type dispersant, 50 parts by weight of lignin sulfonic acid-based dispersant and 80 parts by weight of water to grind to 90% or more of the dye particles to less than 0.5㎛, liquid dye A dispersion was prepared.

실시예Example 2:  2: 청색blue 분산염료의 제조(화학식 1-9) Preparation of Disperse Dyes (Formula 1-9)

상기 실시예 1과 동일한 방법으로 실시하되, 디아조체로서 2-아미노-3-에톡시카르보닐-5-니트로티오펜(2-amino-3-ethoxycarbonyl-5-nitrothiophene)을, 커플러체로 N,N-디아세톡시에틸-아미노 아세트아닐라이드(N,N-diacetoxyethyl-amino acetanilide)를 이용하여 합성하였다.
In the same manner as in Example 1, 2-amino-3-ethoxycarbonyl-5-nitrothiophene as a diazo, N, N as a coupler -Diacetoxyethyl-amino acetanilide (N, N-diacetoxyethyl-amino acetanilide) was synthesized.

실험예Experimental Example 1: 합성된 청색 분산염료의 염색성 평가 1: Evaluation of Dyeability of Synthetic Blue Disperse Dyes

상기 표 2에 표시된 분산염료를 이용하여 PLA 섬유 염색을 실시하였다.PLA fiber dyeing was performed using the dispersion dyes shown in Table 2 above.

PLA 섬유를 각 염료가 용해된 염액에 함침시키고, 2℃/분의 속도로 110℃까지 승온시킨 다음, 온도를 유지하면서 40분간 염색시켰다.PLA fibers were impregnated in the salt solution in which each dye was dissolved, and the temperature was raised to 110 ° C. at a rate of 2 ° C./min, and then dyed for 40 minutes while maintaining the temperature.

상기 염료의 염색시간별 염착율의 변화 및 색상을 도 6 내지 12에 나타내었다.6 to 12 show changes in color and dyeing rate of the dye by dyeing time.

화학식 D1, D3 및 D4는 초기 염착율이 매우 불량하였으며, 화학식 D3, D5는 초기 염착율은 양호하였으나, 각각 보라색(violet)과 적보라색(reddish violet)으로 발색되어 본 발명에 요구되는 청색은 아니었다.Formulas D1, D3, and D4 had very poor initial dyeing rates. Formulas D3 and D5 had good initial dyeing rates, but were not colored blue for the present invention because they were colored violet and reddish violet, respectively. .

반면, 본 발명의 화학식 1-1은 초기 염착율이 매우 양호하였으며, 색상도 선명한 청색(clear blue)으로 발색되어 PLA의 청색 염료로 매우 우수함을 확인할 수 있었다.On the other hand, Formula 1-1 of the present invention was very good initial dyeing rate, the color was also clear blue (clear blue) was confirmed that the blue dye of PLA is very excellent.

본 발명의 화학식 1-9는 적청색(reddish blue)으로 발색되었으나, 초기 염착율 및 심색이 우수함을 확인할 수 있었다.
Formula 1-9 of the present invention was colored in reddish blue, but it was confirmed that the initial dyeing rate and deep color were excellent.

실시예Example 3 내지 10 3 to 10

상기 실시예 1과 동일하게 실시하되, 디아조체 및 커플러의 치환기를 하기 표 3과 같이 변화시켜 분산염료를 합성하였다.In the same manner as in Example 1, the dispersing dye was synthesized by changing the substituents of the diazo body and the coupler as shown in Table 3 below.

