CN106700461A - Antibacterial and mildew-proof artificial marble material - Google Patents
Antibacterial and mildew-proof artificial marble material Download PDFInfo
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- CN106700461A CN106700461A CN201510510522.0A CN201510510522A CN106700461A CN 106700461 A CN106700461 A CN 106700461A CN 201510510522 A CN201510510522 A CN 201510510522A CN 106700461 A CN106700461 A CN 106700461A
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Abstract
The invention provides an antibacterial and mildew-proof artificial marble material. The antibacterial and mildew-proof artificial marble material is prepared from, in parts by weight, 1.5-15 parts of antibacterial and mildew-proof components and 85-99.5 parts of resin, wherein the antibacterial and mildew-proof components are prepared from 55-65 parts of nano zinc oxide and 35-45 parts of an isothiazolinone type antibacterial and mildew-proof agent. The prepared antibacterial and mildew-proof artificial marble material has excellent antibacterial and mildew-proof performance, a kitchen platform made of the material can effectively prevent microbial contamination, and the material provides a beneficial barrier for human health.
Description
【Technical field】
The present invention relates to a kind of antibacterial and mouldproof artificial marble materials, specifically, adopted the present invention relates to one kind
Antibacterial and mouldproof artificial marble materials and its side are prepared with antiseptic and mould inhibitor with cooperative effect
Method.
【Background technology】
Artificial stone is with its abundant color and decorative pattern, nontoxic radiationless, easy cleaning, it is possible to achieve seamless spelling
The advantages of connecing, using very extensively, is main flow cupboard in the market in home decoration especially cabinet table surface
Counter top material, but artificial marble is due to the presence for having macromolecule resin, and very easily pollution is thin to make it again
Bacterium.
Unavoidably there are many remaining foods, these remaining foods in kitchen as the place of processing and fabricating food
Thing is not only attracted fly, mouse, multiplies the insect pests such as cockroach, is also microorganism, bacterium carries out breeding and provide
Suitable condition, the fertility of bacterium is very strong, according to statistics：Under appropriate conditions, a bacterium is by 8
The breeding of hour, can reach 16,000,000, and one of main reason of food pollution is exactly microorganism.How
The microorganism for reducing kitchen cupboard table top also turns into a new demand of the people to health.Possess antibacterial and mouldproof
Therefore the artificial marble of function turns into a new development trend.
Artificial marble is made up of modified resin with rubble, in neutral or meta-alkalescence.By production raw materials
And production technology, generally can be divided into four classes：
Cement mo(u)ld artificial marble：Be using various cement as binding agent, addition sand, crushed marble, granite,
Industrial residue, through dispensing, stir, be molded, pressurize it is steam-cured, polishing, polishing and be made, be commonly called as terrazzo.
Polyester artificial marble：It is with unsaturated polyester (UP) as binding agent, with quartz sand, marble, Fang Xie
Stone flour etc. stirring mixing, cast molding, curing agent effect under produce solidification, through the demoulding, drying,
Polishing etc. operation and be made.Multiplex this method production artificial marble of China.
Method for imitation marble is respectively compound, slug type for other two kinds of production, both approaches because
Complex process, using little.
For above artificial marble production method, the present invention with the addition of a kind of with the new of compound synergy
Type antibacterial mildew inhibitor composition, is successfully prepared the artificial marble materials with antibacterial and antimildew function.This is specially
Antibacterial and mouldproof artificial marble materials prepared by profit not only have excellent antibacterial and mouldproof performance, and sterilized speed
Degree is fast.Do not produce biology drug resistance.
