Vegetable oil-based biodegradable materials and their applications in the preparation of bio-toner

Abstract

The present invention provides a vegetable oil-based biodegradable material and its application in the preparation of biotoner. This material is prepared from vegetable oil, polyol / phenol, and polyacid compounds. They not only maintain the excellent biodegradability and moisture resistance of vegetable oil, but also the introduction of rigid groups greatly improves the comprehensive performance and application fields of the polymer material. Applying such materials to the preparation of biotoner can effectively improve the biodegradability and moisture resistance of the toner, and the biotoner prepared therefrom has excellent biodegradability, moisture resistance, and performance retention.

Description

Technical Field

[0001] The invention belongs to the technical field of laser printing / electrostatic copying color toners and relates to a biodegradable material for toners, in particular to a plant oil-based biodegradable material and application thereof in preparing biological toners. Background Art

[0002] Toner is a high-tech product based on materials science and rheology, composed primarily of resin (typically 70–90 wt.%). With the advent of advanced products, particularly high-speed printers and copiers, traditional styrene-acrylic resins are increasingly unable to meet the demands of low-temperature fusing. The key advantage of polyester resins is their high glass transition temperature and low softening point, resulting in exceptionally good melting properties during low-temperature fusing. These excellent properties have led to their increasing use in toner manufacturing. However, traditionally used polyester resins are primarily petroleum-based, making them difficult to degrade in the natural environment upon disposal. Furthermore, with the development of the global economy, energy shortages and environmental pollution are becoming increasingly prominent, creating an urgent need for the development of inexpensive, environmentally friendly alternatives to non-degradable petroleum-based products.

[0003] Vegetable oil is produced from oil-producing plants. It is not only an important component of edible oil, but also can be used as an industrial raw material. Due to its abundant reserves, environmental friendliness, and ease of modification, it is gradually showing great application potential in the fields of medicine, paints, and polymer materials. Vegetable oil is one of the most promising petroleum substitutes for the synthesis of polymer materials. If it is fully utilized, it can reduce people's dependence on petroleum resources to a certain extent, in order to cope with the threat posed by the increasingly depleted petroleum resources. The long carbon chains of vegetable oil fatty acids have low polarity and strong hydrophobicity, so vegetable oil-based polymers often have the characteristics of low water absorption and good hydrolysis stability. How to obtain vegetable oil-based polymers suitable for the preparation of bio-inks has become a technical problem that needs to be solved urgently in this field. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a class of plant oil-based biodegradable materials and their applications. This method overcomes the technical challenges of traditional toner preparation, such as resistance to degradation and moisture absorption. The toner produced using this method exhibits excellent biodegradability and moisture resistance, and its electrical properties meet the requirements for high-quality laser printing and electrostatic copying.

[0005] The present invention provides a polyester resin obtained by reacting monoglyceride, acid and alcohol, or by reacting monoglyceride, acid and phenol;

[0006] The monoglyceride is the alcoholysis product of vegetable oil and glycerol.

[0007] According to an embodiment of the present invention, the vegetable oil includes, but is not limited to, one or more of soybean oil, peanut oil, corn oil, rapeseed oil, palm oil, and linseed oil, etc.

[0008] According to an embodiment of the present invention, the acid is selected from one or more of C alkyl acids with two or more carbon atoms, C aromatic acids with two or more carbon atoms, and acid anhydrides corresponding to the above acids; preferably selected from C alkyl acids with two or three carbon atoms, C aromatic acids with two or three carbon atoms, and acid anhydrides corresponding to the above acids, for example, the acid can be selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, naphthalene 2,6-dicarboxylic acid, fumaric acid, trimellitic acid, trimellitic anhydride, and their corresponding acid anhydrides, etc. 3～20 alkyl acids, C 6～20 aromatic acids, and one or more of acid anhydrides corresponding to the above acids; preferably selected from C 3～10 alkyl acids with two or three carbon atoms, C 6～12 aromatic acids with two or three carbon atoms, and one or more of acid anhydrides corresponding to the above acids, for example, the acid can be selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, naphthalene 2,6-dicarboxylic acid, fumaric acid, trimellitic acid, trimellitic anhydride, and their corresponding acid anhydrides, etc.

