CN106003309A - Preparing method for antibacterial and ultraviolet-resisting wood and obtained product - Google Patents

Abstract

The invention provides a preparing method for antibacterial and ultraviolet-resisting wood. The method includes the steps that wood impregnation liquid A and wood impregnation liquid B are sequentially used for conducting impregnation treatment on wood, wherein the wood impregnation liquid A is a water solution of zinc salt, and the wood impregnation liquid B is a water solution of alkali. The invention further provides a material prepared through the preparing method. By means of a wood treatment technology, a wet chemistry method is used for generating nano-zinc oxide in the wood in an in-situ manner, the bonding force between nano-particles and wood components is high, running off is not likely to happen, and a modification effect is durable. By means of the wood treatment method, the wood can have good antibacterial performance and ultraviolet-resisting performance, and meanwhile the good heat stability is achieved.

Description

A kind of antibacterial, preparation method of uvioresistant timber and products therefrom

Technical field

The invention belongs to processing and the preservation field of timber, be specifically related to a kind of timber antibacterial and anti- The processing method of ultraviolet.

Background technology

Timber is a kind of natural material, and timber and goods thereof are widely used in interior decoration, furniture In manufacture, building construction and extraneous adornment, but the composition of timber itself and structure thereof cause timber There is hygroscopicity, easily produce drying shrinkage wet rise, strain cracking, be easily subject to antibacterial, mycete Corroding and rotten, simultaneously under ultraviolet irradiates, easily produce degraded variable color, these all affect The using effect of timber, reduces the service life of timber, therefore timber carries out purple antibacterial, anti- Outside line process to prolonging wood using life, improve timber use value, save timber resources with And it is significant to increase timber added value.

At present the main material of timber antimicrobial treatment based on organic antibacterial agent (such as pentachlorophenol), But organic antibacterial agent poor heat resistance, only part strain is had bacteriostasis, additionally, there may be The problem such as safety and environmental pollution.Inorganic antiseptic has obtained more research in recent years, has Good persistence and broad spectrum activity, and safety non-toxic, heat-resist, such as titanium dioxide, But its presoma predominantly has virose Organic substance, it is hidden that this brings bigger safety to Producer Suffer from.By comparison, zinc oxide with synthesis technique simple and safety non-toxic and be widely used in many The field of kind, and zinc oxide can absorb ultraviolet, improves the anti-ultraviolet property of material.Cause This, be applied to treating of wood by zinc oxide and have more superiority.

As the patent of Publication No. CN103481345A discloses a kind of microwave attenuation materials oxidation The method of zinc nanostructured improved wood.Zinc acetate-alcohol solution is stirred with sodium hydroxide-ol solution Mixing uniformly, zinc acetate is 1:1-5 with the mol ratio of sodium hydroxide, prepares zinc oxide crystal seed colloid molten Liquid, is dipped in timber in this solution holding 6-48 hour subsequently, is finally processed by timber stoving, Repeating 1-5 time, obtaining superficial growth has the timber of zinc oxide crystal seed；By zinc salt solution and ammonia Source aqueous solution is mixed in the ratio of zinc salt with ammonia source mol ratio 1:1-5, then by ultrasonic for blended liquid point Dissipate 5-30 minute, then blended liquid is moved in micro-wave diminishing pot, and the superficial growth obtained is had The timber of zinc oxide crystal seed is immersed in blended liquid, at microwave radiation, the water of 1000-1500W Hot temperature carries out microwave hydrothermal and reacts 10-90 minute under conditions of being 40-120 DEG C, take after cooling Go out timber, vacuum drying, obtain the timber of surface in situ growth of zinc oxide nano structure.This kind The improved wood surface property that method obtains is excellent, but complex process, and simply to timber table Face has carried out modification, and top layer is easily damaged and loses modified effect.

The patent of Publication No. CN103302710A discloses a kind of wood nano composite preservative Preparation method, mainly by nanon ball-mill, copper oxide and Zinc oxide powder are carried out ball milling, And add dispersant ammonium citrate and sodium hydrate aqueous solution, and medium oxidizing zirconium bead is utilized to put Enter to refine in the abrading cylinder of nanon ball-mill, grind 2-2.5 with 3500r/min-4000r/min rotating speed Hour, obtain suspension, ultrasonic disperse 30-40 minute after taking-up, i.e. obtain timber nanometer multiple Close preservative.

