AQUEOUS DYEING COMPOSITION AND PROCESS FOR SYNTHETIC SUBSTRATES

Abstract

A composition of matter for aqueous dyeing of synthetic substrates and a method of aqueous dyeing of a synthetic substrate.

Description

This application is a utility application claiming priority from U.S. Provisional patent application Ser. No. 62/013,013, filed Jun. 17, 2014.

BACKGROUND OF THE INVENTION

For years scientist and chemists in the carpet industry have believed aqueous dyeing of polyester carpet was impossible. They have said, the only viable way to color polyester was to solution dye it (adding a pigment when the polymer was in a liquid or molten state).

Some individuals and carpet mills have experimented with aqueous dyeing, but to the inventor's knowledge have not been successful. There is chemistry available that is used in the dyeing of cloth for upholstery fabric and clothing, but the amount of chemical products necessary for the aqueous dyeing of polyester carpet is prohibitive and not practical. In dyeing carpet only light colors can be achieved, using known chemistry.

Prior art chemicals are not environmentally friendly. With the exception of the formulas using naphthenic hydrocarbons, the materials in this invention for dyeing polyester carpet are environmentally friendly. The inventor used a pressure cooker only capable of 17 pounds of pressure at 130 degrees Fahrenheit. Using the pressure cooker was an attempt, to duplicate a dyeing system used by the carpet mills called The Jet Beck Dyeing System, which is capable of reaching temperatures up to 165 degrees Fahrenheit.

The inventor is confident that adjustments can be made to eliminate naphthenic hydrocarbons eventually. The materials of this invention for polypropylene are environmentally friendly aside from the fact, that small amounts of naphthenic hydrocarbons may be required. The first formulas herein used Limonene. Later Pine oil products were substituted because of cost, and better results, although some pine oil products contain natural Limonene.

The carpet industry has looked for an advantage of dyeing polyester (PET and PTT carpet) in a similar aqueous process as nylon, but the chemistry was not available. Solid substrates can be dyed as well as fabrics.

THE INVENTION

What is disclosed and claimed herein is a composition of matter for aqueous dyeing of synthetic substrates. The composition comprises water, and for every 1200 milliliters of water, 500 to 725 milliliters of polypropylene glycol; 167 to 450 milliliters of surfactant; 0 to 250 milliliters of pine oil; 0 to 250 milliliters of acetic acid; 0 to 250 milliliters of limonene; 0 to 350 milliliters of naphthalene hydrocarbon, 0 to 250 milliliters of dye penetrant, and, a predetermined amount of dye can be used.

In addition, this invention comprises a method of aqueous dyeing of a synthetic substrate. The method comprises contacting the synthetic substrate with a composition of matter as set forth Supra for a predetermined period of time, at a predetermined temperature, and at a predetermined pressure until a desired color and color intensity of the synthetic substrate is achieved.

DETAILED DESCRIPTION OF THE INVENTION

Thus, there is disclosed a composition of matter for aqueous dyeing of synthetic substrates. The composition comprises water, and for every 1200 milliliters of water, 500 to 725 milliliters of polypropylene glycol; 167 to 450 milliliters of surfactant; 0 to 250 milliliters of pine oil; 0 to 250 milliliters of acetic acid; 0 to 250 milliliters of limonene; 0 to 350 milliliters of naphthalene hydrocarbon, 0 to 250 milliliters of dye penetrant, and, a predetermined amount of dye are used.

In addition, this invention comprises a method of aqueous dyeing of a synthetic substrate. The method comprises contacting the synthetic substrate with a composition of matter as set forth Supra for a predetermined period of time, at a predetermined temperature, and at a predetermined pressure until a desired color and color intensity of the synthetic substrate is achieved.

