CN113373730A - Amino acid polymer Maillard reaction product double-side coated black cigarette paper and preparation method thereof - Google Patents
Amino acid polymer Maillard reaction product double-side coated black cigarette paper and preparation method thereof Download PDFInfo
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- CN113373730A CN113373730A CN202110785233.7A CN202110785233A CN113373730A CN 113373730 A CN113373730 A CN 113373730A CN 202110785233 A CN202110785233 A CN 202110785233A CN 113373730 A CN113373730 A CN 113373730A
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- amino acid
- cigarette paper
- acid polymer
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- maillard reaction
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/28—Colorants ; Pigments or opacifying agents
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- Paper (AREA)
- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
The invention discloses black cigarette paper coated on two sides of a Maillard reaction product of an amino acid polymer, wherein black dye is used for dyeing two sides of the cigarette paper to obtain the black cigarette paper; the black dye is a Maillard reaction product of an amino acid polymer. The invention also discloses a preparation method of the black cigarette paper of the Maillard product. The amino acid polymer Maillard reaction product double-coated black cigarette paper has uniform and stable color and high wear-resistant color fastness and illumination color fastness.
Description
Technical Field
The invention belongs to the technical field of cigarette materials, and particularly relates to amino acid polymer Maillard reaction product double-side coated black cigarette paper and a preparation method thereof.
Background
The cigarette paper is called coil paper and is mainly used for wrapping cigarette tobacco shred columns. The cigarette paper is used as an important component of a cigarette accessory of three paper rods, not only bears the key image and connotation of a product, but also directly participates in the combustion of cigarettes, and has direct and special influence on smoke. On one hand, the burnt components of the cigarette paper are important components of cigarette smoke and are sucked along with the mainstream smoke, so that the cigarette paper has important influence on the smoking sense of the cigarette combustion; on the other hand, the internal quality of the cigarette paper also influences the combustion condition of the cigarettes, and has important influences on the ash wrapping effect, the color of cigarette ash and the smoke components during smoking of the cigarettes. Therefore, the cigarette paper has important influence on the aspects of the smoldering property, the burning speed, the composition and the release amount of cigarette smoke, the smoking quality of the cigarette and the like of the cigarette.
As the tobacco industry develops, cigarette paper is endowed with more new functions, such as: improving ash coating, improving odor absorption, reducing tar and harm, reducing CO, reducing ignition Load (LIP), keeping moisture, and resisting bacteria. In recent years, with the pursuit of differentiation and individuation of cigarette products, black cigarette paper, special embossed cigarette paper and the like are sequentially appeared.
The currently used black cigarette paper is mainly dyed by synthetic pigments and natural pigments or natural product extracts. Azo dyes are generally adopted for synthesizing the pigments, and the materials and combustion cracking products thereof have safety risks; natural pigments or extracts of natural products have poor color fastness due to their poor stability and are also very expensive.
The Maillard reaction product has the characteristic of strong fragrance, good fragrance effect and good safety. But the reaction speed of common protein and reducing sugar is slow, so that a Maillard product with dark color is difficult to obtain; although the reaction speed of the amino acid monomer and the reducing sugar is high, the obtained Maillard product has light color and is not suitable for the black pigment used for the cigarette paper; meanwhile, Maillard reaction products are easy to volatilize and lose, so that the aroma and color of the product are difficult to maintain stably and durably.
The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide an amino acid polymer obtained by controlling the polycondensation molecular weight of amino acid, and the product obtained by Maillard reaction using the obtained amino acid polymer as a raw material is used as a black pigment and then is used for double-sided coating of cigarette paper to prepare the black cigarette paper with good color fastness, high safety, low cost and specific fragrance.
The purpose of the invention is realized by the following technical scheme:
the invention discloses a black cigarette paper with two sides coated with Maillard reaction products of amino acid polymers, and black dye is used for dyeing the two sides of the cigarette paper to obtain the black cigarette paper; the black dye is a Maillard reaction product of an amino acid polymer.
Preferably, the Maillard reaction product of the amino acid polymer is a product obtained by alcoholizing and aging the Maillard reaction product of the amino acid polymer and reducing sugar.
Preferably, the preparation method of the product of the Maillard reaction product of the amino acid polymer and the reducing sugar after alcoholization and aging comprises the following steps:
firstly, polymerizing amino acid under the action of a catalyst, and controlling the molecular weight of the obtained amino acid polymer to be 500-2000;
dissolving 1 weight part of the amino acid polymer obtained in the step one and 2-5 weight parts of reducing sugar in 4-20 weight parts of solvent, adjusting the pH value to 8-9, heating to 100 ℃ and 180 ℃, and reacting for 5-8 h;
regulating the pH value to 8, alcoholizing and aging for 24-48h in an aerobic environment at the temperature of 60-90 ℃ to obtain a dispersion liquid of the Maillard product.
