Vegetable oil-based biodegradable material and application thereof in preparation of biological powdered ink

Abstract

The invention provides a vegetable oil-based biodegradable material and application thereof in preparation of biological powdered ink. The material is prepared from vegetable oil, polyhydric alcohol / phenol and polybasic acid compounds. The vegetable oil not only keeps excellent biodegradability and moisture resistance of the vegetable oil, but also greatly improves the comprehensive performance and the application field of the high polymer material due to the introduction of rigid groups. When the material is applied to preparation of the biological powdered ink, the biodegradability and moisture resistance of the powdered ink can be effectively improved, and the biological powdered ink prepared from the material has excellent biodegradability, moisture resistance and performance retentivity.

Description

Technical Field

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

[0002] Toner is a high-tech product with resin as the main body (generally accounting for 70-90wt.%), which contains the principles of materials science and rheology. With the upgrading of products, especially the advent of high-speed printers and copiers, traditional styrene-acrylic resins are increasingly unable to meet the needs of low-temperature fixing. The biggest advantage of polyester resin is that it has a high glass transition temperature and a low softening point, and has particularly excellent melting properties during low-temperature fixing. These excellent properties make it more and more widely used in the manufacture of toner. However, the polyester resins traditionally used are mainly petroleum-based products, which are difficult to degrade in the natural environment after being discarded; on the other hand, with the development of the world economy, energy shortages and environmental pollution problems have become increasingly prominent, and there is an urgent need to develop cheap environmentally friendly materials to replace 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 protection, and easy 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 in 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 chain of vegetable oil fatty acids has 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] In view of the shortcomings of the prior art, the present invention aims to provide a class of plant oil-based biodegradable materials and their applications. The method overcomes the technical difficulties of the traditional toner preparation, such as the difficulty in degradation and easy moisture absorption. The toner prepared by the method has good biodegradability and moisture resistance, and can meet the requirements of high-quality laser printing / electrostatic copying in terms of electrical properties and the like.

[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.

[0008] According to an embodiment of the present invention, the acid is selected from divalent or higher C 3～20 Alkyl acids, divalent or higher C 6～20 Aromatic acid, and one or more of the acid anhydrides corresponding to the above acids; preferably selected from dibasic and ternary C 3～10 Alkyl acids, dibasic and tribasic C 6～12 Aromatic acid, and one or more of the 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, isophthalic acid, trimellitic acid and their corresponding acid anhydrides.

[0009] According to an embodiment of the present invention, the alcohol is selected from C 3～20 Alkyl dihydric alcohols and C containing -CH2CH2O- 3～20 One or more than two dihydric alcohols; preferably selected from C 3～10 Alkyl glycols, and C containing -CH2CH2O- 3～10 One or more diols; for example, the alcohol can be selected from one or more of ethylene glycol, propylene glycol, triethylene glycol, neopentyl glycol and diethylene glycol.

[0010] According to an embodiment of the present invention, the phenol is selected from dihydric or higher C 6～20 Phenol, preferably selected from divalent or more C 6～12 The phenol may be, for example, one or more selected from bisphenol A, hydroquinone, resorcinol, and catechol.

[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), exemplarily being 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), exemplified by 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 polyester resin, comprising the following steps:

[0016] (1) preparing monoglyceride by alcoholysis of vegetable oil and glycerol;

[0017] (2) The monoglyceride reacts with an acid and an alcohol to obtain the polyester resin; or, 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 proportions 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] Reaction temperature 180~220℃, and / or

[0023] Reaction time 1 to 3 hours, and / or,

[0024] Stir vigorously.

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

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

[0027] under an inert atmosphere, and / or,

[0028] Reaction temperature 180~220℃, and / or

[0029] The reaction ends when the softening point of the product is not less than 90°C.

[0030] The present invention also provides application of the polyester resin in preparing biological ink powder.

[0031] The invention also provides a bio-ink powder, which contains the polyester resin or is prepared from a raw material containing the polyester resin.

[0032] According to an embodiment of the present invention, the raw material further comprises a release agent, a charge regulator and / or a colorant.

[0033] According to an embodiment of the present invention, the release agent includes but is not limited to paraffin wax, low molecular weight polyolefin wax, Fischer-Tropsch wax and other artificial synthetic waxes, and carnauba wax, montanate wax and other natural waxes. These release agents can be used alone or mixed with at least two to obtain better demolding and anti-sticking effect.

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

[0035] According to an embodiment of the present invention, a colorant is selectively added according to the desired color.