EXAMPLES

Comparison testing was applied on all dispersing/penetrant formulas in an effort to obtain an understanding of which formulas work the best for specific substrates. The highest use synthetic materials were tested, such as polyethylene terephalate, useful in carpets, and other solid polyethylene terephalate articles, polytrimethylene terephalate for carpet, and other solid articles, polypropylene and various solid polypropylene articles.

The following materials were utilized in the examples: Formulas 52—CBG Biotech Ltd., 26400 Broadway Avenue, Unit A, Oakwood Village, Ohio 44146; Naphtha; Florasolv DPE, dipentene, Florachemical Corporation, 5209 San Jose Boulevard, Suite 202, Jacksonville, Fla. 32207; Floresolve LX100C, which is a mixture of dipentene and d′ limonene, Florachemical Corporation; Novoc A-80 and Autoacid A-80, monocaramide dihydrogen sulfate (urea sulfate), Peach State Labs, 180 Burlington Road, Rome, Ga. 30162; Albegal Set, which is C₁₆ to C₁₈ ethoxylated surfactant, Ciba Specialty Chemical Corporation, High Point, N.C. 27281; d′-limonene, Florachemical Corporation; Dowanol PNB glycol ether, which is 95% 1-butoxy-2-propanol and 5% 2-butoxy-1-propanol, Miloport Enterprises, Inc.; Milonic NP 9.5 surfactant, nonylphenyl polyethylene glycol ether less than 97%; polyethylene less than 5% and dinonylphenyl polyethylene oxide 1-2%; Flexisolv 1100C which is benzyl alcohol 50 to 75%, dioctyl sodium sulfosuccinate 10 to 40%, neopentyl alcohol 1 to 25%; Florachemical Corporation; Flexisolve 1120C concentrate, Benzyl alcohol 35 to 60%, dioctyl sodium sulfosuccinate 10 to 40%, neopentyl alcohol 1 to 25%, Invista S.A.R.L., Wichita Kans. 67220; Formula 66, 78H, CBG Technologies.

Comparison testing was applied on all dispersing/penetrant formulas in an effort to obtain a subjective understanding of which formulae work the best for specific substrates. The original goal was to find the best formula for polyethylene terephthalate carpet (PET), solid PET objects, polytrimethylene terephthalate (PTT) carpet, and solid PTT objects. Other polymers and substrates were tested, including olefin carpet, that is polypropylene, and various solid polypropylene objects. Extensive testing was executed to define the best concentration of dispersing agent/penetrant. Each formula was tested using various substrates.

To explain the difference in the results of these tests, a scale was created to identify saturation of color (intensity). This was not a gray scale from white to black. If the primary color blue was being used in the testing, and if the substrate being used was white carpet for example, and the carpet did not absorb any dye, then the color white in this case is zero saturation. However, on a scale of saturation, 10 would be a lush dark blue wherein all the dye was fully absorbed. The point is reached at which the white carpet cannot absorb anymore dye. This result is full saturation. In this example, the resulting color would not be black in a scale of saturation, as opposed to a gray scale, since we are using a primary color. The color black which is the absence of reflected light can only be achieved by creating a tertiary color that is composed of all three primary colors, red, yellow, and blue.

The formula in example 1 was one of the first formulae that showed promise. Prior to the evaluation in example 1, coloration was light, and weak in permanency. Extensive testing indicated previous formulate contained non-synergistic ingredients and lacked adequate crucial ingredients in the dyeing process. All other colors tested were primary or secondary colors initially, then black was tested to see how dark of a color could be achieved. Black is a tertiary color.

The best results were reached in each test one through nine by using the following ingredients: 165 ml of dispersing agent/penetrant, 30 ml of disperse dye, and 2½ gallons of water. All tests were heated in a pressure cooker for 2½ hours at about 130 degrees Fahrenheit under 17 pounds of pressure.

Example 1

100 ml d′ limonene

100 ml glycol ether

100 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Thirty ml of disperse dye was used to dye these substrates. In previous tests, poor color saturation was achieved (about 2 on the saturation scale). In this test, a 4 on this scale was an improvement. This formula still failed to produce both the permanency and color saturation desired, but dyed, a nice lighter primary blue.

