CN103773308B - Long-acting antibacterial and mildew-proof silicone adhesive and preparation method thereof - Google Patents
Long-acting antibacterial and mildew-proof silicone adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a long-acting antibacterial and mildew-proof silicone adhesive and a preparation method thereof. The preparation method comprises the steps: grinding an efficient and environment-friendly organic sterilizing and mildew-proof agent and an inorganic zinc loaded zeolite antibacterial agent with a porous structure at high speed in high-speed grinding equipment and thus organically combining the organic sterilizing and mildew-proof agent and the inorganic zinc loaded zeolite antibacterial agent by using a coupling agent on the basis of comprehensively researching and analyzing the characteristics of all antibacterial and mildew-proof agent systems to obtain a novel composite antibacterial and mildew-proof agent; then, adding the obtained composite antibacterial and mildew-proof agent into a silicone adhesive material by using the traditional silicone adhesive production equipment and a conventional adhesive preparation process to finish the preparation of the long-acting antibacterial and mildew-proof silicone adhesive. The antibacterial and mildew-proof silicone adhesive provided by the invention is low in raw material cost, simple in production process, free of three wastes and capable of meeting the requirement for environment friendliness. The long-acting antibacterial and mildew-proof silicone adhesive prepared by the invention is efficient and durable in antibacterial and mildew-proof performances and capable of meeting the technical requirement for use in fields such as buildings, electronic appliances, automobiles, boats and the like.
Description
Technical field
The present invention relates to seal gum field.More specifically, the present invention relates to a kind of silicone adhesive with long acting antibiotic antimildew function, also relates to the preparation method of described Antimicrobial mildew-proof silicon adhesive.
Background technology
Single-component room-temperature vulcanized (RTV-1) silicone adhesive is with the ageing-resistant performance of its excellence, good elasticity, outstanding water resistance, be widely used in the waterproof sealing of seam between kitchen, bathroom, the sanitary ware of toilet and table top, body of wall, furniture, and consumption is increasing.But because these occasions are throughout the year moister, silicone adhesive is easy to the infringement being subject to the microorganism such as bacterium, mould, cause that adhesive tape is mouldy, variable color, to come off, lose water-tight function, if these unwanted bacterias and human contact also can infect various disease, the health of the threat mankind waits property and electrical insulating property etc.For above problem, scientific worker has prepared mildew-resistant organosilicon sealant by adding some mould inhibitors, to improve the performance that its antifungal corrodes, increases the service life.Antibacterial and mouldproof mould inhibitor available on Vehicles Collected from Market mainly contains two classes: (1) mineral-type, as metal (silver, copper, zinc, tin, rare earth etc.) inorganic salt etc., nano titanium oxide, nano zine oxide, nanometer silver etc.Its remarkable advantage is high security, slow-releasing is good, broad spectrum antibacterial, not easily develop immunity to drugs, good heat resistance and easy to process, therefore its application and research is more and more subject to people's attention.Wherein outstanding with silver-series antibacterial agent performance, but its exist cost high, easy to change, to mould and alga microbial inhibition difference etc. problem.With regard to silicone adhesive, when based on antifungal and algae, so pure inorganic antiseptic has its limitation.(2) organic, as quaternary ammonium salt, biguanides, alcohols, phenols, organo-metallic class, pyridines, imidazoles, isothiazolinone and BIT class etc.Such antiseptic-germicide fungicidal spectrum is wide, speed is fast, but often there is poor heat resistance, easily to decompose and the shortcoming such as work-ing life is short, and what have also has the side effect such as stronger toxicity and environmental pollution.
In recent years, the main report about Antimicrobial mildew-proof silicon adhesive preparation research is as follows:
CN10129855B discloses a kind of nanometer mildewproof sealing neutral silicone resin, and its effective mould inhibitor composition is nano-Ag particles, there is cost high, easy to change, the shortcoming weak to mould inhibition.
CN103130442A discloses a kind of material of construction mildewproof additive, its main component is dimethyl fumarate, this component is with low cost, fungicidal properties is good, but from October, 2008, European Union aspect just circulates a notice of a lot of case producing allergic, acute eczema because human consumer contact footwear, leather sofa etc. containing dimethyl fumarate and burn successively, makes it receive extensive concern.On January 29th, 2009, EU member country have passed draft resolution, started the product of " containing dimethyl fumarate " from May 1st, 2009, and it will be prohibited from entering EU market circulation and sell.
CN102485823A discloses a kind of mildew-resistant organosilicon sealant, and this patent of invention mould inhibitor used is 2n acyl group isothiazolinone and BIT (BIT), finds that its component 2n acyl group isothiazolinone describes inaccurate through great mass of data retrieval.It is said that this invention mildewproof sealant anti-mold effect is excellent, but pure organic mould inhibitor is often too fast migrates to material surface, easily causes loss, therefore affect material mildew-resistant endurance quality.
