CN101705005A - Method for modifying performance of compound resin by using tetrapod-like zinc oxide whiskers - Google Patents
Method for modifying performance of compound resin by using tetrapod-like zinc oxide whiskers Download PDFInfo
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Abstract
The invention discloses a method for modifying the performance of a compound resin by using tetrapod-like zinc oxide whiskers, which comprises the steps of: (1) mixing a compound resin filler and the tetrapod-like zinc oxide whiskers evenly to form a mixture, and adding a surface treatment liquid into the mixture for treatment to obtain an antibacterial filler, wherein the mass percentage of the tetrapod-like zinc oxide whiskers in the mixture is between 1 and 10 percent, and the balance is the compound resin filler; and (2) mixing the antibacterial filler obtained in the step(1) with a resin matrix for solidification to form a solidified antibacterial compound resin, and finally realizing the modification of the performance of the compound resin. The antibacterial compound resin prepared by the method has the advantages of high antibacterial efficacy, good safety and stability, no discoloration, low price and the like; moreover, the tetrapod-like zinc oxide whiskers can improve the mechanical strength of the compound resin while giving the antibacterial ability to the compound resin. At present, a tetrapod-like zinc oxide whisker antibacterial agent is widely applied in industrials of antibacterial plastics, ceramics and textile, just begins to be applied in the pharmaceutical industry, and is not yet applied to dental compound resin materials.
Description
Technical field:
The invention belongs to the composite resin material field, relate to a kind of method of utilizing the antibiotic and mechanical property of four acicular type zinc oxide crystal whisker modification compound resin.
Background technology:
After the composite resin material invention sixties in 20th century, because the performance attractive in appearance of its excellence, physical strength preferably, good advantages such as processing property, and be widely used in clinical, but because the characteristic of compound resin polymerization shrinkage and the little seepage between resin and tissue of tooth of easily causing, simultaneously than silver amalgam, the easier adhesion of repair materials resin surface bacteriums such as glass ion, and resin material itself does not possess anti-microbial effect, therefore the secondary caries problem after the compound resin reparation becomes the major cause that dummy is changed, and has had a strong impact on the repairing effect of compound resin clinically.
For addressing this problem, when reducing the compound resin polymerization shrinkage as far as possible, a lot of scholars attempted compound resin antibacterial modified by way of, main method is matrix components and the filler composition that changes compound resin, fluorinated modified as resin is carried out, methods such as organic polymer modification and interpolation antiseptic-germicide.Wherein fluorinated modified method since material to release the fluorine amount less and can not release fluorine for a long time and be not used widely.In the organic polymer method of modifying, because the antibacterial group is connected by chemical bond with resin monomer, directly the bacterium that sticks to resin surface is played a role, so a big advantage of this type of non-stripping property anti-biotic material is exactly the mechanical property that anti-microbial effect influences material lastingly and not.But also there is certain deficiency in this method, and is complicated as synthesis technique, the cost height, and the material surface protein adsorption influences antibacterial effect and fails to significantly improve resin physical strength etc., therefore also need further research and solve this type of problem.The technology of directly adding antiseptic-germicide in compound resin is simpler, and cost is lower, therefore obtains extensive concern.Chitosan, propolis, Tubulicid, carrying silver antimicrobials, photochemical catalysis class antiseptic-germicide (TiO
2) all once be used to the antibacterial modified of oral cavity material, when having obtained certain antibacterial effect, the material after this type of antiseptic-germicide modification exists weak point in work-ing life, poor heat resistance, easily decomposes, easily produces microorganism anti-(resisting) property of medicine, influences goods color, transparence, physical strength, the more high shortcoming of cost.Selection has higher antibacterial efficacy, and colour stable has the key point that the antiseptic-germicide that strengthens the toughening material effect becomes the antibiotic compound resin of preparation simultaneously.