The patent of Publication No. CN105128117A discloses a kind of ultraviolet shielding agent, mainly becomes It is divided into nano zine oxide, cordierite and Dimethicodiethylbenzalmalonate, and utilizes this ultraviolet shielding agent and silicon Alkane coupling agent composite modified fiber, the sun-proof ageing resistace of sun-proof fibre board made is good, extends In service life, product stability is good simultaneously, can serve as open air, also act as automotive trim, The industries such as packaging, furniture.

Summary of the invention

In place of the deficiencies in the prior art, the present invention proposes a kind of antibacterial, uvioresistant timber And preparation method thereof.Antibacterial, the uvioresistant timber prepared by the present invention not only has wide spectrum and resists Bacterium property, good anti-bacterial effect, persistently, and uvioresistant excellent effect.Preparation method of the present invention Simply, with low cost, pollution-free, treatment temperature is low, saves energy consumption, and the timber prepared Heat stability is good.

Another object of the present invention is to propose the material that preparation method prepares.

The concrete technical scheme realizing the object of the invention is:

A kind of antibacterial, preparation method of uvioresistant timber, it includes using timber pickling liquid successively A and timber pickling liquid B carries out impregnation process to timber, and described timber pickling liquid A is zinc salt Aqueous solution, described timber pickling liquid B is the aqueous solution of alkali.

In this method, described timber can be selected for any timber, and its source is unrestricted, as poplar, Birch, Lignum nanmu, Eucalyptus, Lignum seu Ramulus Cunninghamiae Lanceolatae, Masson Pine etc., the moisture content of pending timber can be 5-15%.

Further, described timber pickling liquid A is zinc salt water-soluble of concentration 0.2-1.0mol/L Liquid, described zinc salt is one or more in zinc nitrate, zinc chloride, zinc sulfate, zinc citrate

Wherein, described timber pickling liquid B is the aqueous solution of the alkali of concentration 0.2-0.8mol/L, institute Stating alkali is ammonia or sodium hydroxide.

Preparation method of the present invention, it is preferable that include step:

1) processing timber with timber pickling liquid A, treatment temperature is 10-30 DEG C, prior to vacuum Impregnation process 10-30 minute under the conditions of 0.08-0.10MPa, impregnates 30-120 under normal pressure Minute；

2) timber is carried out impregnation process, in temperature 10-30 DEG C condition with timber pickling liquid B Lower fully reaction 12-60 hour.

3) by step 2) process after timber carry out cold drying process, dry temperature is 50-80 DEG C, the time is 60-80 hour.

It is highly preferred that step 2) in, with timber pickling liquid B, timber is carried out impregnation process, Fully react 30-50 hour under the conditions of temperature 20-30 DEG C.

Further, described step 2) in, it is soaked in water after impregnation process or rinses timber, Until the water outlet of the water soaked or flushing is neutral.

Wherein, described step 3) in, the temperature being dried is 55-70 DEG C, and the time is 70-75 Hour.More preferably drying time is 72 hours.

The material that preparation method of the present invention prepares.

The beneficial effects of the present invention is:

(1) wood treatment process proposed by the present invention is to utilize wet chemical method in timber Portion's in-situ preparation nano zine oxide, the adhesion between nano-particle and wood component is relatively strong, no Being easy to run off, modified effect is lasting.

(2) wood treatment process that the present invention proposes not only can give the antibiotic property that timber is excellent Energy, anti-ultraviolet property, have preferable heat stability simultaneously.The oxidation of wood internal set Zinc is that the luminous energy of nature is converted to the energy required for chemical reaction, directly occurs with antibacterial During chemical reaction, can not only the endotoxin that produces of decomposing bacteria, and can be by its organic nutrition base The thorough mineralising of matter, thus reach to decompose, destroy the purpose of bacterial structure, sterilization process realizes certainly Cleaning, environmentally safe, and there is sterilizing and the multiple effect such as antibacterial, not only environmental protection, and And saving energy consumption.Further, zinc oxide can absorb ultraviolet, it is possible to the fall of protection wood component Solution, variable color etc..