【The content of the invention】
It is an object of the invention to provide a kind of artificial marble materials with antibacterial and antimildew function.And provide one
Plant antibacterial and mouldproof manufacture method for artificial marble
Technical scheme：
The present invention is achieved by the following technical solutions, and antibacterial and mouldproof artificial marble materials recipe ingredient is such as
Under (in parts by weight)：
1.5-15 parts of antibacterial and mouldproof component
Resin 85-99.5 parts
Antibacterial and mouldproof component composition is as follows：
Nano zine oxide 55-65 parts
35-45 parts of OIT system antibacterial mildew inhibitor
For polyester artificial marble, above-mentioned resin can be various unsaturated polyester (UP)s, such as epoxy resin,
Phenolic resin, acryl resin, polyurethane resin etc..First step of the present invention is to add antibacterial and mouldproof component
Enter in resin, stir, then filler, curing agent, pigment etc. will be added to be sufficiently stirred in above-mentioned resin
Uniformly, moulding by casting, under curing agent effect, marble curing molding, it is possible to antibacterial and mouldproof people is obtained
Make marble.The ratio of filler and curing agent and resin is matched somebody with somebody according to common artificial marble producting proportion
Material.
For cement mo(u)ld artificial marble, binding agent uses various cement, then can be by above-mentioned formula
Resin replacement is cement, and antibacterial and mouldproof component is added in cement, then with mixing and stirrings such as fillers,
Shaping, you can antibacterial and mouldproof artificial marble is obtained.The also referred to as artificial terrazzo of antibacterial and mouldproof.
Description technical scheme in further detail below：
Antibacterial and mouldproof artificial marble materials recipe ingredient is following (in parts by weight),
0.5-15 parts of antibacterial and mouldproof component
Resin 85-99.5 parts
By antiseptic according to aforementioned proportion add resin in, be uniformly mixed, then artificial marble is filled out
Material and curing agent, pigment etc. are in strict accordance with common artificial marmorean formula rate with resin made above
Mixed, produced according to conventional production artificial marble technique.Antibacterial mildew inhibitor adds resin
In after, be well mixed extremely important, uniformity of the antiseptic in resin can directly affect the anti-of final products
Bacterium fungicidal properties.
Antibacterial and mouldproof component composition is as follows：
Nano zine oxide 55-65 parts
35-45 parts of OIT system antibacterial mildew inhibitor
Nano zine oxide refers to zinc oxide of its granular size at 1~100 nanometer, due to the granular of crystal grain,
Its Electronic Structure and crystal structure change, generate skin effect that macro object do not have,
The features such as bulk effect, quantum size effect and macroscopical tunnel-effect and the high grade of transparency, polymolecularity.This
A little features assign its excellent antibacterial and mouldproof.Heretofore described nano zine oxide, preferable particle size is
30-80 nanometers.Nano zine oxide used herein is that Zhejiang is converged in thousand nanosecond science and technology Co., Ltds or Shaanxi
The product of Nono-material Science ＆ Technology Ltd. of section.
According to the present invention, described OIT antibacterial mildew inhibitor is one or two 2- octyl group -4- isothiazole
The mixture of the chloro- 2- n-octyls -3- OITs (DCOIT) of quinoline -3- ketone (OIT), 4,5- bis-.
Preferably, described OIT antibacterial mildew inhibitor is the chloro- 2- n-octyls -3- isothiazolines of 4,5- bis-
Ketone (DCOIT).
The CAS numberings of 2- octyl groups -4- isothiazoline -3- ketone (OIT) are 26530-20-1, yellowish to amber
Transparency liquid, is dissolved in organic solvent, is slightly soluble in water, be a kind of low toxicity, efficiently, broad spectrum type mould inhibitor, it is right
Mould have very strong killing action, preferable anti-mold effect can be reached, can be widely applied to coating, paint,
In all multi-products such as lubricating oil, shoe polish, leather chemistry, timber-work and historical relic's protection.What the present invention was used
It is the product of Shandong De Lan Chemical Co., Ltd.s or Beijing Tianqing Chemical Co., Ltd.'s production.