Four acicular type zinc oxide crystal whisker (T-ZnOw) is a kind of novel antibacterial material, and it has, and antibacterial efficacy height, security and stability are good, nondiscoloration, advantage such as cheap, the more important thing is that it can improve the physical strength of material when giving the material antibacterial ability.The four acicular type zinc oxide crystal whisker antiseptic-germicide is widely used in antibiotic plastic, pottery, textile industry at present, and it is at the early-stage to use ability in pharmaceutical industries, does not see its application in the composite resin material of oral cavity as yet.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance is provided, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 1-10%, and the compound resin filler is a surplus; Compound added obtain antibiotic filler after surface treatment liquid is handled;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 10-80%, and the mass percent of resinous substrates is 20-90%.
Needles length≤30 μ m, the needles base diameter of four acicular type zinc oxide crystal whisker are 0.5-2 μ m in the described step (1).
Specific practice is: is 2% solution with γ-An Bingjisanyiyangjiguiwan as being made into the volumetric concentration ratio in the solute adding hexanaphthene, obtains surface treatment liquid behind the described solution hydrolysis 20-45min; Secondly, according to mass percent, the compound resin filler of 90-99% and the four acicular type zinc oxide crystal whisker of 1-10% are mixed the acquisition compound, compound added in the described surface treatment liquid obtain solidliquid mixture, behind the liquid in the rotatory evaporator removal solidliquid mixture, residuum 80 ℃ of dry down, scarifyings, 120 ℃ of activation 2 hours, is obtained antibiotic filler then.
The four acicular type zinc oxide crystal whisker that the present invention adopts is a kind of whisker with 3-D solid structure, and it has a centrosome and four needle-like crystals, and four needless all launch to three-dimensional (positive tetrahedron summit) from tetrahedral center of gravity.Be subjected to the influence of its unique texture, it shows the function of multiple uniqueness, as strengthening and toughening, broad-spectrum antimicrobial, antistatic, wear-resisting, microwave absorbing etc.As a kind of novel antibacterial material, be applied to oral cavity material antibiosis T-ZnOw and have lot of advantages, it had both overcome the allochroic shortcoming of general silver-based inorganic antibacterial agent, being different from photocatalysis antibacterial material again like that need be antibiotic by ultraviolet catalytic ability, more can as organic antibacterial agent, not bring secondary pollution and other side effects, and because the atomic arrangement structure of high-sequential makes its intensity and modulus approach the theoretical strength of valence link between the atom of material, thereby matrix material had very strong enhancing toughening effect, its four the needle point positions with nano effect can not produce reunion simultaneously, it is uniformly dispersed in matrix material easilier, so the four acicular type zinc oxide crystal whisker antiseptic-germicide become the antibacterial modified ideal of dental prosthetic material and select.
Embodiment:
Embodiment 1: a kind of method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 1%, and the compound resin filler is a surplus; Is 2% solution with γ-An Bingjisanyiyangjiguiwan as being made into the volumetric concentration ratio in the solute adding hexanaphthene, obtains surface treatment liquid behind the described solution hydrolysis 20min; Compound added in the described surface treatment liquid obtain solidliquid mixture, remove liquid in the solidliquid mixture with rotatory evaporator after, residuum 80 ℃ of dry down, scarifyings, 120 ℃ of activation 2 hours, is obtained antibiotic filler then;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 10%, and the mass percent of resinous substrates is 90%.
Embodiment 2: a kind of method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 10%, and the compound resin filler is a surplus; Is 2% solution with γ-An Bingjisanyiyangjiguiwan as being made into the volumetric concentration ratio in the solute adding hexanaphthene, obtains surface treatment liquid behind the described solution hydrolysis 45min; Compound added in the described surface treatment liquid obtain solidliquid mixture, remove liquid in the solidliquid mixture with rotatory evaporator after, residuum 80 ℃ of dry down, scarifyings, 120 ℃ of activation 2 hours, is obtained antibiotic filler then;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 80%, and the mass percent of resinous substrates is 20%.
Embodiment 3: a kind of method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 5%, and the compound resin filler is a surplus; Is 2% solution with γ-An Bingjisanyiyangjiguiwan as being made into the volumetric concentration ratio in the solute adding hexanaphthene, obtains surface treatment liquid behind the described solution hydrolysis 30min; Compound added in the described surface treatment liquid obtain solidliquid mixture, remove liquid in the solidliquid mixture with rotatory evaporator after, residuum 80 ℃ of dry down, scarifyings, 120 ℃ of activation 2 hours, is obtained antibiotic filler then;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 75%, and the mass percent of resinous substrates is 25%.