(3) present invention proposes wood treatment process simply, and energy-conserving and environment-protective are the most easy to control, It is different from traditional wood surface to process simultaneously, but effective ingredient is deep into wood internal, wood Material secondary operations postmenstruation will not destroy its antibacterial, anti-ultraviolet property.

Accompanying drawing explanation

Fig. 1 is the stereoscan photograph of reference examples.

Fig. 2 is the stereoscan photograph of embodiment 1.

Fig. 3 is the stereoscan photograph of embodiment 2.

Fig. 4 is the collection of illustrative plates that the timber to embodiment 1-3 and reference examples carries out X-ray diffraction detection.

Detailed description of the invention

Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.

In embodiment, unless otherwise noted, the method used is the method that this area is conventional.

Timber handled in following example and reference examples uses poplar, derives from Beijing, system Become a size of 30mm (T, tangential) × 10mm (R, radially) × 100mm (L, rift grain) poplar Wood wooden unit, moisture content 7%-9%.

Embodiment 1

1, preparation timber pickling liquid

Impregnation liquid A: joined by zinc nitrate in distilled water, stirs to fully dissolving, prepares wood Material impregnation liquid A；Wherein the amount mark of the material of zinc nitrate solution is 0.6mol/L.

Impregnation liquid B: configuration sodium hydroxide solution, the amount mark of material is 0.4mol/L.

2, timber pickling processes

The wooden unit made is placed in equipped with in the vacuum pressed tank of impregnation liquid A, and is immersed in wood In material impregnation liquid, connect vaccum-pumping equipment, evacuation, timber carried out the impregnation process that reduces pressure, Make timber adsorptive liquid A, prepare impregnated timber；The temperature that wherein decompression impregnation process process is Degree is 20 DEG C, and vacuum is 0.095Mpa, and the time is 20 minutes, impregnates under normal pressure 120 minutes.

3, cured

Impregnated timber is soaked in impregnation liquid B, carries out curing reaction.Impregnation liquid A and B In effective ingredient can be fully contacted and react；Wherein cured temperature is 20 DEG C, Time is 48 hours.Subsequently wooden unit is taken out, is soaked in distilled water, and constantly changes water, Until distilled water presents neutrality.

4, dried

Timber after curing reaction is put into drying baker is dried process；Wherein dried Temperature be 60 DEG C, the time is 72 hours.

Comparative example

1, preparation timber pickling liquid

Impregnation liquid A: joined by zinc nitrate in distilled water, stirs to fully dissolving, prepares wood Material impregnation liquid A；Wherein the amount mark of the material of zinc nitrate solution is 0.6mol/L.

Impregnation liquid B: configuration sodium hydroxide solution, the amount mark of material is 0.4mol/L.

2, timber pickling processes

The temperature of decompression impregnation process process is 20 DEG C, and vacuum is 0.095Mpa, and the time is 20 minutes, impregnate 20 minutes under normal pressure.

Other operations are with embodiment 1.

By the observation of scanning electron microscope, it was observed that the wood internal zinc oxide distribution that this test prepares Uneven.It is too short that its reason is probably the impregnation process time, causes zinc solution infiltration not exclusively, Have impact on modified effect.

Embodiment 2

1, preparation timber pickling liquid

Impregnation liquid A: joined by zinc nitrate in distilled water, stirs to fully dissolving, prepares wood Material impregnation liquid A；Wherein the amount mark of the material of zinc nitrate solution is 1.0mol/L.

Impregnation liquid B: configuration sodium hydroxide solution, the amount mark of material is 0.4mol/L.

2, timber pickling processes

The wooden unit made is placed in equipped with in the vacuum pressed tank of impregnation liquid A, and is immersed in wood In material impregnation liquid, connect vaccum-pumping equipment, evacuation, timber carried out the impregnation process that reduces pressure, Make timber adsorptive liquid A, prepare impregnated timber；The temperature that wherein decompression impregnation process process is Degree is 20 DEG C, and vacuum is 0.08Mpa, and the time is 30 minutes, impregnates 120 under normal pressure Minute.

3, cured

Impregnated timber is soaked in impregnation liquid B, carries out curing reaction.Impregnation liquid A and B In effective ingredient can be fully contacted and react；Wherein cured temperature is 20 DEG C, Time is 48 hours.Subsequently wooden unit is taken out, is soaked in distilled water, and constantly changes water, Until distilled water presents neutrality.