Figure 112011100441488-pat00019
Figure 112011100441488-pat00019
RR 1One RR 22 RR 33 RR 44 RR 55 화학식 1-21-2 -NO2 -NO 2 -CH3 -CH 3 -H-H -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH3 -CH 2 CH 3 화학식 1-31-3 -NO2 -NO 2 -CH3 -CH 3 -H-H -CH2CH2-O-CH2CH2OH-CH 2 CH 2 -O-CH 2 CH 2 OH -CH2CH2-O-CH2CH2OH-CH 2 CH 2 -O-CH 2 CH 2 OH 화학식 1-4Formula 1-4 -NO2 -NO 2 -NH-CO-CH3 -NH-CO-CH 3 -H-H -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 화학식 1-51-5 -NO2 -NO 2 -NH-CO-CH3 -NH-CO-CH 3 -OCH3 -OCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 화학식 1-6Formula 1-6 -COOCH2CH3 -COOCH 2 CH 3 -H-H -H-H -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 화학식 1-7Formula 1-7 -COOCH2CH3 -COOCH 2 CH 3 -CH3 -CH 3 -H-H -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH3 -CH 2 CH 3 화학식 1-8Formula 1-8 -COOCH2CH3 -COOCH 2 CH 3 -CH33 -CH 33 -H-H -CH2CH2-O-CH2CH2OH-CH 2 CH 2 -O-CH 2 CH 2 OH -CH2CH2-O-CH2CH2OH-CH 2 CH 2 -O-CH 2 CH 2 OH 화학식 1-101-10 -COOCH2CH3 -COOCH 2 CH 3 -NH-CO-CH3 -NH-CO-CH 3 -OCH3 -OCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3 -CH2CH2-O-COCH3 -CH 2 CH 2 -O-COCH 3

상기 합성된 염료들로 PLA 를 염색한 결과, 화학식 1-2, 1-3, 1-4, 1-5는 녹청색(greenish blue)로 발색되고, 화학식 1-6, 1-7, 1-8, 1-10은 청색으로 발색되었다. 초기 염착율은 화학식 1-1의 청색 염료에 비해서는 다소 저하되었으나, PLA 염색용으로는 비교적 양호하였음을 확인하였다.
As a result of dyeing PLA with the synthesized dyes, Chemical Formulas 1-2, 1-3, 1-4, and 1-5 are colored in greenish blue, and Chemical Formulas 1-6, 1-7, and 1-8 , 1-10 was colored blue. The initial dyeing rate was slightly lower than that of the blue dye of Chemical Formula 1-1, but was confirmed to be relatively good for PLA staining.

적색계열 분산염료 개발Developed red series disperse dye

본 발명자들은 적색계열 분산염료를 개발하여 위하여 프탈이미드계 유도체를 합성하여 PLA 적용성을 확인한 결과, 하기 화학식 2의 구조를 가지는 적색계열의 분산염료 화합물의 물성이 우수한 것을 확인하였다.The present inventors synthesized a phthalimide-based derivative to develop a red-based dispersion dye, and confirmed the PLA applicability, it was confirmed that the physical properties of the red-based dispersion dye compound having the structure of formula (2).

[화학식 2](2)

Figure 112011100441488-pat00020
Figure 112011100441488-pat00020

상기 화학식에서, R1은 -CH3 또는 -NH-CO-CH3 이고, R2는 -H 또는 -OCH3 이고, R3 및 R4 는 독립적으로 -CH2CH=CH2, -CH2CH3 또는 -CH2CH2-O-COCH3 이다.
In the above formula, R 1 is -CH 3 Or -NH-CO-CH 3 , R 2 is -H or -OCH 3 , and R 3 and R 4 are independently -CH 2 CH = CH 2 , -CH 2 CH 3 or -CH 2 CH 2 -O -COCH 3 .

실시예Example 11: 적색 분산염료의 제조(화학식 2-1) 11: Preparation of red dispersion dye (Formula 2-1)

[반응식 1][Reaction Scheme 1]

Figure 112011100441488-pat00021
Figure 112011100441488-pat00021

상기 반응식 1과 같이 반응시켜 화학식 2-1의 적색 분산염료를 합성하였다.The reaction was carried out as in Scheme 1 to synthesize a red dispersion dye of Chemical Formula 2-1.

A. 4-A. 4- 니트로프탈이미드의Of nitrophthalimide 제조 Produce

진한 황산 280ml와 발연질산 48ml을 얼음 중탕을 이용하여 10~15℃로 유지하면서 혼합한 후, 프탈이미드 40g을 서서히 첨가하고 교반하여 실온에서 15시간 동안 반응시켰다. 반응 완료 후 얼음물에 천천히 교반한 후 얻어진 침전물을 감압여과하고 수세하여 4-니트로프탈이미드를 합성하였다(수율:81.2%).After mixing 280 ml of concentrated sulfuric acid and 48 ml of fuming nitric acid while maintaining the mixture at 10 to 15 ° C. using an ice bath, 40 g of phthalimide was slowly added and stirred to react at room temperature for 15 hours. After completion of the reaction, the mixture was stirred slowly in iced water, and the obtained precipitate was filtered under reduced pressure and washed with water to synthesize 4-nitrophthalimide (yield: 81.2%).