Embodiment 4: a kind of method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 5%, and the compound resin filler is a surplus; Is 2% solution with γ-An Bingjisanyiyangjiguiwan as being made into the volumetric concentration ratio in the solute adding hexanaphthene, obtains surface treatment liquid behind the described solution hydrolysis 30min; Compound added in the described surface treatment liquid obtain solidliquid mixture, remove liquid in the solidliquid mixture with rotatory evaporator after, residuum 80 ℃ of dry down, scarifyings, 120 ℃ of activation 2 hours, is obtained antibiotic filler then;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 70%, and the mass percent of resinous substrates is 30%.
Compound resin filler and resinous substrates all are materials well known in the art among the present invention, can contain the silicon-dioxide that particle diameter is 5-12 μ m in the compound resin filler, resinous substrates can be made of respectively following substances, and according to mass percent: (1) light-cured composite resinous substrates is mixed by the (dimethylamino)-ethyl benzoate of the camphorquinone of the methacrylate triethyleneglycol ester of the maleic anhydride modified epoxy dimethacrylate of 14.31-14.41%, 4.78-9.61%, 0.1-0.19% and 0.24-0.57% to be formed; (2) chemosetting compound resin resinous substrates is by the maleic anhydride modified epoxy dimethacrylate of 24.04-24.60%, the methyl methacrylate of 4.34-8.01%, the benzoyl peroxide of 0.32-0.58% and the N of 0.32-0.58%, and the N-dihydroxyethyl p-toluidine constitutes.
Four acicular type zinc oxide crystal whisker of the present invention and have following characteristics through the compound resin of its modification:
1. four acicular type zinc oxide crystal whisker (T-ZnOw) is 156.25 μ g/ml to the minimal inhibitory concentration (MIC) of streptococcus mutans, and minimal bactericidal concentration (MBC) is 312.5 μ g/ml.
2. four acicular type zinc oxide crystal whisker is made an addition in the compound resin when its mass percent in filler is 1%, 3%, 5%, 7%, 10%, resin is respectively 33.32 ± 1.12%, 84.85 ± 5.16%, 94.22 ± 3.73%, 92.33 ± 2.36%, 99.43 ± 0.48% to the antibiotic rate of streptococcus mutans
3. with above-mentioned compound resin burin-in process after 3 months, its antibiotic rate is respectively 30.56 ± 3.47%, 80.08 ± 4.39%, 89.89 ± 5.55%, 89.14 ± 4.28%, 90.33 ± 5.24%
4.T-ZnOw enhancement to compound resin:
Table 1T-ZnOw antiseptic-germicide addition to the influence of compound resin physical strength (X ± SD, α=0.05, n=10)
5.T-ZnOw interpolation to the influence of compound resin color
The color distortion of experimental group and control group before table 2 is aging (X ± SD)
#: Δ E＜1.0, color distortion do not show; 1.0＜Δ E＜3.3, color distortion can be distinguished in clinical tolerance interval; Δ E＞3.3, color distortion are obviously and can not be by clinical acceptance.
The color distortion of table 3 aging back experimental group and control group (X ± SD)
#: Δ E＜1.0, color distortion do not show; 1.0＜Δ E＜3.3, color distortion can be distinguished in clinical tolerance interval; Δ E＞3.3, color distortion are obviously and can not be by clinical acceptance.
Above content is to further describing that the present invention did in conjunction with concrete preferred implementation; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by claims of being submitted to.
Claims (2)
1. a method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance is characterized in that, according to following steps:
(1) compound resin filler and four acicular type zinc oxide crystal whisker are mixed the composition compound, the four acicular type zinc oxide crystal whisker mass percent in the described compound is 1-10%, and the compound resin filler is a surplus; Compound added obtain antibiotic filler after surface treatment liquid is handled;
(2) antibiotic filler and the mixing cured back of resinous substrates with step (1) gained forms the curing antibiotic compound resin, realizes the modification of compound resin performance; Wherein the mass percent of antibiotic filler is 10-80%, and the mass percent of resinous substrates is 20-90%.