CN102604586A discloses a kind of production method of double glazing mildew-resistant silicone sealant, mildew-resistant composition is not added in its production process, it is said that it is never mouldy in moist place, but actually operating is not necessarily so, the siloxanes organism contained in its component is easy to become the nutritive substance of microorganism growth in temperature, humidity proper environment, and the active nano-calcium carbonate contained in component does not almost have inhibition to microorganism.
CN103013354A discloses a kind of preparation method of neutral mildew-resistant glass cement, and its effective constituent it is said a kind of Antisepticize and mildew preventive being called A2, does not find its actual component structure.
266 ~ 268 pages, " organosilicon material " (2013,27 (4)) report interpolation 3 kinds of mould inhibitor massfractions when being less than 1%, and the mildew-resistant grade of gained mildew-resistant organosilicon sealant reaches 1-0 level, undeclared 3 kinds of mould inhibitor component structures in literary composition.
CN103122238A discloses a kind of Antimicrobial mildew-proof silicon adhesive and preparation method thereof, its antiseptic-germicide used is that Cubic zirconium phosphate carries silver compound, but this component belongs to silver-series antibacterial agent kills excellent effect to bacterium, but on the weak side to mould effect, and it is dangerous to there is silver-colored yellowing variable color in use procedure.
At present, mildew-resistant silicone adhesive product mostly is external import or a few large factory production domestic on the market, production cost is higher, often prop up sebific duct price about 30 yuan, other is beyond affordability for ordinary people, and its mildew-resistant mechanism mainly relies on silica gel material self inertia resist microorganism growth and play mildew-proof function, often occurs the phenomenon of " mildew-resistant glue " not mildew-resistant in the actual use procedure of human consumer is as moist especially rugged environment.So market is badly in need of a kind of safety, environmental protection, efficient, long acting antibiotic mildew-resistant ketone glue, and also need material produce manufacture craft simple, cost is lower, meets other service requirements of ordinary people, can apply on a large scale.For this reason, the present inventor completes the present invention finally through lot of experiments.
Summary of the invention
The object of this invention is to provide a kind of long acting antibiotic mildew-resistant silicone adhesive.
Another object of the present invention is to provide the preparation method of described long acting antibiotic mildew-resistant silicone adhesive.
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of long acting antibiotic mildew-resistant silicone adhesive, it is characterized in that what described long acting antibiotic mildew-resistant silicone adhesive was made up of following component by weight:
Basis glue 40-90 part;
Linking agent 2-10 part;
Filler 2-40 part;
Catalyzer 0.05-1 part;
Softening agent 0-20 part;
Coupling agent 0.5-5 part;
Composite antimicrobial mould inhibitor 0.5-2 part;
Described basic glue is α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue); Described linking agent is the one in methyl triacetoxysilane, methyl tributanoximo silane, methyltrimethoxy silane or methyl isopropyl alkene TMOS; Described filler is the one in gas-phase silica or nano-calcium carbonate; Described catalyzer be two acetic acid acid dibutyl tins or diisopropoxy-bis-(acetylacetone based) titanium in one; Described softening agent is polydimethylsiloxane; Described coupling agent is the one in γ-(2,3-epoxy third oxygen) (KH-560) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570).
The Antimicrobial mildew-proof silicon adhesive that the present invention relates to, is characterized in that what described composite antimicrobial mould inhibitor was made up of following component by weight:
Carry zinc zeolite inorganic antiseptic 75-94.5 part;
Organic bactericide mould inhibitor 5-20 part;
Coupling agent 0.5-5 part;
Described organic bactericide mould inhibitor is N-(2, 2-dichloroethylene) salicylic amide (A26), derosal (methyl-benzoimidazole-2-Urethylane, BCM), m-tetrachlorophthalodinitrile (2, 4, 5, 6 one tetrachloros 1, 3 one benzene dicarbonitriles), Zinc Pyrithione (ZPT), N-octyl-isothiazolinone (OIT), 4, the chloro-N-octyl group of 5-bis--4-isothiazoline-3-ketone (DCOIT), 1, 2-benzisothiazole-3-ketone (BIT), n-butyl-1, at least one in 2-isothiazoline-3-ketone (BBIT) or IPBC (IPBC), described coupling agent is three stearic acid isopropyl titanates.
The invention still further relates to the preparation method of long acting antibiotic mildew-resistant silicone adhesive, it is characterized in that the step of the method is as follows:
A, first by organic bactericide mould inhibitor, carry zinc zeolite inorganic antiseptic, coupling agent and a grinding aid dehydrated alcohol add in blue-type mulling machine together, under 1000-2000rpm rotating speed, grind 60-120min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 30-60min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor, for subsequent use.