[0009] According to an embodiment of the present invention, the alcohol is selected from one or more of C alkyl diols with two or more carbon atoms and C diols containing -CH2CH2O-; preferably selected from C alkyl diols and C diols containing -CH2CH2O-; for example, the alcohol can be selected from one or more of ethylene glycol, propylene glycol, triethylene glycol, neopentyl glycol, and diethylene glycol, etc. 3～20 alkyl diols with two or more carbon atoms, and C 3～20 diols containing -CH2CH2O-; preferably selected from C 3～10 alkyl diols, and C 3～10 diols containing -CH2CH2O-; for example, the alcohol can be selected from one or more of ethylene glycol, propylene glycol, triethylene glycol, neopentyl glycol, and diethylene glycol, etc.

[0010] According to an embodiment of the present invention, the phenol is selected from C phenols with two or more carbon atoms, preferably selected from C phenols with two or more carbon atoms, for example, it can be selected from one or more of bisphenol A, hydroquinone, resorcinol, and catechol, etc. 6～20 phenols, preferably selected from C 6～12 phenols with two or more carbon atoms, for example, it can be selected from one or more of bisphenol A, hydroquinone, resorcinol, and catechol, etc.

[0011] According to an embodiment of the present invention, the mass ratio of the monoglyceride, acid, and alcohol is (40 - 80):(20 - 50):(1 - 20), for example, (40 - 70):(20 - 40):(1 - 10), (45 - 65):(25 - 35):(2 - 8), or (50 - 60):(25 - 35):(2 - 8), and an example is 11.7:6.4:1.

[0012] According to an embodiment of the present invention, the mass ratio of the monoglyceride, acid, and phenol is (30 - 70):(10 - 50):(1 - 30), for example, (30 - 60):(10 - 40):(5 - 20), (35 - 55):(15 - 35):(10 - 20), or (40 - 50):(20 - 30):(10 - 20), and an example is 10.9:6.7:3.9.

[0013] According to an exemplary embodiment of the present invention, the polyester resin is obtained by reacting monoglyceride, trimellitic acid, isophthalic acid and ethylene glycol;

[0014] Alternatively, the polyester resin is obtained by reacting monoglyceride, fumaric acid, phthalic anhydride and bisphenol A.

[0015] The present invention also provides a method for preparing the above polyester resin, comprising the following steps:

[0016] (1) Vegetable oil and glycerol are subjected to alcoholysis reaction to prepare monoglyceride;

[0017] (2) The monoglyceride reacts with an acid and an alcohol to obtain the polyester resin; alternatively, the monoglyceride reacts with an acid and a phenol to obtain the polyester resin.

[0018] According to an embodiment of the present invention, the vegetable oil, acid, alcohol and phenol have the definitions and ratios as shown above.

[0019] According to an embodiment of the present invention, the alcoholysis reaction is carried out under an alkaline catalyst, for example, the alkaline catalyst is sodium hydroxide or potassium hydroxide.

[0020] According to an embodiment of the present invention, the reaction conditions of the alcoholysis reaction include:

[0021] The molar ratio of the vegetable oil to glycerol is (1.5 - 2.5):1 (for example, 2:1), and / or,

[0022] The reaction temperature is 180 - 220 °C, and / or,

[0023] The reaction time is 1 - 3 h, and / or,

[0024] Strong stirring.

[0025] According to an embodiment of the present invention, after the alcoholysis reaction is completed, an acid solution (such as hydrochloric acid solution) is added to the system to neutralize the alkaline catalyst and ensure that the product composition remains unchanged.

[0026] According to an embodiment of the present invention, the reaction conditions in step (2) include:

[0027] It is carried out under an inert atmosphere, and / or,

[0028] The reaction temperature is 180 - 220 °C, and / or,

[0029] When the softening point of the product is not lower than 90 °C, it is the end point of the reaction.

[0030] The present invention also provides the application of the above polyester resin in the preparation of biotoner.

[0031] The present invention also provides a biological toner, which contains the above polyester resin or is prepared from raw materials containing the above polyester resin.

[0032] According to an embodiment of the present invention, the raw materials further include a release agent, a charge control agent, and / or a colorant.