B. 4-B. 4- 아미노프탈이미드의Of aminophthalimide 제조 Produce

3구 플라스크에 150ml의 증류수와 염산(35%) 450ml를 혼합하였다. 플라스크에 SnCl 84g을 첨가하고, 교반하여 완전히 용해시킨다. 이 용액을 20℃로 유지하면서 위에 합성된 4-니트로프탈이미드 20g을 넣고 90분간 교반하면서 프탈이미드 아미노화물의 염산염을 석출하였다. 2l의 비이커에 얼음을 잘게 부수어 넣고, 아미노화 반응 용액을 서서히 첨가하여 교반하여 아미노화 염산염을 침전시킨 후 감압 여과 하여 4-아미노프탈이미드를 합성하였다(수율:61.2%).In a three-necked flask, 150 ml of distilled water and hydrochloric acid (35%) were mixed with 450 ml. 84 g of SnCl is added to the flask and stirred to dissolve completely. While maintaining the solution at 20 ° C., 20 g of 4-nitrophthalimide synthesized above was added thereto, followed by stirring for 90 minutes to precipitate hydrochloride of phthalimide amino acid. The ice was crushed into a 2 l beaker, the amination reaction solution was slowly added and stirred to precipitate the amino hydrochloride, followed by filtration under reduced pressure to synthesize 4-aminophthalimide (yield: 61.2%).

C. 염료 합성C. Dye Synthesis

진한 황산(농도 98%) 80중량부에 아질산나트륨 3.8중량부를 실온에서 천천히 가입하고, 60~70℃를 유지하면서 1시간 동안 교반 하였다. 반응물을 10℃ 이하로 냉각시킨 후, 같은 온도에서 위에서 합성한 디아조체인 4-아미노프탈이미드 8.1중량부를 약 30분 동안 천천히 가입하였다. 5~10℃에서 1시간 교반하여 디아조화 반응을 완결하였다. 물 200ml, 황산 5ml의 혼합액을 만든 후 커플러체인 3-dipropenyl amino-4-methoxy acetanilide 13중량부를 완전히 용해시킨 다음 10℃미만으로 냉각시켰다. 디아조 화합물을 0~10℃에서 약 1시간 동안 가입하고, 같은 온도에서 5~6시간 동안 교반 하였다. 10% 희석시킨 소듐 하이드록시드를 pH 3~4가 될때까지 첨가하였다. 그 후 감압여과 및 물로 수세하였다(수율:89.24%).80 parts by weight of concentrated sulfuric acid (concentration 98%) was added slowly 3.8 parts by weight of sodium nitrite at room temperature, and stirred for 1 hour while maintaining 60 ~ 70 ℃. After the reaction was cooled to 10 ° C. or lower, 8.1 parts by weight of 4-aminophthalimide, which was synthesized above, at the same temperature was slowly added for about 30 minutes. It stirred at 5-10 degreeC for 1 hour, and completed the diazotization reaction. A mixture of 200 ml of water and 5 ml of sulfuric acid was prepared, and then 13 parts by weight of 3-dipropenyl amino-4-methoxy acetanilide, a coupler chain, was completely dissolved and then cooled to less than 10 ° C. The diazo compound was joined at 0-10 ° C. for about 1 hour and stirred at the same temperature for 5-6 hours. 10% diluted sodium hydroxide was added until pH 3-4. Thereafter, the mixture was filtered under reduced pressure and washed with water (yield: 89.24%).

D. 염료 분산액 제조D. Dye Dispersion Preparation

상기 화학식 2-1의 순수 적색 염료 30중량부를 나프탈렌 설포산 포름알데히드 축합형 분산제 15중량부와 리그닌 설폰산계 분산제 15중량부 및 물 40중량부에 가입하여 염료입자의 90% 이상의 0.5㎛미만이 되도록 분쇄하여 액상의 염료 분산액을 제조하였다.
30 parts by weight of the pure red dye of Chemical Formula 2-1 is added to 15 parts by weight of naphthalene sulfoic acid formaldehyde condensation type dispersant, 15 parts by weight of lignin sulfonic acid-based dispersant and 40 parts by weight of water so as to be less than 0.5 µm of 90% or more of the dye particles. Grinding to prepare a liquid dye dispersion.