B, first the composite antimicrobial mould inhibitor prepared by basic glue, softening agent, steps A to be dropped in multifunctional mixer by proportioning, vacuum stirring 15-30min at 80-120 DEG C; Then linking agent and filler continuation stirring 30-60min is added; Secondly catalyzer and coupling agent is added by proportioning, vacuum stirring 30-60min at 100-150 DEG C; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant silicone adhesive.
The principle of institute of the present invention foundation is: make the anti-mold effect that silicone adhesive reaches good, and its key is screening and the efficient combination of added mould inhibitor, and namely technological core of the present invention is the preparation of composite antimicrobial mould inhibitor.In the process of preparation, the feature of the existing inorganic antiseptic of comprehensive analysis and organic bactericide mould inhibitor self, the two is organically combined by any special measures, makes it with the advantage of inorganic antiseptic high safety, good endurance, there is again the advantage of has a broad antifungal spectrum, quick-acting antibacterial and mouldproof.Consider expensive, the allochroic shortcoming of silver-series antibacterial agent in addition, determine to select zinc series antibacterial agent as inorganic antiseptic component, and select year zinc zeolite antibacterial agent with vesicular structure, cost is lower, colourless change problem.Selecting organic bactericide mould inhibitor to be pay close attention to its hypotoxicity, the feature of environmental protection and high-efficiency broad spectrum simultaneously.The preparation of composite antimicrobial mould inhibitor completes on basket-type grinder, use dehydrated alcohol as grinding aid, itself and organic bactericide mould inhibitor have certain consistency, can ensure that organic biocide mildewcide forms ultra-fine particles under speed lapping state, penetrate into dehydrated alcohol in the vesicular structure carrying zinc zeolite, titanate coupling agent that the present invention adds both can form firm keyed jointing with organic bactericide mould inhibitor polar groups or atom by covalent linkage or hydrogen bond simultaneously, also can form firm keyed jointing with carrying activity hydroxy in zinc zeolite cavity structured calcium silicate simultaneously, so titanate coupling agent can be keyed to zeolite cavity surface securely by entering the organic bactericide mould inhibitor carried in zinc zeolite cavity, ensure that it in use equally with zine ion slowly releases, improve useful life longevity, simultaneously together with zine ion to bacterium, the harmful microorganisms such as mould form collaborative inhibitory or killing effect, there is good synergistic effect.
Antimicrobial mildew-proof silicon adhesive type of the present invention is that single-component takes off acetic acid type, single-component ketoxime removing type, single-component dealcoholization-type or single-component deacetone, can meet the different technical requirements in silicone adhesive different application field.
Product stock stable performance of the present invention, raw materials safety and environmental protection, in use the antibiotic rate of Antimicrobial mildew-proof silicon adhesive to intestinal bacteria and streptococcus aureus is greater than 99%, 1 ~ 0 grade is reached to the mildew-resistant grade of aspergillus niger, terreus etc. six kinds mixing mould, and antibacterial and mouldproof lasting effect excellent performance.
In more detail the present invention will be described below.
The present invention relates to a kind of long acting antibiotic mildew-resistant silicone adhesive, it is characterized in that what described long acting antibiotic mildew-resistant silicone adhesive was made up of following component by weight:
Basis glue 40-90 part;
Linking agent 2-10 part;
Filler 2-40 part;
Catalyzer 0.05-1 part;
Softening agent 0-20 part;
Coupling agent 0.5-5 part;
Composite antimicrobial mould inhibitor 0.5-2 part.
According to a kind of optimal way of the present invention, described basic glue is α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue); Described linking agent is the one in methyl triacetoxysilane, methyl tributanoximo silane, methyltrimethoxy silane or methyl isopropyl alkene TMOS; Described filler is the one in gas-phase silica or nano-calcium carbonate; Described catalyzer be two acetic acid acid dibutyl tins or diisopropoxy-bis-(acetylacetone based) titanium in one; Described softening agent is polydimethylsiloxane; Described coupling agent is the one in γ-(2,3-epoxy third oxygen) (KH-560) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570).The above basic material preparing silicone adhesive of the present invention is commercially available conventional products.
The Antimicrobial mildew-proof silicon adhesive that the present invention relates to, is characterized in that what described composite antimicrobial mould inhibitor was made up of following component by weight:
Carry zinc zeolite inorganic antiseptic 75-94.5 part;
Organic bactericide mould inhibitor 5-20 part;
Coupling agent 0.5-5 part.
According to a kind of optimal way of the present invention, the described zinc zeolite antibacterial agent that carries is that zine ion is loaded to the novel compositions being formed in porous natural zeolite or synthetic zeolite and have antibacterial effect by ion-exchange, the median size of the present invention's used year zinc zeolite is 1-10 μm, is the product of market sale.