Example 1A

100 ml d′ limonene

350 ml glycol ether

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

It was originally thought the d′ limonene was the crucial ingredient to acquire both permanency and saturation. Then, three hundred fifty ml of glycol ether was found to be far more important in driving the dye into the substrate. This test yielded a saturation score of 6, a marked improvement over previous testing. The color was more permanent and yielded, a nice, somewhat darker, medium primary blue.

Example 2

100 ml Flexsolv 1120C

350 ml glycol ether PNB

100 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

400 ml water

This formula separated. The Flexsolv 1120C exhibits insolubility. This formula was less successful than previous testing, particularly on PET or PTT. The Resistance to Bleach Testing results were 1.5 to 2.5. The saturation score dropped to four again, back to a lighter color. The color came out mottled. The substrate was dyed black, red, and green in this test. For black, 15 ml of yellow, 8 ml of red and 15 ml of blue was used. For green, 15 ml of yellow and 8 ml of blue disperse dyes were used. For red, 15 ml of red was used. All colors were lighter colors.

Example 3

100 ml Flexsolv 1120C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

The same amount of dye was used in this test as were used, in example number 2. All other factors remained the same, except more NP 9.5 surfactant was added. The formula displayed the same insolubility results as example 2. The black, red and green dye did not penetrate to the base of the PET and PTT carpet and the color was not evenly dispersed into the yarn. Other substrates showed uneven results as well. The saturation score in this test was 4 overall. Resistance to Bleach Test score was 1.0 to 2.0.

Resistance to Bleach Testing was performed on all carpet samples. This was executed, by either a professional testing lab, or by the inventor herein using the professional laboratory testing standards. The standards are as follows: A 4″×6″ specimen is placed face up in a tray and immersed in bleach for 24 hours with the tray covered. Specimen is thoroughly rinsed and extracted twice, then soaked for 10 minutes in a 1% sodium thiosulfate solution followed by a third extraction. A final five minute rinse and extraction using cold tap water is performed to remove all residue.

The specimen is air dried then rated using the AATCC Gray Scale. The AATCC Evaluation Procedures are as follows:

This evaluation procedure uses a Gray Scale for visually evaluating changes in color of textiles resulting from colorfastness tests or resistance to bleach testing. A precise colormetric specification of the differences between the reference and a 9 step scale is given as a permanent record. The 9 step scale is first compared to the reference portion of the carpet sample, and a numerical value is given by comparing one of the nine gray numbered tones to the reference. The exposed, treated or damaged portion of the carpet sample is then compared to the gray scale and a second numerical evaluation is determined. The amount of change is the calculated difference between the two numbers. The following numerical scale is then used and the specimen is then given one of the following as a numerical score:

• 5=no change
• 4=slight change
• 3=noticeable change
• 2=considerable change
• 1=severe change.

Solid substrates with these formulae do not bleach, thus the Resistance to Bleach Testing is not necessary. Although many dye colors were tested, only the results of blue, black, green and red dye testing are listed in this summary. A pressure cooker was used, to dye the substrate, duplicating as closely as possible a dyeing system used at carpet mills called the Jet Beck System. The pressure cooker reached a maximum of 17 lbs. and about 130 degrees. The same procedure with the formulae and dyes were used in all of the following tests.

Example 4

100 ml Flexsolv 1100C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

400 ml water

This formula also mixed poorly in water. The dyeing is consistent to the dyeing of examples 2 and 3. The same amounts of black, red, and green dye were used as in the previous example. The saturation score was 4.

Example 5

100 ml Florasolv Lx 100C

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

This formulae dyeing results were greatly improved. The black red and green colors were more intense. The colors were starting to move toward darker colors. A saturation score of 6 was achieved yielding a darker richer looking medium black, medium red and medium green. The colors also dyed more evenly. Resistance to Bleach Testing was 2.0 to 3.5.