2. a kind of according to claim 1 method of utilizing four acicular type zinc oxide crystal whisker modification compound resin performance is characterized in that: needles length≤30 μ m, the needles base diameter of four acicular type zinc oxide crystal whisker are 0.5-2 μ m in the described step (1).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030947A (en) * | 2010-12-23 | 2011-04-27 | 美的集团有限公司 | Composite material for manufacturing antibacterial polypropylene absorbent paper |
| CN103040631A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Antibacterial type inorganic whisker functional composite as well as preparation method and application thereof |
| CN104387654A (en) * | 2014-11-24 | 2015-03-04 | 苏州市贝克生物科技有限公司 | Medical antibacterial HDPE and preparation method thereof |
| CN105785714A (en) * | 2016-03-30 | 2016-07-20 | 华中科技大学 | Photosensitive resin for 3D printing and preparation and application method thereof |
| CN106361580A (en) * | 2016-08-31 | 2017-02-01 | 李健 | Anti-bacterial resin composite material for dental department and preparation method of anti-bacterial resin composite material |
| CN109161224A (en) * | 2018-08-21 | 2019-01-08 | 张玉英 | A kind of composite antibacterial filler and preparation method for plastics |
| CN111925593A (en) * | 2020-08-04 | 2020-11-13 | 日丰企业集团有限公司 | Antibacterial pipe and preparation method thereof |
| CN115192466A (en) * | 2022-06-02 | 2022-10-18 | 西南交通大学 | Preparation method of lamellar flower-shaped zinc oxide antibacterial dental composite resin |
| CN115838556A (en) * | 2022-12-16 | 2023-03-24 | 山东新升实业发展有限责任公司 | Metal support anti-corrosion treatment material and production process thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209971C (en) * | 2003-03-21 | 2005-07-13 | 西南交通大学 | Zinc oxide whisker compound germicide composition |
| CN101347386B (en) * | 2008-08-28 | 2012-05-30 | 成都军区昆明总医院 | Dentistry compound resin ceramic whisker stuffing surface modification and method of preparing the same |
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- 2009-11-13 CN CN2009102189411A patent/CN101705005B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030947A (en) * | 2010-12-23 | 2011-04-27 | 美的集团有限公司 | Composite material for manufacturing antibacterial polypropylene absorbent paper |
| CN103040631A (en) * | 2013-01-23 | 2013-04-17 | 常州南京大学高新技术研究院 | Antibacterial type inorganic whisker functional composite as well as preparation method and application thereof |
| CN103040631B (en) * | 2013-01-23 | 2016-03-30 | 常州南京大学高新技术研究院 | A kind of antimicrobial form inorganic crystal whisker functional composite material and method for making thereof and purposes |
| CN104387654A (en) * | 2014-11-24 | 2015-03-04 | 苏州市贝克生物科技有限公司 | Medical antibacterial HDPE and preparation method thereof |
| CN105785714A (en) * | 2016-03-30 | 2016-07-20 | 华中科技大学 | Photosensitive resin for 3D printing and preparation and application method thereof |
| CN106361580A (en) * | 2016-08-31 | 2017-02-01 | 李健 | Anti-bacterial resin composite material for dental department and preparation method of anti-bacterial resin composite material |
| CN109161224A (en) * | 2018-08-21 | 2019-01-08 | 张玉英 | A kind of composite antibacterial filler and preparation method for plastics |
| CN111925593A (en) * | 2020-08-04 | 2020-11-13 | 日丰企业集团有限公司 | Antibacterial pipe and preparation method thereof |
| CN115192466A (en) * | 2022-06-02 | 2022-10-18 | 西南交通大学 | Preparation method of lamellar flower-shaped zinc oxide antibacterial dental composite resin |
| CN115838556A (en) * | 2022-12-16 | 2023-03-24 | 山东新升实业发展有限责任公司 | Metal support anti-corrosion treatment material and production process thereof |
| CN115838556B (en) * | 2022-12-16 | 2024-01-23 | 山东新升实业发展有限责任公司 | Metal support anti-corrosion treatment material and production process thereof |
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