The CAS numberings of 4,5- bis- chloro- 2- n-octyls -3- OITs (DCOIT) are 64359-81-5, in vain
To pale yellow powder, it is a kind of wide-spectrum bactericide to color, can effectively kill blue or green germ, basidiomycetes, black Qu bacterium,
Fusarium, Wan Bao Mildew, green gluing sweep mould etc..The compounds such as the organo-arsenic of huge poison are may replace, oil is widely used in
The plastic industries such as paint, coating, polyethylene, Polyurethane, leather, paint, coating, sewage, papermaking, wood
The fields such as material, adhesive, ink.The DCOIT that the present invention is used is the proud chemical company in Dalian hundred or three rich lifes
Change the product of Shanghai Co., Ltd production.
Two kinds of antibacterial mildew inhibitors selected in the present invention be have passed through scientific experiment screen meticulously one of development it is multiple
Close formula.Said composition not only can quickly kill the microorganisms such as bacterium mould, and be wrapped according to the present invention
Both proportions for containing have extraordinary synergistic function.
Nano zine oxide belongs to inorganic antimicrobial mildew preventive agent, and its antibacterial and mouldproof Performance comparision is good, but sterilization speed with
All of inorganic antiseptic is the same, and action speed is slow, generally requires competence exertion bactericidal action in 24 hours,
And it is so slow for family is used as the marble material that kitchen countertop etc. is often contacted with people and food
Anti-microbial property is far from being enough., used as a kind of organic antibacterial agent, its sterilization speed is fast, fungicidal properties for DCOIT
Also it is very good, but exclusive use organic antibacterial agent can produce biology drug resistance, and the time is long.Bacterium is to this
Antiseptic produces resistance, causes the reduction of its bactericidal effect.Antibacterial and mouldproof composition of the present invention is effective
Solution the two drawbacks.Killing machine of the inorganic antimicrobial mildew preventive agent nano zine oxide to microorganisms such as bacterium moulds
Reason determines that it will not produce biology drug resistance, and the effect of the quick sterilization of DCOIT is quickly gone out there is provided one
The process of bacterium.Meet our requirements to health.The antibacterial and mouldproof composition shows non-under study for action
Normal preferably synergistic function.This is also one of innovative point that the present invention is different from other inventions.
The synergistic function of antibacterial and mouldproof composition of the invention can be by determining the minimum suppression of one-component
The minimum inhibitory concentration of bacteria concentration and compounding ingredients judges.
This experiment have references to the conventional classification Mlc index method (fractional of antibiotic synergy
Inhibitory concentration, FIC) it is compound to nano zine oxide and OIT antibacterial mildew inhibitor
The antibacterial synergistic function of component is evaluated.
The computing formula of FIC indexes：
FIC indexes=MIC (A groups joint)/MIC (A groups are alone)+MIC (B groups joint)/MIC (B groups are alone)
FIC index interpretation standards：When FIC indexes are less than 0.5, two kinds of medicines are synergy；Work as FIC
When index is 0.5~1, two kinds of medicines are summation action；When FIC indexes are more than 1 and during less than 2, two kinds
Medicine is unrelated effect；When FIC indexes are more than 2, two kinds of medicines are antagonism.
Minimum inhibitory concentration experiment is carried out according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.1.7.3,
The minimal inhibitory concentration of one-component, its result of the test is listed in Table 1 below；Then again respectively by nano zine oxide
Mix according to a certain ratio with both OIT antibacterial mildew inhibitors, it is equally minimum using test mentioned above
The method of Mlc, the minimal inhibitory concentration of test compounding component.Each component respectively with the third alcohol-water solution (1:
1) mother liquor that solvent is diluted to 10000ppm is done, and the concentration of each component is also 10000ppm in mixed liquor.