[0033] According to an embodiment of the present invention, the release agent includes, but is not limited to, synthetic waxes such as paraffin wax, low molecular weight polyolefin wax, and Fischer-Tropsch wax, as well as natural waxes such as carnauba wax and montanic acid ester wax. These release agents can be used alone or at least two of them can be mixed to obtain a better release and anti-sticking effect.

[0034] According to an embodiment of the present invention, the charge control agent includes a metal complex of salicylic acid, such as zinc salicylate, zirconium salicylate, calcium salicylate, or chromium salicylate.

[0035] According to an embodiment of the present invention, a colorant is selected and added according to the required color.

[0036] According to an embodiment of the present invention, the mass ratio of the polyester resin, the release agent, the charge control agent, and the colorant is (30-90):(1-15):1:(1-20), such as 80:7:2:14 or 82:5:1:14.

[0037] According to an embodiment of the present invention, the raw materials may further include inorganic nano powders, such as one or more of nano powders of silica, titanium dioxide, alumina, zinc oxide, strontium oxide, and magnesium oxide.

[0038] The present invention also provides a preparation method of the above biological toner, which is prepared from raw materials containing the above polyester resin.

[0039] According to an embodiment of the present invention, the raw materials have the limitations as shown above.

[0040] According to an embodiment of the present invention, the preparation method includes the following steps:

[0041] S1: Mix the polyester resin, the release agent, the charge control agent, and the colorant, melt, extrude, and pulverize to obtain color powder particles;

[0042] S2: Mix the color powder particles with the inorganic nano powders to obtain the biological toner.

[0043] Beneficial effects

[0044] The polyester resin provided by the present invention is a vegetable oil-based biodegradable material, which is prepared from vegetable oil, polyols / phenols and polybasic acid compounds. It not only maintains the excellent biodegradability and moisture resistance of vegetable oil, but also the introduction of rigid groups greatly improves the comprehensive performance and application fields of the polymer material. This polyester resin is used to prepare biodegradable toner, which can effectively improve the biodegradability and moisture resistance of the toner. The biodegradable toner prepared with it has excellent biodegradability, moisture resistance, performance retention and fixing strength, and can meet the requirements of high-quality laser printing / electrostatic copying in terms of electrical properties and other aspects.

[0045] Term Definition and Explanation

[0046] The "acid anhydride corresponding to the above acid" in the above text can be, for example, terephthalic anhydride, isophthalic anhydride, phthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, azelaic anhydride, naphthalene 2,6-dicarboxylic anhydride, fumaric anhydride, trimellitic anhydride, trimellitic anhydride. Specific Embodiments

[0047] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to illustrate and explain the present invention exemplarily, and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0048] Unless otherwise specified, the raw materials and reagents used in the following embodiments are commercially available products, or can be prepared by known methods.

[0049] Example 1

[0050] Preparation of monoglyceride: Charge according to the molar ratio n(glycerol):n(soybean oil)=2:1, add the catalyst NaOH, and carry out alcoholysis reaction at 200°C with strong stirring for 1.5 hours. Then add an appropriate amount of hydrochloric acid to neutralize the catalyst to ensure that the product composition remains unchanged, and reserve the reaction product monoglyceride.

[0051] Preparation of vegetable oil-based polyester resin: Put ethylene glycol, monoglyceride, trimellitic acid and isophthalic acid into a four-necked flask according to the mass ratio of 1:11.7:2.4:4, fill with N2, and react at 200°C. When the softening point of the product reaches 100°C, it is the end point of the reaction, and the vegetable oil-based polyester resin is obtained.

[0052] Preparation of biodegradable toner particles by physical melting method: Vegetable oil-based polyester resin, paraffin, zinc salicylate and red pigment (Pigment Red 122) are mixed evenly in a high-speed mixer according to the mass ratio of 80:7:2:14, then subjected to high-temperature melting mixing, and then extruded and pressed into tablets by an extruder, and input into a ball mill for coarse crushing, and further crushed and classified by a jet mill to obtain 5μm - 10μm red toner particles.

[0053] Preparation of red biological toner: 40 g of red toner particles are mixed evenly with 0.4 g of nano-titanium dioxide powder to obtain red biological toner suitable for laser printing / electrostatic copying.