According to another kind of optimal way of the present invention, described organic bactericide mould inhibitor is N-(2, 2-dichloroethylene) salicylic amide (A26), derosal (methyl-benzoimidazole-2-Urethylane, BCM), m-tetrachlorophthalodinitrile (2, 4, 5, 6 one tetrachloros 1, 3 one benzene dicarbonitriles), Zinc Pyrithione (ZPT), N-octyl-isothiazolinone (OIT), 4, the chloro-N-octyl group of 5-bis--4-isothiazoline-3-ketone (DCOIT), 1, 2-benzisothiazole-3-ketone (BIT), n-butyl-1, at least one in 2-isothiazoline-3-ketone (BBIT) or IPBC (IPBC), described coupling agent is three stearic acid isopropyl titanates.
N-(2,2-dichloroethylene) salicylic amide (A26), have another name called fungi spirit or trichlamide, CAS is numbered 70193-21-4, and molecular formula is C
13h
16cl
5nO
3, pale powder, is a kind of excellent High-efficiency low-toxicity moldproof agent, is widely used in the antimycotic antiseptics such as leather, coating, cloth plastic cement, spinning sizing agent.Extremely strong inhibition is had to Aspergillus and Penicillium fungi and chactomium globosum, bread mould, reaping hook are mould etc., all having extremely strong killing action to various microorganisms such as intestinal bacteria, streptococcus aureus, tangerine grass bacillus, is 50 ~ 500ppm to the minimum inhibitory concentration (MIC) of various bacterium.The present invention mould inhibitor A26 used is the product of Shandong Ai Pu chemical company production and sales.
Derosal, have another name called carbendazol, carbendazol, CAS is numbered 10605-21-7, formal name used at school methyl-benzoimidazole-2-Urethylane, is called for short BCM.Derosal is a kind of broad-spectrum germicide, has prevention effect to the disease that various crop is caused by fungi (as imperfect fungi, many ascomycetess).Can be used for foliar spray, seed treatment and soil treatment etc.The present invention's derosal used is the product of Huayang Agricultural Chemial Group Co Ltd, Shandong or the production and sales of Jiangsu Tai Cang agrochemical company limited.
M-tetrachlorophthalodinitrile (2,4,5,6 one tetrachloro one 1,3 one benzene dicarbonitrile), CAS is numbered 1897-45-6, and molecular formula is C
8n
2cl
4, be a kind of low toxicity, non-internal-absorting wide-spectrum bactericide, to various crop fungal disease, there is prophylactic effect.
ZPT, English name is Pyrithionc Zinc, writes a Chinese character in simplified form ZPT, and call as Pyrithionc Zinc, CAS is numbered 13463-41-7, and molecular formula is C
10h
8n
2o
2s
2zn, molecular weight is 317.7.For shampoo anti-dandruff, the growth of Gram-positive, negative bacteria and mould can be suppressed.Can hair conditioning effectively, delay the aging of hair, control the generation of white hair and alopecia.Also be used as makeup preservatives or finish, coating biocide in addition; As the biocide mildewcide of the product such as coating and plastics, use also very extensive.The present invention's ZPT used (ZPT) sets a prairie fire the product of Chemical Co., Ltd.'s production and sales in Hebei KeYu biochemical industry company limited or Jiangsu.
N-octyl-isothiazolinone, CAS is numbered 26530-20-1, is called for short OIT, is dissolved in organic solvent, is slightly soluble in water, is a kind of low toxicity, efficient, broad spectrum type biocide mildewcide, has very strong killing action, can reach desirable anti-mold effect to bacterium, mould etc.Can be widely used in all multi-products such as coating, paint, lubricating oil, shoe polish, leather chemistry, timber-work and historical relic's protection.VOC free, high light and high temperatures, broad-spectrum is efficient, effectively can prevent the bacterium in plastics and fungi.The present invention OIT used is the product of the proud chemical company in Dalian hundred or Beijing Tianqing Chemical Co., Ltd.'s production and sales.
The chloro-N-octyl group of 4,5-bis--4-isothiazoline-3-ketone, CAS is numbered 64359-81-5, and being called for short DCOIT, is a kind of wide-spectrum bactericide.Can be widely used in paint, coating, polyethylene, the plastic industries such as polyurethane, leather, paint, coating, sewage, papermaking, timber, tackiness agent, the fields such as ink, can replace the compounds such as the organoarsenic of huge poison.The present invention DCOIT used is the product of the proud chemical company in Dalian hundred or Beijing Tianqing Chemical Co., Ltd.'s production and sales.
BIT, CAS is numbered 2634-33-5, and being called for short BIT, is main commercial sterilization, anticorrosion, anti-enzyme agent.There is outstanding the grow effect of microorganism in organic medium such as mould fungus inhibition (fungi, bacterium), algae, solve that the organic products that microbial growth causes is mouldy, fermentation, rotten, breakdown of emulsion, smelly, etc. series of problems.The present invention DCOIT used is the product of the proud chemical company in Dalian hundred production and sales.