Minimal inhibitory concentration (MIC) of the antiseptic single composition of table 1. to bacterium
The antiseptic of table 2. compounds composition dividing to the minimal inhibitory concentration (MIC) of bacterium and point between be re-dubbed
Level Mlc index (FIC)
General material can be assumed that to be with anti-microbial property, such as to the minimal inhibitory concentration of bacterium less than 800ppm
Professional standard HG/T3794-2005《Inorganic antiseptic-performance and evaluation》Specified in minimal inhibitory concentration must
800ppm must be less than.This can be seen that by minimal inhibitory concentration (MIC) result of the single antibacterial components of table 1
The minimal inhibitory concentration for inventing selected antimicrobial moiety is far smaller than 800ppm, therefore has been showed good
Bacteriostatic activity.Table 2 shows, when independent role compared with, the minimum suppression of antiseptic system composition after compounding
Bacteria concentration all reduces more.According to classification Mlc index method judge organic antibacterial agent and nano zine oxide it
Between interaction：For two kinds of bacteriums, selected isothiazolinone antibacterial mildew inhibitor and nano oxygen
The FIC indexes for changing zinc composite parts are respectively less than 0.5, and there is the selected composite parts of this explanation present invention collaboration to increase
Effect is acted on.
The superior function of this patent product is described below in detail
1st, antibacterial and mouldproof excellent performance, through the artificial marble that this patent method is prepared, according to
QB/T2591-2003《Antibiotic plastic Anti-microbial Performance Tests method and antibacterial effect》Standard testing, to large intestine bar
Bacterium, antibiotic rate >=99% of staphylococcus aureus, to 6 kinds of fungicidal properties of mixing mould up to 0 grade, survey
Test result is shown in Table 3, and antibiotic rate is higher, and the anti-microbial property that represents is more excellent, and antibiotic rate is generally considered to be more than 90%
Qualified anti-biotic material.Fungicidal properties is also the superlative degree with 0 grade.1 grade of fungicidal properties is regarded as mildew resistance
Can be qualified.
Fungicidal properties test fungal species are the mixture of following 6 kinds of moulds.
The equivalent ATCC 6275 of aspergillus niger (Aspergillus niger) AS 3.4463
Aspergillus terreus (Aspergillus terreus) AS 3.3935
Paecilomyces varioti (Paecilomyces Varioti) AS3.4253
Penicillium funiculosum (Penicillium funicolosum) AS3.3875
Aureobasidium pullulans (Aureobasium Pullulans) AS3.3984
Ball hair shell (Chaetoomium globsum) AS3.4254 or ATCC6205
The antibacterial and mouldproof artificial marble antibacterial and mouldproof performance test of table 3.
2nd, sterilized action speed is fast
Common inorganic antiseptic works and wants nearly 24 hours, and the artificial marble that the present invention is developed is at 3
Hour antibiotic rate can just reach more than 90.It is shown in Table 4,5 artificial marbles made for purely inorganic antiseptic
The antibiotic rate test result of times of contact different with patented product of the present invention
The antibiotic rate of the artificial marble difference time of contact that the common inorganic antiseptic of table 4. makes
| Time of contact (hour) | 0 hour | 3 hours | 20 hours | 24 hours |
| Escherichia coli (%) | 0 | 0 | 78% | 98% |
| Staphylococcus aureus (%) | 0 | 0 | 82% | 95% |
The antibiotic rate of this patent of table 5. artificial antibacterial and mouldproof marble difference time of contact
| Time of contact (hour) | 0 hour | 2 hours | 3 hours | 24 hours |
| Escherichia coli (%) | 0 | 86% | 95% | 99.9% |
| Staphylococcus aureus (%) | 0 | 92% | 97% | 99.9% |
【Specific embodiment】
Embodiment 1
It is first according to following weight ratio and prepares antibacterial and mouldproof component：
55 parts of nano zine oxide
45 parts of 2- octyl groups -4- isothiazoline -3- ketone (OIT)
Then said components are mixed according to following ratio (weight portion) with resin again, are stirred,
The uniformity can have directly influence to the antibacterial and mouldproof performance of final products.
Antibacterial and mouldproof artificial marble materials recipe ingredient is following (in parts by weight),
1.5 parts of antibacterial and mouldproof component
98.5 parts of resin
By antiseptic according to aforementioned proportion add resin in, be uniformly mixed, then artificial marble is filled out
Material and curing agent, pigment etc. are in strict accordance with common artificial marmorean formula rate with resin made above
Mixed, carrying out production according to conventional production artificial marble technique can be prepared by antibacterial and mouldproof artificial stone.