실험예Experimental Example 2: 합성된 적색 분산염료의 염색성 평가 2: Evaluation of Dyeability of Synthetic Red Disperse Dyes

상기 실험예 1과 동일한 방법으로 상기 합성된 적색계열 분산염료를 사용하여 PLA 염색을 실시하였다.PLA staining was performed using the red-based dispersion dye synthesized in the same manner as in Experimental Example 1.

도 13에 보이는 바와 같이, 화학식 2-1의 분산염료는 초기 염착율이 매우 양호하였으며, 순수 적색으로 발색되었고, 색도도 우수하였음을 확인할 수 있다.
As shown in FIG. 13, the disperse dye of Chemical Formula 2-1 had a very good initial dyeing rate, was developed in pure red color, and had excellent chromaticity.

황색계열 분산염료 개발Developed yellow disperse dye

본 발명자들은 황색계열 분산염료를 개발하여 위하여 프탈이미드계 유도체를 합성하여 PLA 적용성을 확인한 결과, 하기 화학식 3의 구조를 가지는 황색계열의 분산염료 화합물의 물성이 우수한 것을 확인하였다.The present inventors synthesized a phthalimide-based derivative to develop a yellow-based dispersion dye, and confirmed the PLA applicability, it was confirmed that the physical properties of the yellow-based dispersion dye compound having a structure of the formula (3).

[화학식 3](3)

Figure 112011100441488-pat00022
Figure 112011100441488-pat00022

실시예Example 12: 황색 분산염료의 제조 12: Preparation of Yellow Disperse Dyes

[반응식 2][Reaction Scheme 2]

Figure 112011100441488-pat00023
Figure 112011100441488-pat00023

상기 반응식 2와 같이 반응시켜 화학식 3의 적색 분산염료를 합성하였다.Reaction as in Scheme 2 to synthesize a red dispersion dye of formula (3).

HCl 28.2ml와 400ml 증류수에 위에서 합성한 중간체 4-아미노프탈이미드 0.13mol을 넣고 교반하였다. 완전 용해후 혼합물을 5℃이하로 냉각시키고 여기에 NaNO2 0.13mol을 첨가한 후 5~10℃로 1시간 이상 교반하였다.0.13 mol of the intermediate 4-aminophthalimide synthesized above was added to 28.2 ml of HCl and 400 ml of distilled water, followed by stirring. After complete dissolution, the mixture was cooled to 5 ° C. or less, and 0.13 mol of NaNO 2 was added thereto, followed by stirring at 5˜10 ° C. for at least 1 hour.

증류수 200ml에 HCl 20ml을 첨가하여 커플링 성분 1,4-디메틸-2-하이드록시-5-시아노-6-피리돈(1,4-dimethyl-2-hydroxy-5-cyano-6-pyridone) 0.13 mol을 완전히 용해시키고 0℃ 이하로 냉각하였다. 위에서 미리 준비한 디아조늄 염 용액을 한 방울씩 천천히 첨가하되 온도는 10℃로 유지하였다. 5~6시간 충분히 반응 시킨 후 10% 소듐 하이드록시드를 pH 3~4가 될때까지 첨가하였다. 그 후 감압여과 및 물로 수세하였다(수율:90.65%).20 ml of HCl is added to 200 ml of distilled water to form a coupling component 1,4-dimethyl-2-hydroxy-5-cyano-6-pyridone (1,4-dimethyl-2-hydroxy-5-cyano-6-pyridone) 0.13 mol was completely dissolved and cooled to 0 ° C. or below. The diazonium salt solution prepared above was slowly added dropwise, but the temperature was maintained at 10 ° C. After fully reacting for 5-6 hours, 10% sodium hydroxide was added until pH 3-4. Thereafter, the mixture was washed with reduced pressure filtration and washed with water (yield: 90.65%).