N-butyl-1,2-isothiazoline-3-ketone, CAS is numbered CAS 4299-07-4, be called for short BBIT, be exclusively used in and kill erosion and be attached to microorganism on the macromolecular materials such as urethane (PU), polyvinyl chloride (PVC), polysiloxane (silicone), polyethylene (PE), polypropylene (PP), can be miscible with softening agent, organic carrier and thinner, easy to use.The present invention BBIT used is the product of Shandong Ai Pu chemical company production and sales.
IPBC (IPBC), No. CAS is numbered 55406-53-6, and molecular formula is C
8h
12iNO
2, be a kind of effective fungicidal preservative, be mainly used in the variable color control, textiles, paper-making industry, ink, tackiness agent etc. of makeup, household chemicals, paint, leather, plastics, timber, metal cutting solution, timber.The present invention IPBC used is the product of Hangzhou Shang You Chemical Co., Ltd. production and sales.
Preferably, organic bactericide mould inhibitor of the present invention is N-(2,2-dichloroethylene) salicylic amide (A26), Zinc Pyrithione (ZPT), 4, the chloro-N-octyl group of 5-bis--4-isothiazoline-3-ketone (DCOIT), 1, at least one in 2-benzisothiazole-3-ketone (BIT), n-butyl-1,2-isothiazoline-3-ketone (BBIT) or IPBC (IPBC).
More preferably, organic bactericide mould inhibitor of the present invention is N-(2,2-dichloroethylene) at least one in salicylic amide (A26), Zinc Pyrithione (ZPT), n-butyl-1,2-isothiazoline-3-ketone (BBIT) or IPBC (IPBC).
According to another kind of optimal way of the present invention, described coupling agent is three stearic acid isopropyl titanates, belong to titante coupling agent, its CAS is numbered 61417-49-0, and the active group contained in this compounds can form strong chemical bond linkage easily with the active group that contains in inorganic materials, organic materials etc.The present invention's three stearic acid isopropyl titanates used are trades mark of Nanjing Xu Yang Chemical Co., Ltd. production and sales is the commerical prod of XY-32.
The invention still further relates to the preparation method of long acting antibiotic mildew-resistant silicone adhesive, it is characterized in that the step of the method is as follows:
A, first by organic bactericide mould inhibitor, carry zinc zeolite inorganic antiseptic, coupling agent and a grinding aid dehydrated alcohol add in blue-type mulling machine together, under 1000-2000rpm rotating speed, grind 60-120min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 30-60min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor, for subsequent use.
B, first the composite antimicrobial mould inhibitor prepared by basic glue, softening agent, steps A to be dropped in multifunctional mixer by proportioning, vacuum stirring 15-30min at 80-120 DEG C; Then linking agent and filler continuation stirring 30-60min is added; Secondly catalyzer and coupling agent is added by proportioning, vacuum stirring 30-60min at 100-150 DEG C; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant silicone adhesive.
According to a kind of preferred implementation that this law is bright, be that the basket-type grinder in described preparation method's steps A is still blue-type mulling machine, belong to wet grinding device, be applicable to the industry that coating, ink, pigment, mill base, makeup, agricultural chemicals, medicine etc. are high to fineness requirement.This equipment changes traditional production technique, former dispersion sand milling two procedures is united two into one, decreases technological process, improve production efficiency, decrease material waste.The present invention's still basket-type grinder used is the equipment of Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd production and sales.
According to the another kind of preferred implementation that this law is bright, be that described grinding aid is dehydrated alcohol, its add-on is organic bactericide mould inhibitor, the 10-15% carrying zinc zeolite inorganic antiseptic, coupling agent three gross weight, and this proportional range can ensure that material is fully wetting, and avoids causing waste.
According to a kind of preferred implementation that this law is bright, be that described multifunctional mixer is for two frames two dispersion multifunctional mixer, the two closed-in construction of this machine has scrapes end function, and the also rotation while revolution of its stirring rake, make material up and down and surrounding motion, thus mixed effect can be reached in a short period of time; It is a kind of high-efficiency appliance collecting reaction, mix, be separated into one, be applicable to electronics, chemical industry, pharmacy, the building materials such as tackiness agent, rubber tool glue, silicone sealant, polyurethane sealant, ointment, the technique such as the liquid of pesticide industry and liquid, solid mixing with liquid material, reaction, dissolving.The present invention's used pair of frame two dispersion multifunctional mixer is the equipment of Shanghai Suowei Electromechanical Equipment Co., Ltd.'s production and sales.