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

[0037] According to an embodiment of the present invention, the raw material may further include inorganic nanopowders, such as one or more of nanopowders of silicon dioxide, titanium dioxide, aluminum oxide, zinc oxide, strontium oxide, and magnesium oxide.

[0038] The present invention also provides a method for preparing the above-mentioned biological ink powder, which is prepared from raw materials containing the above-mentioned polyester resin.

[0039] According to an embodiment of the present invention, the raw material has the definitions as shown above.

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

[0041] S1: mixing the polyester resin, the release agent, the charge regulator and the colorant, melting, extruding and crushing to obtain toner particles;

[0042] S2: mixing the toner particles with the inorganic nanopowder to obtain the bio-toner.

[0043] Beneficial Effects

[0044] The polyester resin provided by the present invention is a plant oil-based biodegradable material, which is prepared from plant oil, polyol / phenol and polyacid compounds. It not only maintains the excellent biodegradability and moisture resistance of plant oil, but also introduces rigid groups, which greatly improves the comprehensive performance and application field of polymer materials. The polyester resin is used to prepare bio-ink, which can effectively improve the biodegradability and moisture resistance of the toner. The bio-ink prepared by the polyester resin 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 the like.

[0045] Definition and explanation of terms

[0046] The “acid anhydrides corresponding to the above acids” mentioned above may be, for example, terephthalic anhydride, isophthalic anhydride, phthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, azelaic anhydride, naphthalene 2,6-dicarboxylic anhydride, fumaric anhydride, isophthalic anhydride, and trimellitic anhydride. DETAILED DESCRIPTION

[0047] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

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

[0049] Example 1

[0050] Preparation of monoglyceride: feed materials at a molar ratio of n (propylene glycol): n (soybean oil) = 2:1, add catalyst NaOH, and carry out alcoholysis reaction at 200°C with strong stirring for 1.5 hours, then add appropriate amount of hydrochloric acid to neutralize the catalyst to ensure that the product composition remains unchanged, and keep the reaction product monoglyceride for later use.

[0051] Preparation of vegetable oil-based polyester resin: Ethylene glycol, monoglyceride, trimellitic acid and isophthalic acid are put into a four-necked bottle in a mass ratio of 1:11.7:2.4:4, filled with N2, and reacted at 200°C. The reaction end point is when the softening point of the product reaches 100°C, and the vegetable oil-based polyester resin is obtained.

[0052] The biological toner particles were prepared by physical melting method: vegetable oil-based polyester resin, paraffin, zinc salicylate and red pigment (Pigment Red 122) were uniformly mixed in a high-speed mixer at a mass ratio of 80:7:2:14, and then melt-mixed at high temperature. After that, they were extruded and pressed into tablets by an extruder, and were input into a ball mill for coarse crushing. Furthermore, they were crushed and graded by a jet mill to obtain red toner particles of 5μm to 10μm.

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

[0054] Example 2

[0055] Preparation of monoglyceride: feed materials at a molar ratio of n (propylene glycol): n (palm oil) = 2:1, add catalyst KOH, stir vigorously at 210°C for alcoholysis reaction for 2 hours, then add appropriate amount of phosphoric acid to neutralize the catalyst to ensure that the product composition remains unchanged, collect the main product of the reaction, monoglyceride, and set aside.

[0056] Preparation of vegetable oil-based polyester resin: Under nitrogen protection, bisphenol A, monoglyceride, fumaric acid and phthalic anhydride were put into a four-necked bottle in a mass ratio of 3.9:10.9:1:5.7, and reacted at 210°C. The reaction end point was when the softening point reached 110°C, and the vegetable oil-based polyester resin was obtained.

[0057] The biological toner particles were prepared by physical melting method: vegetable oil-based polyester resin, paraffin, zinc salicylate and black pigment (carbon black) were evenly mixed in a high-speed mixer at a mass ratio of 82:5:1:14, and then melt-mixed at high temperature. After that, they were extruded into tablets through an extruder, and coarsely crushed in a ball mill. Furthermore, they were crushed and graded in a jet mill to obtain black toner particles of 5μm to 10μm.

[0058] Preparation of black bio-toner: 0.25 g of a flow enhancer nano-silicon dioxide additive was added to 50 g of black toner particles to obtain a black bio-toner suitable for laser printing / electrostatic copying.

[0059] Comparative Example 1

[0060] Except that monoglyceride is not used, the remaining 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 bottle in a mass ratio of 1:2.4:4, filled with N2, and reacted at 200°C. The reaction end point is when the softening point reaches 100°C, and polyester resin is obtained.

[0062] Comparative Example 2

[0063] Except that soybean oil was used instead of monoglyceride to prepare the vegetable oil-based polyester resin, the remaining steps were the same as those in Example 1.