상기 화학식 3의 순수 황색염료 80중량부를 나프탈렌 설포산 포름알데히드 축합형 분산제 30중량부와 리그닌 설폰산계 분산제 40중량부 및 물 50중량부에 가입하여 염료입자의 90% 이상의 0.5㎛미만이 되도록 분쇄하여 액상의 염료 분산액을 제조하였다.
80 parts by weight of the pure yellow dye of Chemical Formula 3 is added to 30 parts by weight of naphthalene sulfoic acid formaldehyde condensing dispersant, 40 parts by weight of lignin sulfonic acid-based dispersant and 50 parts by weight of water, and then pulverized to less than 0.5 μm of dye particles. A liquid dye dispersion was prepared.

실험예Experimental Example 3: 합성된 황색 분산염료의 염색성 평가 3: Dyeability Evaluation of Synthetic Yellow Disperse Dyes

상기 실험예 1과 동일한 방법으로 상기 합성된 황색계열 분산염료를 사용하여 PLA 염색을 실시하였다.PLA staining was performed using the yellow-based dispersion dye synthesized in the same manner as in Experimental Example 1.

도 14에 보이는 바와 같이, 화학식 3의 분산염료는 초기 염착율이 매우 양호하였으며, 순수 황색으로 발색되었고, 색도도 우수하였음을 확인할 수 있다.
As shown in FIG. 14, the disperse dye of Chemical Formula 3 was found to have a very good initial dyeing rate, developed a pure yellow color, and had excellent chromaticity.

실시예Example 13: 흑색 염료 제조 13: black dye manufacturing

상기 화학식 1-1의 청색 염료 화합물 70중량부, 화학식 2-1의 적색 분산염료 20중량부, 화학식 3의 황색 분산염료 10중량부를 나프탈렌 설포산 포름알데히드 축합형 분산제 45중량부와 리그닌 설폰산계 분산제 45중량부 및 물 100중량부에 가입하여 염료입자의 90% 이상의 0.5㎛미만이 되도록 분쇄하여 액상의 흑색 염료 분산액을 제조하였다.
70 parts by weight of the blue dye compound of Formula 1-1, 20 parts by weight of red dispersion dye of Formula 2-1, 10 parts by weight of yellow dispersion dye of Formula 3, 45 parts by weight of naphthalene sulfoic acid formaldehyde condensing dispersant and lignin sulfonic acid dispersant 45 parts by weight and 100 parts by weight of water were added and pulverized to less than 0.5 µm of 90% or more of the dye particles to prepare a liquid black dye dispersion.

실험예Experimental Example 4: 흑색 분산염료 조성물의 염색성 평가 4: Evaluation of Dyeability of Black Disperse Dye Composition

상기 실시예 13에 따라 제조된 흑색 분산염료로 PLA 섬유를 실험예 1과 같이 염색한 다음, 생산기술연구원에 의뢰하여 견뢰도 시험을 실시하였다.The PLA fiber was dyed as in Experimental Example 1 with the black dispersion dye prepared according to Example 13, and then a color fastness test was performed by a production technology research institute.

도 15a는 본 발명에 따른 흑색 분산염료(시료명: ② "A")와 종래 상업용 PET용 흑색 염료(시료명: ① "Black")로 염색한 PLA 섬유에 대하여 표준시험 방식에 따른 세탁견뢰도, 마찰견뢰도, 일광견뢰도, 땀견뢰도 및 승화견뢰도를 테스트한 결과이다.Figure 15a is a fastness to wash, friction fastness according to the standard test method for the PLA fiber dyed with a black dispersion dye (sample name: ② "A") and a conventional black dye for commercial PET (sample name: ① "Black") according to the present invention The results were tested for the light fastness, sweat fastness and sublimation fastness.

도 15b는 종래 상업용 PET용 흑색 염료(시료명: ① "Black")의 PLA 견뢰도 테스트 사진이고, 도 15c는 본 발명에 따른 흑색 분산염료(시료명: ② "A")의 PLA 테스트 사진이다.15B is a PLA fastness test photograph of a conventional black dye for commercial PET (sample name: ① "Black"), and FIG. 15C is a PLA test photograph of a black dispersion dye (sample name: ② "A") according to the present invention.

도 15a 및 도 15c에 보이는 바와 같이, 본 발명에 따른 블랙 분산염료는 세탁견뢰도, 마찰견뢰도, 일광견뢰도, 땀견뢰도 및 승화견뢰도 등 제반 사항에서 견뢰도가 매우 우수한 것으로 확인되었다.As shown in Figure 15a and 15c, the black dispersion dye according to the present invention was confirmed to have a very good fastness in various matters, such as washing fastness, friction fastness, daylight fastness, sweat fastness and sublimation fastness.