According to the another kind of preferred implementation that this law is bright, described in described preparation technology, the vacuum tightness of multifunctional mixer is-0.07 ~ 0.12MPa, and rotating speed is 500-800rpm.In product of the present invention preparation, material system must remain in high vacuum state, departed from away by contained humidity in material, otherwise can affect the storage effect of moulding product; It is moderate that material spoils speed, both ensured that material is mediated fully, do not wasted energy again, think that equipment mixing speed controls at 500-800rpm most suitable through great many of experiments.
The detection experiment of the antibacterial and mouldproof performance of the long acting antibiotic mildew-resistant silicone adhesive prepared the following detailed description of the present invention.
Detection method and detected result as follows: the film applicator coating that the anti-bacterial effect evaluation test of Antimicrobial mildew-proof silicon adhesive prepared by the present invention specifies by GB/T 21866-2008 " antibiotic paint (paint film) germ resistance assay method and antibacterial effect " standard is tested, and test bacterial classification is intestinal bacteria (ATCC25922) and streptococcus aureus (ATCC6538); And the measurement of test method that anti-mold effect evaluation specifies by GB/T 1741-2007 " paint film fungus resistance assay method " standard, bacterial classification is aspergillus niger (AS 3.4463), terreus (AS 3.3935), paecilomyces varioti (AS 3.4253), penicillium funiculosum (AS 3.3875), ball hair shell (AS 3.4254), Aureobasidium pullulans (AS 3.3984) etc. six kinds mixing mould.In addition, the water treatment condition (soaking print 16h in the distilled water water-bath of 50 ± 2 DEG C) of evaluation building water pipe endurance quality that reference standard JC/T939-2004 " antibacterium plastics tubing antibacterium performance for building " specifies processes Antimicrobial mildew-proof silicon adhesive print prepared by the present invention and namely evaluates its water-fast antibacterial and mouldproof effect; Namely Antimicrobial mildew-proof silicon adhesive print prepared by the UV Light condition process the present invention simultaneously evaluating the antibacterial endurance quality method of paint film in reference standard GB/T 21866-2008 evaluates its fast light antibacterial and mouldproof effect.Its test-results is listed in table 1.
Table 1: the antibacterial and mouldproof test-results of Antimicrobial mildew-proof silicon adhesive of the present invention
When using single zeolite to carry zinc inorganic antiseptic as can be seen from Table 1 in silicone adhesive, before and after water treatment and optical processing, anti-microbial property decreases but still keeps antibiotic rate more than 90%, but all very poor before and after anti-mold effect process, illustrate that this type of antiseptic-germicide is to mould inhibition deviation; When using single organic bactericide mould inhibitor in silicone adhesive, before and after water treatment and optical processing, antibacterial and mouldproof effect occurs to reduce largely, and antibiotic rate is below 90%, and fungicidal properties has reduced to 2 ~ 3 grades by 0 grade; The long acting antibiotic mildew-resistant silicone adhesive that large the present invention obtains after tested before and after water, photo-irradiation treatment antibiotic rate and mildew-resistant change of rank less, all remain on very high level, antibiotic rate is all greater than 99%, mildew-resistant grade reaches 1 ~ 0 grade, this illustrates that the intermediate product NEW TYPE OF COMPOSITE antibacterial mildew inhibitor obtained through preparation technology of the present invention is provided with better activity, higher water-fast light fastness than single zeolite inorganic antiseptic or organic bactericide mould inhibitor, therefore the Antimicrobial mildew-proof silicon adhesive of the present invention prepared by it just has more durable, long-acting antibacterial and mouldproof effect.
The present invention has following beneficial effect:
First the present invention analyzes in synthetic study on the basis of various system antibacterial mildew inhibitor feature, utilizes coupling agent efficient, environmental protection organic bactericide mould inhibitor and the zinc zeolite inorganic antiseptic that carries with vesicular structure to be combined together; Then utilize existing silicone adhesive production unit, frequent for gained composite antimicrobial mould inhibitor regulation adhesive process is added in silicone adhesive material and goes, namely complete long acting antibiotic mildew-resistant silicone adhesive and produce.Production technique is simple, and facility investment is few, is easy to suitability for industrialized production, and production cost is low, environmentally friendly, has the very strong market competitiveness.The present invention is by adjustment basic material kind, easily realize the production of multiple types algae silicone adhesive as anti-in de-acetic acid type, ketoxime removing type, dealcoholizing-type and deacetone, meet different field without technical requirements, be specially adapted to the environment that the kitchen of house decoration, toilet, bathroom etc. are very moist.Antimicrobial mildew-proof silicon adhesive storge quality prepared by the present invention is stablized, antibacterial and mouldproof performance efficiency, lasting.
Embodiment
The present invention will be understood better by these embodiments following.
embodiment 1:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 10 parts of A26,5 parts of OIT, 82 parts carry zinc zeolite, 3 parts of XY-32 coupling agents and 10 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 1500rpm rotating speed, grind 60min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (A26/OIT/ carries zinc zeolite), for subsequent use.