Embodiment 2
It is first according to following weight ratio and prepares antibacterial and mouldproof component：
65 parts of nano zine oxide
4,5- bis- chloro- 35 parts of 2- n-octyls -3- OITs (DCOIT)
Then said components are mixed according to following (weight portion) ratio with resin again, is stirred.
Antibacterial and mouldproof artificial marble materials recipe ingredient is following (in parts by weight),
14 parts of antibacterial and mouldproof component
86 parts of resin
By antiseptic according to aforementioned proportion add resin in, be uniformly mixed, then artificial marble is filled out
Material and curing agent, pigment etc. are carried out according to common artificial marmorean formula rate with resin made above
Mixing, carries out production and can be prepared by antibacterial and mouldproof artificial marble according to conventional production artificial marble technique.
Embodiment 3
It is first according to following weight ratio and prepares antibacterial and mouldproof component：
60 parts of nano zine oxide
4,5- bis- chloro- 20 parts of 2- n-octyls -3- OITs (DCOIT)
20 parts of 2- octyl groups -4- isothiazoline -3- ketone (OIT)
Then said components are mixed according to following (weight portion) ratio with resin again, is stirred.
Antibacterial and mouldproof artificial marble materials recipe ingredient is following (in parts by weight),
8 parts of antibacterial and mouldproof component
92 parts of resin
By antiseptic according to aforementioned proportion add resin in, be uniformly mixed, then artificial marble is filled out
Material and curing agent, pigment etc. are carried out according to common artificial marmorean formula rate with resin made above
Mixing, carries out production and can be prepared by antibacterial and mouldproof artificial marble according to conventional production artificial marble technique.
Embodiment 4
It is first according to following weight ratio and prepares antibacterial and mouldproof component：
62 parts of nano zine oxide
4,5- bis- chloro- 10 parts of 2- n-octyls -3- OITs (DCOIT)
28 parts of 2- octyl groups -4- isothiazoline -3- ketone (OIT)
Then said components are mixed according to following (weight portion) ratio with cement again, is stirred.
Antibacterial and mouldproof artificial marble materials recipe ingredient is following (in parts by weight),
5 parts of antibacterial and mouldproof component
99 parts of cement
By antiseptic according to aforementioned proportion add cement in, be uniformly mixed, then by filler and solidification
Agent, pigment etc. are mixed according to common artificial marmorean formula rate with cement made above, according to
The conventional mode of production carries out production and can be prepared by antibacterial and mouldproof terrazzo.
Antibacterial and mouldproof artificial marble to embodiment 1-4 carries out antibacterial and mouldproof performance test, the results are shown in Table 6：
The embodiment product antibacterial and mouldproof performance table of table 6.
The embodiment product quick sterilization rate performance table of table 7.
Antibacterial and mouldproof artificial marble materials prepared by above-mentioned 4 embodiments, test result shows.It is to leather
Lan Shi negative bacterium E. colis, the antibiotic rate of gram-positive bacteria staphylococcus aureus are all higher than 99%, to six
The mould proof grade for planting mixing mould is 0 grade, and product also shows the performance of very quick sterilization simultaneously,
Its sterilizing rate of hour of contact three is all higher than 95%, and after 5 hours of contact, antibiotic rate is more than 99%.
Claims (3)
1. a kind of antibacterial and mouldproof artificial marble materials, it is characterised in that each component including following mass fraction：
1.5-15 parts of antibacterial and mouldproof component
Resin 85-99.5 parts
Antibacterial and mouldproof component composition is as follows：
Nano zine oxide 55-65 parts
35-45 parts of OIT system antibacterial mildew inhibitor.
2. nano zine oxide as claimed in claim 1, it is characterised in that Particle Size of Nanometer ZnO is 30-80 nanometers.