The amino acid in the step I can be selected in any type and proportion, the requirement can be met only by controlling the molecular weight of the amino acid polymer to be 500-2000, and the Maillard product obtained is light in color because the molecular weight of the amino acid polymer is too low (such as less than 500); if the molecular weight of the amino acid polymer is too high (e.g., more than 2000), the reaction rate is slow, and therefore, the molecular weight of the resulting amino acid polymer needs to be controlled. Amino acids are generally not selected for sulfur-containing amino acids because the resulting maillard products of sulfur-containing amino acids may burn to produce an unpleasant odor.
Preferably, the catalyst in the step (i) is phosphoric acid, and the reducing sugar is one or more of fructose, xylose, galactose or honey.
Preferably, the solvent of step (c) is one or more of water, propylene glycol or glycerol.
Preferably, KOH is used for adjusting the pH value in the step II, and K is used for adjusting the pH value in the step III2CO3。
The invention discloses a preparation method of amino acid polymer Maillard reaction product double-sided coated black cigarette paper, which comprises the following steps:
(1) adding water into the dispersion liquid of the Maillard product to adjust the mass ratio of the Maillard product to the water to be 1: 1-10, and carrying out ultrasonic treatment for 1-3h to obtain a colorant solution;
(2) coating and dyeing the double surfaces of the cigarette paper by using the colorant solution in the step (1); and drying to obtain the amino acid polymer Maillard reaction product double-side coated black cigarette paper.
Preferably, a cigarette paper auxiliary agent is added into the colorant solution before double-sided coating and dyeing of the cigarette paper, and the cigarette paper auxiliary agent is one or two of potassium citrate or potassium malate.
The invention has the beneficial effects that:
1. the alcoholized and aged Maillard product is used as a black pigment for coating the cigarette paper on two sides for the first time, and the obtained cigarette paper has the advantages of high wear-resistant color fastness and illumination color fastness, high safety, low cost and special fragrance, and is not easy to fade. The black pigment can be used together with other pigments to improve the color, luster and other qualities of the cigarette paper. The cigarette paper of the present invention may also be used in the packaging of foodstuffs for the mouth.
2. The invention controls the variety and proportion of amino acid, controls the molecular weight of the amino acid polymer between 500-2000, and then uses the amino acid polymer to react with reducing sugar to obtain Maillard reaction product; the reaction speed is high, and the obtained Maillard product has a dark color; secondly, carrying out alcoholization and aging on the Maillard reaction product, and applying the obtained alcoholized and aged Maillard product to double-sided coating of cigarette paper, wherein the color is uniform and stable, the color fastness to abrasion and illumination is high, and the Maillard reaction product is not easy to fade; has the function of improving the smoking quality of the cigarettes.
3. The amino acid of the invention can be selected from any kind and proportion of amino acid, and the molecular weight of the amino acid polymer can be controlled to be 500-2000, because the molecular weight of the amino acid polymer is too low (such as less than 500), the Maillard product obtained is light in color; if the molecular weight of the amino acid polymer is too high (e.g., more than 2000), the reaction rate is slow, and therefore, the molecular weight of the resulting amino acid polymer needs to be controlled. Sulfur containing amino acids are generally not selected because the resulting Maillard product combustion of sulfur containing amino acids can produce unpleasant odors.
4. The preparation method of the black cigarette paper has simple process, can be directly produced by the existing cigarette paper production equipment, has low cost and is easy for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
Adding a certain amount of amino acid into a three-neck flask, adding catalyst concentrated phosphoric acid (the concentration is 85 wt%) which is 0.5% of the total weight of the amino acid, stirring, introducing nitrogen to blow for 30min, heating to 150 ℃, vacuumizing until the vacuum degree is lower than 20Pa, heating to 210 ℃, reacting for a period of time, and taking out to obtain the amino acid polymer with the molecular weight of about 600. The amino acid selected in this example was a mixture of proline, glutamic acid, serine and phenylalanine in a ratio of 1mol proline to 0.2mol glutamic acid to 0.2mol serine to 0.4mol alanine.
Weighing 1 part by weight of the obtained amino acid polymer and 2 parts by weight of fructose, adding 2 parts by weight of solvent water and 2 parts by weight of glycerol, completely dissolving, adding into a hydrothermal reaction kettle, adjusting the pH value to 9 with potassium hydroxide, sealing, heating to 150 ℃, and reacting for 5 hours. Then potassium carbonate is used for adjusting the pH value to 8, and the dispersion liquid of the Maillard product is obtained after stirring, alcoholizing and aging for 24 hours at the temperature of 60 ℃ in an open aerobic environment.