Claims (10)

삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 하기 화학식 3의 구조를 가지는 황색계열의 분산염료 화합물.
[화학식 3]
Figure 112011100441488-pat00029

Yellow-based dispersion dye compound having a structure of formula (3).
(3)
Figure 112011100441488-pat00029

 제6항에 있어서,
상기 분산염료는 폴리락트산(PLA) 섬유의 염색에 사용되는 것인 분산염료 화합물.
The method according to claim 6,
The disperse dye is a disperse dye compound that is used for dyeing polylactic acid (PLA) fibers.
제6항에 따른 분산염료 화합물을 포함하는 분산염료 조성물.
Disperse dye composition comprising the disperse dye compound according to claim 6.
제6항의 화학식 3의 구조를 가지는 황색계열의 분산염료 화합물;
하기 화학식 1의 구조를 가지는 청색계열의 분산염료 화합물; 및
하기 화학식 2의 구조를 가지는 적색계열의 분산염료 화합물을 포함하는 흑색계열 분산염료 조성물.

[화학식 1]
Figure 112013118037929-pat00050

상기 화학식 1에서,
R1은 -NO2 또는 -COOCH2H3 이고,
R2는 -H, -CH3 또는 -NH-CO-CH3 이고,
R3는 -H 또는 -OCH3 이고,
R4는 -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이고,
R5는 -CH2CH3, -CH2CH2-O-COCH3 또는 -CH2CH2-O-CH2CH2OH 이다.

[화학식 2]
Figure 112013118037929-pat00051

상기 화학식 2에서,
R1은 -CH3 또는 -NH-CO-CH3 이고,
R2는 -H 또는 -OCH3 이고,
R3 및 R4 는 독립적으로 -CH2CH=CH2, -CH2CH3 또는 -CH2CH2-O-COCH3 이다.
Yellow-based dispersion dye compound having a structure of Formula 6;
A blue-based dispersed dye compound having a structure of Formula 1; And
Black-based dispersion dye composition comprising a red-based dispersion dye compound having a structure of formula (2).

[Chemical Formula 1]
Figure 112013118037929-pat00050

In Formula 1,
R 1 is -NO 2 or -COOCH 2 H 3,
R 2 is —H, —CH 3 or —NH—CO—CH 3 ,
R 3 is -H or -OCH 3 ,
R 4 is —CH 2 CH 2 —O—COCH 3 or —CH 2 CH 2 —O—CH 2 CH 2 OH,
R 5 is —CH 2 CH 3 , —CH 2 CH 2 —O—COCH 3 or —CH 2 CH 2 —O—CH 2 CH 2 OH.

(2)
Figure 112013118037929-pat00051

In Formula 2,
R 1 is —CH 3 or —NH—CO—CH 3 ,
R 2 is -H or -OCH 3 ,
R 3 and R 4 are independently —CH 2 CH═CH 2 , —CH 2 CH 3 or —CH 2 CH 2 —O—COCH 3 .
제9항에 있어서,
전체 분산염료 화합물 100 중량%를 기준으로
상기 청색계열의 분산염료 화합물이 40 ~ 90 중량%이고, 상기 적색계열의 분산염료 화합물이 5 ~ 40 중량%이고, 상기 황색계열의 분산염료 화합물이 5 ~ 30 중량%인 흑색계열 분산염료 조성물.10. The method of claim 9,
Based on 100% by weight of the total dispersed dye compound
The black-based dispersion dye composition of the blue-based dispersion dye compound is 40 to 90% by weight, the red-based dispersion dye compound is 5 to 40% by weight, and the yellow-based dispersion dye compound is 5 to 30% by weight.
KR1020110136747A 2011-12-16 2011-12-16 Disperse dye for polylactic acid fibers and black dye composition comprising thereof KR101387104B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020110136747A KR101387104B1 (en) 2011-12-16 2011-12-16 Disperse dye for polylactic acid fibers and black dye composition comprising thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020110136747A KR101387104B1 (en) 2011-12-16 2011-12-16 Disperse dye for polylactic acid fibers and black dye composition comprising thereof

Publications (2)