B, first by 78.4 parts of α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 5 parts of polydimethylsiloxanes, A26/OIT/ prepared by 1.5 parts of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 80 DEG C; Then 2 parts of methyl triacetoxysilanes and 10 parts of thermal silicas continuation stirring 30-40min are added; Secondly 0.1 part of two acetic acid acid dibutyl tin and 3 parts of KH560 vacuum stirring 50-60min at 120 DEG C are added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation that long acting antibiotic mildew-resistant takes off acetic acid type silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 600rpm.
embodiment 2:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 15 parts of BCM, 3 parts of DCOIT, 78 parts carry zinc zeolite, 4 parts of XY-32 coupling agents and 12 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 2000rpm rotating speed, grind 100min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (BCM/DCOIT/ carries zinc zeolite), for subsequent use.
B, first by 63.5 parts of α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 3 parts of polydimethylsiloxanes, BCM/DCOIT/ prepared by 1 part of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 90 DEG C; Then 5 parts of methyl tributanoximo silanes and 15 parts of nano-calcium carbonates continuation stirring 50-60min are added; Secondly 0.5 diisopropoxy-bis-(acetylacetone based) titanium and 5 parts of KH570 vacuum stirring 50-60min at 150 DEG C are added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant ketoxime removing type silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 800rpm.
embodiment 3:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 20 parts of ZPT, 75 parts carry zinc zeolite, 5 parts of XY-32 coupling agents and 15 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 2000rpm rotating speed, grind 120min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (ZPT/ carries zinc zeolite), for subsequent use.
B, first by 43.8 parts of α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 15 parts of polydimethylsiloxanes, ZPT/ prepared by 1.1 parts of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 90 DEG C; Then 8 parts of methyltrimethoxy silanes and 30 parts of thermal silicas continuation stirring 50-60min are added; Secondly 0.1 part of dibutyltin diacetate and 2 parts of KH560 vacuum stirring 50-60min at 150 DEG C are added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant dealcoholizing-type silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 700rpm.
embodiment 4:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 10 parts of m-tetrachlorophthalodinitriles, 5 parts of IPBC, 81 parts carry zinc zeolite, 4 parts of XY-32 coupling agents and 13 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 1000rpm rotating speed, grind 50min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (m-tetrachlorophthalodinitrile/IPBC/ carries zinc zeolite), for subsequent use.
B, first by 75.1 parts of α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 8 parts of polydimethylsiloxanes, m-tetrachlorophthalodinitrile/IPBC/ prepared by 0.8 part of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 90 DEG C; Then 5 parts of methyl isopropyl alkene TMOSs and 10 parts of thermal silicas continuation stirring 50-60min are added; Secondly 0.6 part of dibutyl tin laurate and 0.5 part of KH560 vacuum stirring 50-60min at 100 DEG C is added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant deacetone silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 500rpm.
embodiment 5:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 10 parts of BBIT, 89.5 parts carry zinc zeolite, 0.5 part of XY-32 coupling agent and 10 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 1000rpm rotating speed, grind 60min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (BBIT/ carries zinc zeolite), for subsequent use.
B, first by 56.2 parts of part α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 5 parts of polydimethylsiloxanes, BBIT/ prepared by 0.8 part of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 90 DEG C; Then 2 parts of vinyl tributyl ketoximyl silanes and 30 parts of nano-calcium carbonates continuation stirring 50-60min are added; Secondly 1 part of diisopropoxy-bis-(acetylacetone based) titanium and 5 parts of KH570 vacuum stirring 50-60min at 150 DEG C are added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant ketoxime removing type silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 600rpm.
embodiment 6:the preparation of long acting antibiotic mildew-resistant silicone adhesive of the present invention
A, first by 10 parts of BCM, 10 parts of BIT, 75 parts carry zinc zeolite, 5 parts of XY-32 coupling agents and 15 parts of dehydrated alcohols and add together in the still blue-type mulling machine that Shanghai Ai Feng mechanical & electronic equipment corporation, Ltd produces, under 1500rpm rotating speed, grind 100min under normal temperature; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 40-50min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor (BCM/BIT/ carries zinc zeolite), for subsequent use.
B, first by 79.3 parts of α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue), 8 parts of polydimethylsiloxanes, BCM/BIT/ prepared by 0.8 part of steps A carry zinc zeolite and drop into by proportioning that two frames that Shanghai Suowei Electromechanical Equipment Co., Ltd. produces are two to be disperseed in multifunctional mixer, vacuum stirring 20-30min at 100 DEG C; Then 5 parts of methyltrimethoxy silanes and 6 parts of thermal silicas continuation stirring 50-60min are added; Secondly 5 parts of dibutyltin diacetates and 0.5 part of KH560 vacuum stirring 50-60min at 100 DEG C is added by proportioning; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant deacetone silicone adhesive.The vacuum tightness of stirrer is-0.07 ~ 0.12MPa, and rotating speed is 700rpm.