Adding a proper amount of potassium citrate into the dispersion liquid of the Maillard product, adding water to adjust the mass ratio of the Maillard product to the water to be 1: 5, and carrying out ultrasonic mixing for 1h to obtain a colorant solution; then dyeing the two sides of the cigarette paper, and drying to obtain black cigarette paper of the required Maillard product; the obtained cigarette paper has light black color, certain luster and baking fragrance.
Example 2
The difference from example 1 is: the amino acid selection and proportion in this example are 1mol proline, 0.2mol threonine, 0.3mol tryptophan and 0.5mol alanine; adding a certain amount of amino acid into a three-neck flask, adding catalyst concentrated phosphoric acid (the concentration is 85 wt%) which is 0.5% of the total weight of the amino acid, stirring, introducing nitrogen to blow for 30min, heating to 150 ℃, vacuumizing until the vacuum degree is lower than 20Pa, heating to 180 ℃, reacting for a period of time, and taking out to obtain the amino acid polymer with the molecular weight of about 1000.
Weighing 1 part by weight of the amino acid polymer, 2 parts by weight of xylose and 3 parts by weight of honey, adding 20 parts by weight of water, adding into a hydrothermal reaction kettle, adjusting the pH value to 9 with potassium hydroxide, sealing, heating to 180 ℃, and reacting for 5 hours. Then potassium carbonate is used for adjusting the pH value to 8, and the dispersion liquid of the Maillard product is obtained after stirring, alcoholizing and aging for 24 hours at the temperature of 80 ℃ in an open aerobic environment.
Adding a proper amount of potassium malate into the dispersion liquid of the Maillard product, adding water to adjust the mass ratio of the Maillard product to the water to be 1: 10, carrying out ultrasonic mixing for 1h to obtain a colorant solution, and carrying out double-sided dyeing on the cigarette paper to obtain the black cigarette paper of the required Maillard product; the obtained cigarette paper is black brown and has nut flavor.
Example 3
The difference from example 1 is: the amino acid selection and proportion of the amino acid selection in the embodiment is 1mol of proline, 0.1mol of aspartic acid, 0.1mol of valine and 0.2mol of tyrosine; adding a certain amount of amino acid into a three-neck flask, adding catalyst concentrated phosphoric acid (the concentration is 85 wt%) which is 0.5% of the total weight of the amino acid, stirring, introducing nitrogen to blow for 30min, heating to 150 ℃, vacuumizing until the vacuum degree is lower than 20Pa, heating to 210 ℃, reacting for a period of time, and taking out to obtain the amino acid polymer with the molecular weight of about 2000.
Weighing 1 part by weight of the amino acid polymer, 1 part by weight of fructose, 2 parts by weight of xylose and 2 parts by weight of galactose, adding 20 parts by weight of water, adding into a hydrothermal reaction kettle, adjusting the pH value to 9 by potassium hydroxide, sealing, heating to 120 ℃, and reacting for 5 hours. And then potassium carbonate is used for adjusting the pH value to 8.5, and the dispersion of the Maillard product is obtained after stirring, alcoholizing and aging for 24 hours at the temperature of 90 ℃ in an open aerobic environment.
Adding a proper amount of potassium malate into the dispersion liquid of the Maillard product, adding water to adjust the mass ratio of the Maillard product to the water to be 1: 2, carrying out ultrasonic mixing for 1h to obtain a colorant solution, and carrying out double-sided dyeing on the cigarette paper to obtain the black cigarette paper of the required Maillard product; the obtained cigarette paper is black brown, frosty, and has nut fragrance.
Comparative example 1
The same preparation method as that of example 3 is adopted, but the maillard product is not subjected to alcoholization and aging steps, so as to prepare the control black cigarette paper, the black cigarette paper obtained in example 3 and the control black cigarette paper are placed in a constant temperature and humidity box with the temperature of 40 ℃ and the relative humidity of 60 percent for a week, and then the chromatic aberration of the black cigarette paper and the control black cigarette paper is analyzed by a chromatic aberration meter, and the obtained data is shown in the following table 1:
TABLE 1 color fastness data
| ID | Black cigarette paper obtained in example 3 | Contrast black cigarette paper |
| Color difference Δ E | 2.058 | 9.128 |
As can be seen from Table 1, the color fastness of the cigarette paper obtained without subjecting the Maillard product to the alcoholization and aging steps is significantly reduced.