3. OIT system as claimed in claim 2 antibacterial mildew inhibitor, it is characterized in that mould inhibitor can be the mixture of any of which in 2- octyl groups -4- isothiazoline -3- ketone (OIT) or the chloro- 2- n-octyls -3- OITs (DCOIT) of 4,5- bis- or both any ratio.
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| CN108126231A (en) * | 2017-12-01 | 2018-06-08 | 高产明 | A kind of preparation method of the antibacterial hospital gauze of high intensity |
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| CN110358147A (en) * | 2019-07-11 | 2019-10-22 | 广州佳伲斯防霉抗菌科技有限公司 | A kind of antimildew and antibacterial algaecide and its preparation method and application |
| CN110944959A (en) * | 2017-07-31 | 2020-03-31 | 乐天尖端材料株式会社 | Resin composition for engineering stone and engineering stone formed therefrom |
| CN111497409A (en) * | 2020-05-22 | 2020-08-07 | 美盈森集团股份有限公司 | Antibacterial mildew preventive, mildew-proof starch glue, mildew-proof antibacterial corrugated paper and preparation method thereof |
| CN111869681A (en) * | 2020-08-12 | 2020-11-03 | 高时(厦门)石业有限公司 | Method for preparing antibacterial agent, antibacterial agent and antibacterial artificial stone using same |
| CN111919857A (en) * | 2020-08-12 | 2020-11-13 | 高时(厦门)石业有限公司 | Preparation method of sterilization powder, sterilization powder and antibacterial inorganic artificial stone using sterilization powder |
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| CN112428643A (en) * | 2020-12-04 | 2021-03-02 | 东莞承达家居有限公司 | Antibacterial and mildewproof furniture material |
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| US11505674B2 (en) | 2017-11-08 | 2022-11-22 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article produced from same |
| CN108126231A (en) * | 2017-12-01 | 2018-06-08 | 高产明 | A kind of preparation method of the antibacterial hospital gauze of high intensity |
| US12084569B2 (en) | 2018-11-30 | 2024-09-10 | Lotte Chemical Corporation | Thermoplastic resin composition and molded article formed therefrom |
| CN110358147A (en) * | 2019-07-11 | 2019-10-22 | 广州佳伲斯防霉抗菌科技有限公司 | A kind of antimildew and antibacterial algaecide and its preparation method and application |
| CN110283407A (en) * | 2019-07-22 | 2019-09-27 | 芜湖海螺型材科技股份有限公司 | A kind of antibacterial and mouldproof ecological floor and preparation method thereof |
| CN111497409A (en) * | 2020-05-22 | 2020-08-07 | 美盈森集团股份有限公司 | Antibacterial mildew preventive, mildew-proof starch glue, mildew-proof antibacterial corrugated paper and preparation method thereof |
| CN111919857A (en) * | 2020-08-12 | 2020-11-13 | 高时(厦门)石业有限公司 | Preparation method of sterilization powder, sterilization powder and antibacterial inorganic artificial stone using sterilization powder |
| CN111869681A (en) * | 2020-08-12 | 2020-11-03 | 高时(厦门)石业有限公司 | Method for preparing antibacterial agent, antibacterial agent and antibacterial artificial stone using same |
| CN112143087A (en) * | 2020-09-14 | 2020-12-29 | 成都金发科技新材料有限公司 | Antibacterial and mildewproof automobile sound insulation material and preparation method thereof |
| CN112428643A (en) * | 2020-12-04 | 2021-03-02 | 东莞承达家居有限公司 | Antibacterial and mildewproof furniture material |
| CN112568238A (en) * | 2020-12-22 | 2021-03-30 | 常州山由帝杉防护材料制造有限公司 | Industrial antibacterial liquid, preparation method thereof and special preparation device |
| CN114933843A (en) * | 2022-03-30 | 2022-08-23 | 温州环诺新材料科技有限公司 | Antibacterial environment-friendly water-based paint and preparation method thereof |
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