[0054] Example 2

[0055] Preparation of monoglyceride: Charge according to the molar ratio n(glycerol):n(palm oil)=2:1, add catalyst KOH, and carry out alcoholysis reaction with strong stirring at 210 °C for 2 hours. Then add an appropriate amount of phosphoric acid to neutralize the catalyst to ensure that the product composition remains unchanged, and collect the main reaction product monoglyceride for standby.

[0056] Preparation of vegetable oil-based polyester resin: Under nitrogen protection, bisphenol A, monoglyceride, fumaric acid and phthalic anhydride are put into a four-necked flask according to the mass ratio of 3.9:10.9:1:5.7, and react at 210 °C. When the softening point reaches 110 °C, it is the reaction end point, and vegetable oil-based polyester resin is obtained.

[0057] Preparation of biological toner particles by physical melting method: Vegetable oil-based polyester resin, paraffin, zinc salicylate and black pigment (carbon black) are mixed evenly in a high-speed mixer according to the mass ratio of 82:5:1:14, and then subjected to high-temperature melting mixing. After that, it is extruded and pressed into tablets by an extruder, and input into a ball mill for coarse crushing, and further crushed and classified by a jet mill to obtain black toner particles with a size of 5 μm - 10 μm.

[0058] Preparation of black biological toner: Add 0.25 g of nano-silica as an external additive for fluidity enhancer to 50 g of black toner particles to obtain black biological toner suitable for laser printing / electrostatic copying.

[0059] Comparative Example 1

[0060] Except for not using monoglyceride, the other steps are the same as those in Example 1.

[0061] That is, preparation of polyester resin: Ethylene glycol, trimellitic acid and isophthalic acid are put into a four-necked flask according to the mass ratio of 1:2.4:4, filled with N2, and react at 200 °C. When the softening point reaches 100 °C, it is the reaction end point, and polyester resin is obtained.

[0062] Comparative Example 2

[0063] Except for using soybean oil instead of monoglyceride to prepare vegetable oil-based polyester resin, the other steps are the same as those in Example 1.

[0064] Test Example

[0065] Evaluation of fixing strength:

[0066] The fixing strength test refers to GB / T 29300-2012.

[0067] The fixing strength is evaluated according to the following criteria:

[0068] Excellent: The fastness ≥ 93%;

[0069] Good: The fastness is 90% - 93%;

[0070] Poor: The fastness < 90%.

[0071] Biodegradability test:

[0072] The degradation performance test refers to GB / T 20197 - 2006.

[0073] The biodegradability is evaluated according to the following criteria:

[0074] Excellent: The biodegradation rate ≥ 80%;

[0075] Good: The biodegradation rate is 60% - 80%;

[0076] Poor: The biodegradation rate < 60%.

[0077] Storage stability test:

[0078] Put 30 g of the biological toner into a bottle, place it in an environment with constant temperature and humidity of 50°C and 50% for 72 h, gently transfer it to the container for holding the toner, and visually check whether the toner agglomerates. The storage stability is evaluated according to the following criteria:

[0079] Excellent: No agglomeration is observed on the surface of the toner;

[0080] Good: There is agglomeration on the surface of the toner, but it can be eliminated without vibration during transfer, and it does not affect the printing effect;

[0081] Poor: There is agglomeration on the surface of the toner, which cannot be eliminated during transfer, seriously affecting the printing effect.

[0082] Moisture resistance test:

[0083] The moisture resistance test refers to GB / T 8262.3 - 2013.

[0084] The moisture resistance is evaluated according to the following criteria:

[0085] Excellent: The water content of the product < 0.8%;

[0086] Good: The water content of the product is 0.8% - 1.2%;

[0087] Poor: The water content of the product > 1.2%.

[0088] Table 1 Evaluation results of fixing strength, biodegradability, storage stability and moisture resistance of the biological toner in Examples 1 - 2 and Comparative Examples 1 - 2

[0089]

[0090]

[0091] As can be seen from the data in Table 1, the quality evaluation of the sample printed by the toner prepared based on the vegetable oil-based polyester resin of the present invention meets the standard requirements. The test data of Examples 1-2 and Comparative Examples 1-2 in Table 1 show that the toner without the addition of vegetable oil-based polyester resin has poor biodegradability; the toner directly without vegetable oil and the toner using vegetable oil instead of vegetable oil-based biodegradable polyester resin have poor fixing strength, storage stability and moisture resistance.