Control experiment 2
The following control tests were carried out by selecting a white paper sheet a, an imported synthetic pigmented black paper sheet b, a domestic natural pigmented black paper sheet c and the black paper sheet obtained in example 3, which had the same physical properties as those of example 3.
And (3) azo detection:
the data obtained according to YQ/T62-2015 gas chromatography-Mass Spectrometry combination for determination of azo dyes which release specific aromatic amines in cigarette paper are shown in Table 2 below:
TABLE 2 aromatic amine content data
| ID | a | b | c | Black cigarette paper obtained in example 3 |
| Total aromatic amine content: ng/Kg | 1.2 | 243.5 | 24.3 | 9.2 |
As can be seen from Table 2, the aromatic amine content of the black cigarette paper obtained by the invention is far lower than that of the control sample, and the black cigarette paper has better safety.
And (3) detecting color fastness:
according to the method of the standard GB/T8427-2008, white cigarette paper a, imported certain brand synthetic pigment black cigarette paper b, domestic certain brand natural pigment black cigarette paper c and black cigarette paper obtained in example 3 with the same physical characteristics are selected to be subjected to solarization for 10 days to detect the light color fastness of the cigarette paper, and the obtained data are shown in the following table 3:
TABLE 3 color fastness data
| ID | a | b | c | Black cigarette paper obtained in example 3 |
| Color difference Δ E | 0.412 | 1.321 | 6.871 | 0.932 |
As can be seen from Table 3, the black cigarette paper obtained by the invention has obviously better sunshine color fastness than a control sample and better color fastness.
Sensory evaluation of cigarettes:
white cigarette paper a with the same physical characteristics, synthetic pigment black cigarette paper b of a certain imported brand, natural pigment black cigarette paper c of a certain domestic brand and black cigarette paper 3# obtained in example 3 are prepared into cigarette cigarettes by adopting a leaf group formula of a certain brand of Yunan tobacco industry Limited liability company for sensory evaluation, and the aroma evaluation result is shown in Table 4:
TABLE 4 sensory evaluation data
As can be seen from Table 4, the cigarettes rolled by the black cigarette paper obtained by the invention have obvious characteristic fragrance style.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The black cigarette paper with the amino acid polymer Maillard reaction product coated on the two sides is characterized in that black dye is used for dyeing the two sides of the cigarette paper to obtain the black cigarette paper; the black dye is a Maillard reaction product of an amino acid polymer.
2. The amino acid polymer Maillard reaction product double-coated black cigarette paper according to claim 1, wherein the amino acid polymer Maillard reaction product is a product of an amino acid polymer and a reducing sugar Maillard reaction product after alcoholization and aging.
3. The amino acid polymer Maillard reaction product double-sided coated black cigarette paper according to claim 2, wherein the preparation method of the product of the Maillard reaction product of the amino acid polymer and reducing sugar after alcoholization and aging comprises the following steps:
firstly, polymerizing amino acid under the action of a catalyst, and controlling the molecular weight of the obtained amino acid polymer to be 500-2000;
dissolving 1 weight part of the amino acid polymer obtained in the step one and 2-5 weight parts of reducing sugar in 4-20 weight parts of solvent, adjusting the pH value to 8-9, heating to 100 ℃ and 180 ℃, and reacting for 5-8 h;
regulating the pH value to 8, alcoholizing and aging for 24-48h in an aerobic environment at the temperature of 60-90 ℃ to obtain a dispersion liquid of the Maillard product.
4. The amino acid polymer Maillard reaction product double-sided coated black cigarette paper according to claim 3, characterized in that the catalyst in step (r) is phosphoric acid, and the reducing sugar is one or more of fructose, xylose, galactose or honey.
5. The amino acid polymer Maillard reaction product double-sided coated black cigarette paper according to claim 3, wherein the solvent of step (c) is one or more of water, propylene glycol or glycerol.
6. The amino acid polymer Maillard reaction product double-coated black cigarette paper according to claim 3, characterized in thatIn the second step, KOH is used for adjusting the pH value, and K is used for adjusting the pH value2CO3。
7. The method for preparing the amino acid polymer Maillard reaction product double-coated black cigarette paper according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) adding water into the dispersion liquid of the Maillard product to adjust the mass ratio of the Maillard product to the water to be 1: 1-10, and carrying out ultrasonic treatment for 1-3h to obtain a colorant solution;
(2) coating and dyeing the double surfaces of the cigarette paper by using the colorant solution in the step (1); and drying to obtain the amino acid polymer Maillard reaction product double-side coated black cigarette paper.
8. The preparation method according to claim 7, characterized in that a cigarette paper auxiliary agent is added into the colorant solution, and the cigarette paper auxiliary agent is one or two of potassium citrate or potassium malate.
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