Example 6

100 ml Florasolv DPE

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

The test results showed improvement in intensity of color, achieving 8 in the saturation test. The black, red and green in this test were medium dark colors, and had a richer appearance. The black became a true black instead of a dark gray. The red was a nice primary red, a bright but rich looking color. The green was a bright grass green. Resistance to Bleach testing results was 2.0 to 3.5.

Example 7

100 ml CBG formula 5

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Results in this test were as good as the results in example 6. Saturation results were the same (8). All other factors were the same except the colors were more permanent. Bleach Testing results were 3.0 to 3.5.

Example 8

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

500 ml water

Best results for PET and PTT polyester carpet were achieved. Other solid substrates were tested as well. The saturation result was 10. The same amount of dyes as used in examples 2 to 5 were used. In this test after the carpet was dyed, the dye bath was relatively clear showing all the dye was absorbed by the carpet pieces. In the solid substrate tests the results were the same. The dye bath was not exhausted. The colors in this test came out the darkest of any test using the same amount of dye which indicates that this formula is the best. The colors black, red and green were darker, richer, and more vibrant colors than in any other tests. All the colors were richer looking, and shiny in appearance. The black was a true deep dark black, the red was a dark maroon in appearance, characteristic of red disperse dye when used as a darker color. The green in this test was more of a hunter green rather than the grass green in the previous test. The Resistance to Bleach Testing was 3.0 to 4.0.

Example 8A

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set 500 ml water

The same dye colors and precess was used as in the above test, with an additional step. A carpet protector was applied after the dyeing process.

The carpet pieces were first rinsed and air dried. The pieces were then placed in the pressure cooker and heated. The same amount of time and temperature were used as when the carpet pieces were dyed. This protector process was used for each color group. The two black carpets were processed together, as well as the two green and the two red. Resistance to Bleach testing was 5.0 generally with the exception of the black carpet pieces (PET that scored 4.5)

Example 9

50 ml Florosolv DPE

50 ml CBG Biotech Formula 52

50 ml CBG Biotech Formula 78

50 ml CBG Biotech Formula 66

350 ml glycol ether PNB

200 ml Milonic NP 9.5

100 ml Novoc A-80

100 ml Albegal Set

600 ml water

The very best results on Polypropylene Berber carpet and solid substrates was tested. In previous tests the inventor could not achieve dark colors on polypropylene substrates, especially on Berber carpet. Saturation was 7 in this test. This formula yielded darker colors and dyeing was very even. Only black was dyed to see what the results would be. The black olefin carpet did not dye quite as dark as the polyester carpet in example 8, although the same amount of dye was used. But the color was black and not gray. Polypropylene carpet is generally harder to dye than other substrates. Other substrates that were in a solid form were dyed as well. The solid objects showed various results. Some objects such, as a Frisbee™, for example, dyed completely. When a section was sliced off the color was fairly consistent all the way through the object. Other substrates were only coated by the dye.

Claims

1. A composition of matter for solution dyeing of synthetic substrates, said composition comprising:

i. water, and for every 1200 milliliters of water,

ii. 500 to 725 milliliters of propylene glycol;

iii. 167 to 450 milliliters of surfactant;

iv. 0 to 250 milliliters of pine oil;

v. 0 to 2 50 milliliters of acetic acid;

vi. 0 to 250 milliliters of limonene;

vii. 0 to 350 milliliters of naphthalene hydrocarbon,

viii. 0 to 250 milliliters of dye penetrant, and

ix. a predetermined amount of dye.

2. A method of aqueous dyeing of a synthetic substrate, said method comprising contacting said synthetic substrate with a composition of matter as claimed in claim 1 for a predetermined period of time at a predetermined temperature and pressure until a desired color and color intensity of said synthetic substrate is achieved.