Publication Number Publication Date
KR20130069162A KR20130069162A (en) 2013-06-26
KR101387104B1 true KR101387104B1 (en) 2014-04-24

Family

ID=48864607

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020110136747A KR101387104B1 (en) 2011-12-16 2011-12-16 Disperse dye for polylactic acid fibers and black dye composition comprising thereof

Country Status (1)

Country Link
KR (1) KR101387104B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109440490A (en) * 2018-10-12 2019-03-08 山东理工大学 Polylactic acid fiber dyeing azo structure lactic acid ester type disperse dyes and preparation method thereof and dyeing
CN109468861A (en) * 2017-06-01 2019-03-15 苏州大学 A kind of PRINTED FABRIC and textile printing process

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105566940A (en) * 2016-01-27 2016-05-11 杭州福莱蒽特精细化工有限公司 Phthalimidyl azo dye and preparation method and application thereof
CN114773877B (en) * 2022-05-20 2023-12-22 上海鸿源鑫创材料科技有限公司 Disperse blue dye composition and product thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5779781A (en) * 1996-04-25 1998-07-14 Zeneca Limited Ink and toner compositions containing substituted phenyl AZO thiophene dye
US6087480A (en) * 1998-01-13 2000-07-11 Ciba Specialty Chemcals Corporation Process for preparing sparingly soluble aromatic amines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5779781A (en) * 1996-04-25 1998-07-14 Zeneca Limited Ink and toner compositions containing substituted phenyl AZO thiophene dye
US6087480A (en) * 1998-01-13 2000-07-11 Ciba Specialty Chemcals Corporation Process for preparing sparingly soluble aromatic amines

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109468861A (en) * 2017-06-01 2019-03-15 苏州大学 A kind of PRINTED FABRIC and textile printing process
CN109440490A (en) * 2018-10-12 2019-03-08 山东理工大学 Polylactic acid fiber dyeing azo structure lactic acid ester type disperse dyes and preparation method thereof and dyeing
CN109440490B (en) * 2018-10-12 2021-01-01 山东理工大学 Lactic acid ester type disperse dye with azo structure for dyeing polylactic acid fiber, and preparation method and dyeing process thereof

Also Published As

Publication number Publication date
KR20130069162A (en) 2013-06-26

Similar Documents

Publication Publication Date Title
KR101387104B1 (en) Disperse dye for polylactic acid fibers and black dye composition comprising thereof
DE1644370A1 (en) Process for the production of dyes that are poorly soluble in water
CN102618084B (en) Heterocyclic ring blue disperse dye and synthesizing method and application thereof
US2843580A (en) Metallized azo dyes prepared by coupling amino-phenols to diphenylamines
US2662074A (en) Copper complexes of monosulfonamido formazyl dyes
US2022579A (en) 2,3-hydroxy-naphthoic acid arylamide
KR20130092721A (en) Disperse dye for polylester fibers and composition comprising thereof
DE2604220A1 (en) 1 TO 2 COBALT COMPLEX DISAZO DYES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR COLORING NATURAL AND SYNTHETIC POLYAMIDE FIBERS
DE853321C (en) Process for the preparation of disazo dyes
AT214547B (en) Process for the production of new azo dyes
US1828737A (en) Monoazodyestuffs
CN110408234B (en) Environment-friendly disazo acid red dye and preparation method thereof
KR102282524B1 (en) Azo based reactive-disperse dyes for supercritical fluid dyeing and supercritical fluid dyeing using the same
DE1644333A1 (en) Process for the preparation of disperse dyes of the monoazo series
US1363886A (en) Disazo dye
US2112405A (en) Polyazo-dyestuffs
JPS6344868B2 (en)
JPS59170143A (en) Monoazo dye for polyester fiber
US2622175A (en) Trisazo-dyestuffs
KR960005658B1 (en) Process for producing reactive azo-dye
US873798A (en) Red azo dye and process of making same.
DE951527C (en) Process for the preparation of metallizable disazo dyes
KR100256321B1 (en) New blue azo dyes of high fastness
CN116178988A (en) High-fastness disperse dye composition, high-fastness disperse dye product and application thereof
US644292A (en) Black polyazo dye.

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20170413

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20190124

Year of fee payment: 6

FPAY Annual fee payment

Payment date: 20200130

Year of fee payment: 7