[0092] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A biological toner, characterized in that, The biological toner is prepared from raw materials containing a polyester resin, a release agent, a charge control agent, and a colorant; The polyester resin is obtained by reacting monoglyceride, an acid, and an alcohol, or by reacting monoglyceride, an acid, and a phenol; the mass ratio of the monoglyceride, the acid, and the alcohol is (40-80):(20-50):(1-20), and the mass ratio of the monoglyceride, the acid, and the phenol is (30-70):(10-50):(1-30); The monoglyceride is an alcoholysis product of vegetable oil and glycerol; The vegetable oil is selected from one or more of soybean oil, peanut oil, corn oil, rapeseed oil, palm oil, and linseed oil; The acid is selected from dibasic and tribasic C 3~10 alkyl acids, terephthalic acid, isophthalic acid, phthalic acid, naphthalene 2,6-dicarboxylic acid, trimellitic acid, trimellitic anhydride, and one or more of the acid anhydrides corresponding to the above acids; The alcohol is selected from C 3~10 alkyl diols and C 3~10 diols containing -CH2CH2O-, one or more of them; The phenol is selected from phenols having two or more carbon atoms 6~20 phenol; The mass ratio of the polyester resin, the release agent, the charge control agent, and the colorant is (30-90):(1-15):1:(1-20).

2. The biologic toner according to claim 1, characterized in that, The acid is selected from one or more of terephthalic acid, isophthalic acid, phthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, naphthalene 2,6-dicarboxylic acid, fumaric acid, trimellitic acid, trimellitic anhydride, and their corresponding anhydrides; And / or, the alcohol is selected from one or more of ethylene glycol, propylene glycol, triethylene glycol, neopentyl glycol, and diethylene glycol; And / or, the phenol is selected from one or more of bisphenol A, hydroquinone, resorcinol, and catechol.

3. The biological toner according to claim 1, wherein The mass ratio of the monoglyceride, the acid, and the alcohol is (40-70):(20-40):(1-10), (45-65):(25-35):(2-8), or (50-60):(25-35):(2-8); The mass ratio of the monoglyceride, the acid, and the phenol is (30-60):(10-40):(5-20), (35-55):(15-35):(10-20), or (40-50):(20-30):(10-20).

4. The biologic toner according to claim 1, wherein The polyester resin is obtained by reacting monoglyceride, trimellitic anhydride, isophthalic acid, and ethylene glycol; Or, the polyester resin is obtained by reacting monoglyceride, fumaric acid, phthalic anhydride, and bisphenol A.

5. The preparation method of the biological toner according to any one of claims 1-4, characterized in that, The preparation method is prepared from raw materials containing the polyester resin according to any one of claims 1-4.

6. The preparation method according to claim 5, characterized in that, The raw materials further contain inorganic nano powder.

7. The preparation method according to claim 6, wherein The preparation method includes the following steps: S1: Mix the polyester resin, the release agent, the charge control agent, and the colorant, melt, extrude, and pulverize to obtain toner particles; S2: Mix the toner particles with the inorganic nano powder to obtain the biological toner.

8. The preparation method according to claim 5, characterized in that, The preparation method of the polyester resin includes the following steps: (1) Alcoholize vegetable oil and glycerol to prepare monoglyceride; (2) React the monoglyceride with an acid and an alcohol to obtain the polyester resin; or react the monoglyceride with an acid and a phenol to obtain the polyester resin.

9. The preparation method according to claim 8, characterized in that, The alcoholysis reaction is carried out under an alkaline catalyst; And / or, the reaction conditions of the alcoholysis reaction include: The molar ratio of glycerol to vegetable oil is (1.5-2.5):1, and / or, The reaction temperature is 180-220 °C, and / or, The reaction time is 1-3 h, and / or, Strong stirring; And / or, after the alcoholysis reaction is completed, an acid solution is added to the system; And / or, the conditions of the reaction in step (2) include: Carried out in an inert atmosphere, and / or, The reaction temperature is 180-220 °C, and / or, When the softening point of the product is not lower than 90 °C, it is the end point of the reaction.

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