[0064] Test Case

[0065] Evaluation of fixing strength:

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

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

[0068] Excellent: firmness ≥93%;

[0069] Good: firmness 90% to 93%;

[0070] Poor: firmness <90%.

[0071] Biodegradation performance test:

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

[0073] The biodegradability was evaluated according to the following standards:

[0074] Excellent: Biodegradation rate ≥ 80%;

[0075] Good: biodegradation rate 60% to 80%;

[0076] Poor: Biodegradation rate <60%.

[0077] Preservation test:

[0078] Put 30g of bio-toner into a bottle, place it in a constant temperature and humidity environment of 50℃ and 50% for 72h, gently transfer it to a container containing toner, and visually observe whether the toner has agglomerated. Evaluate the storage performance according to the following standards:

[0079] Excellent: No toner surface aggregation was observed;

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

[0081] Poor: There is condensation on the toner surface, 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 performance was evaluated according to the following standards:

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

[0086] Good: The moisture content of the product is 0.8% to 1.2%;

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

[0088] Table 1 Evaluation results of fixing strength, biodegradability, storage property and moisture resistance of the bio-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 samples printed by the toner made of 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 relatively poor biodegradability; the toner without vegetable oil or with vegetable oil instead of vegetable oil-based bio-polyester resin has relatively poor fixing strength, storage property and moisture resistance.

[0092] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A polyester resin, characterized in that The polyester resin is obtained by reacting monoglyceride, acid and alcohol, or by reacting monoglyceride, acid and phenol; The monoglyceride is the alcoholysis product of vegetable oil and glycerol.

2. The polyester resin according to claim 1, characterized in that The vegetable oils include but are not limited to one or more of soybean oil, peanut oil, corn oil, rapeseed oil, palm oil and linseed oil; And / or, the acid is selected from divalent or higher C 3～20 Alkyl acids, divalent or higher C 6～20 Aromatic acid, and one or more of the acid anhydrides corresponding to the above acids; preferably selected from dibasic and ternary C 3～10 Alkyl acids, dibasic and tribasic C 6～12 Aromatic acid, and one or more of the acid anhydrides corresponding to the above acids; And / or, the alcohol is selected from C 3～20 Alkyl dihydric alcohols and C containing -CH2CH2O- 3～20 One or more than two dihydric alcohols; preferably selected from C 3～10 Alkyl glycols, and C containing -CH2CH2O- 3～10 One or more diols; And / or, the phenol is selected from dihydric or higher C 6～20 Phenol, preferably selected from divalent or more C 6～12 phenol.

3. The polyester resin according to claim 1 or 2, 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 acid 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.

4. The polyester resin according to claim 1, characterized in that The mass ratio of the monoglyceride, acid and alcohol is (40-80):(20-50):(1-20); The mass ratio of the monoglyceride, acid and phenol is (30-70):(10-50):(1-30).

5. The method for preparing the polyester resin according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) preparing monoglyceride by alcoholysis of vegetable oil and glycerol; (2) The monoglyceride reacts with an acid and an alcohol to obtain the polyester resin; or, the monoglyceride reacts with an acid and a phenol to obtain the polyester resin.

6. The preparation method according to claim 5, 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 the vegetable oil to glycerol is (1.5-2.5):1 (for example, 2:1), and / or, Reaction temperature 180~220℃, and / or Reaction time 1 to 3 hours, and / or, Stir vigorously; and / or, after the alcoholysis reaction is completed, adding an acid solution to the system; And / or, the reaction conditions in step (2) include: under an inert atmosphere, and / or, Reaction temperature 180~220℃, and / or The reaction ends when the softening point of the product is not less than 90°C.

7. Use of the polyester resin according to any one of claims 1 to 4 in the preparation of bio-ink.

8. A bio-toner, characterized in that: The bio-ink contains the polyester resin according to any one of claims 1 to 4 or is prepared from a raw material containing the polyester resin according to any one of claims 1 to 4; Preferably, the raw material further comprises a release agent, a charge regulator, a colorant and / or an inorganic nanopowder.

9. The method for preparing the bio-ink according to claim 8, characterized in that: The preparation method is prepared from raw materials containing the polyester resin according to any one of claims 1 to 4.

10. The preparation method according to claim 9, characterized in that: The preparation method comprises the following steps: S1: mixing the polyester resin, the release agent, the charge regulator and the colorant, melting, extruding and crushing to obtain toner particles; S2: mixing the toner particles with the inorganic nanopowder to obtain the bio-toner.

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