Adopt the testing method described in this specification sheets, test the antibacterial and mouldproof performance of long acting antibiotic mildew-resistant silicone adhesive prepared by the present embodiment 1-6, its test result is listed in table 2.
The antibacterial and mouldproof performance test results of Antimicrobial mildew-proof silicon adhesive prepared by table 2: embodiment 1-6
Claims (4)
1. a long acting antibiotic mildew-resistant silicone adhesive, is characterized in that what described long acting antibiotic mildew-resistant silicone adhesive was made up of following component by weight:
Basis glue 40-90 part;
Linking agent 2-10 part;
Filler 2-40 part;
Catalyzer 0.05-1 part;
Softening agent 0-20 part;
Coupling agent 0.5-5 part;
Composite antimicrobial mould inhibitor 0.5-2 part;
Described basic glue is α, alpha, omega-dihydroxy polydimethyl siloxane (107 glue); Described linking agent is the one in methyl triacetoxysilane, methyl tributanoximo silane, methyltrimethoxy silane or methyl isopropyl alkene TMOS; Described filler is the one in gas-phase silica or nano-calcium carbonate; Described catalyzer be two acetic acid acid dibutyl tins or diisopropoxy-bis-(acetylacetone based) titanium in one; Described softening agent is polydimethylsiloxane; Described coupling agent is the one in γ-(2,3-epoxy third oxygen) (KH-560) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane (KH-570);
Described composite antimicrobial mould inhibitor is made up of following component by weight:
Carry zinc zeolite inorganic antiseptic 75-94.5 part;
Organic bactericide mould inhibitor 5-20 part;
Coupling agent 0.5-5 part;
Described organic bactericide mould inhibitor is N-(2, 2-dichloroethylene) salicylic amide (A26), derosal (methyl-benzoimidazole-2-Urethylane, BCM), m-tetrachlorophthalodinitrile (2, 4, 5, 6 one tetrachloros 1, 3 one benzene dicarbonitriles), Zinc Pyrithione (ZPT), N-octyl-isothiazolinone (OIT), 4, the chloro-N-octyl group of 5-bis--4-isothiazoline-3-ketone (DCOIT), 1, 2-benzisothiazole-3-ketone (BIT), n-butyl-1, at least one in 2-isothiazoline-3-ketone (BBIT) or IPBC (IPBC), described coupling agent is three stearic acid isopropyl titanates,
Described silicone adhesive type is that single-component takes off acetic acid type, single-component ketoxime removing type, single-component dealcoholization-type or single-component deacetone;
The antibiotic rate of described Antimicrobial mildew-proof silicon adhesive to intestinal bacteria and streptococcus aureus is greater than 99%, reaches 1 ~ 0 grade to the mildew-resistant grade of aspergillus niger, terreus, paecilomyces varioti, penicillium funiculosum, ball hair shell, Aureobasidium pullulans six kinds mixing mould.
2. the preparation method of long acting antibiotic mildew-resistant silicone adhesive according to claim 1, is characterized in that the step of the method is as follows:
(A) first organic bactericide mould inhibitor, year zinc zeolite inorganic antiseptic, coupling agent and a grinding aid dehydrated alcohol are added in basket-type grinder together, under normal temperature, under 1000-2000rpm rotating speed, grind 60-120min; Then heat to 60-80 DEG C of unlatching vacuum, continue to stir 30-60min and remove ethanol, and reclaim ethanol; Finally release material and can obtain composite antimicrobial mould inhibitor, for subsequent use;
(B) first the composite antimicrobial mould inhibitor prepared by basic glue, softening agent, steps A is dropped in multifunctional mixer by proportioning, vacuum stirring 15-30min at 80-120 DEG C; Then linking agent and filler continuation stirring 30-60min is added; Secondly catalyzer and coupling agent is added by proportioning, vacuum stirring 30-60min at 100-150 DEG C; Finally be cooled to 30-40 DEG C of extrusion material to pack, namely complete the preparation of long acting antibiotic mildew-resistant silicone adhesive.
3. preparation method according to claim 2, it is characterized in that the basket-type grinder in described preparation method's steps A is still basket-type grinder, the add-on of described grinding aid dehydrated alcohol is organic bactericide mould inhibitor, the 10-15% carrying zinc zeolite inorganic antiseptic, coupling agent three gross weight.
4. preparation method according to claim 3, it is characterized in that in described preparation method B, multifunctional mixer is two frames two dispersion multifunctional mixer, the vacuum tightness of described stirrer is-0.07 ~ 0.12MPa, and rotating speed is 500-800rpm.
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