4, dried

Timber after curing reaction is put into drying baker is dried process；Wherein dried Temperature be 60 DEG C, the time is 72 hours.

Embodiment 3

1, preparation timber pickling liquid

Impregnation liquid A: joined by zinc nitrate in distilled water, stirs to fully dissolving, prepares wood Material impregnation liquid A；Wherein the amount mark of the material of zinc nitrate solution is 0.6mol/L.

Impregnation liquid B: configuration ammonia spirit, mass fraction is 25%.

2, timber pickling processes

The wooden unit made is placed in equipped with in the vacuum pressed tank of impregnation liquid A, and is immersed in wood In material impregnation liquid, connect vaccum-pumping equipment, evacuation, timber carried out the impregnation process that reduces pressure, Make timber adsorptive liquid A, prepare impregnated timber；The temperature that wherein decompression impregnation process process is Degree is 20 DEG C, and vacuum is 0.095Mpa, and the time is 20 minutes, impregnates under normal pressure 120 minutes.

3, cured

Impregnated timber is soaked in impregnation liquid B, carries out curing reaction.Impregnation liquid A and B In effective ingredient can be fully contacted and react；Wherein cured temperature is 20 DEG C, Time is 60 hours.Subsequently wooden unit is taken out, is soaked in distilled water, and constantly changes water, Until distilled water presents neutrality.

4, dried

Timber after curing reaction is put into drying baker is dried process；Wherein dried Temperature be 60 DEG C, the time is 72 hours.

Reference examples

Use undressed poplar wooden unit as reference examples.

Test example 1 is antibacterial, uvioresistant timber rate of body weight gain determination test

1, the poplar wooden unit before treatment of embodiment 1-3 is placed in drying baker, is dried to over dry, Weigh (being designated as Wu)；

2, timber prepared by embodiment 1-3 is weighed (being designated as Wt) respectively；

3, calculate timber rate of body weight gain (WPG) according to equation below to test:

$WPG\left(\%\right)=\[\frac{Wt-Wu}{Wu}\]\×100$

Test result is shown in Table 1.

Table 1 processes the rate of body weight gain of timber

Experimental example	Experimental example 1	Experimental example 2	Experimental example 3
				Rate of body weight gain (%)	1.08	5.02	8.56

The result of table 1 shows: antibacterial, the weightening finish of uvioresistant timber prepared by the inventive method Rate is affected by zinc salt concentration and impregnation liquid B component, due to wood component in the basic conditions Have Partial digestion, cause timber rate of body weight gain to decrease, but the timber after processing has certain Rate of body weight gain, the rate of body weight gain that experimental example 3 obtains is maximum, it may be possible to wood degradation is less.

Test example 2 is antibacterial, the detection of uvioresistant timber scanning electron microscope

Embodiment 1,2 processes the timber of timber and reference examples and cuts along horizontal, is placed in metal On platform, metal spraying processes and is placed on sample platform of scanning electronic microscope observation.Then scanning electron microscope (day is used Vertical high and new technology company, S3400N) sample microstructure is scanned, observes, result See Fig. 1-3.

Test result shows:

As shown in Figure 1, the wood transverse section in reference examples shows smooth, and cellularity is obvious, There is not nano granular of zinc oxide.And the wood internal after Fig. 2 and 3 shows impregnation process generates More flower-shaped nano zine oxide, and along with the increase of zinc salt concentration, nano-particle increases.

Test example 3X x ray diffraction analysis x

Use X-ray diffractometer (Brooker D8 Advance) to embodiment 1-3 and reference examples Timber carries out X-ray diffraction detection, zinc oxide configuration in wood in analysis of material. XRD figure spectrum is shown in Fig. 4.

Result shows, each wood materials is diffraction maximum all occur near 15.8 ° and 22.1 ° at 2 θ Peak, it is respectively cellulose (101) and the diffraction maximum of (002) crystal face.And 3 embodiments , in addition to having cellulose diffraction maximum, there is again a series of new diffraction maximum, is in sample collection of illustrative plates The characteristic peak of nano zine oxide, has illustrated at wood internal fabricated in situ nano zine oxide, and Along with the increase of zinc salt content, the nano zine oxide diffracted intensity of generation gradually strengthens.

Test example 4 anti-microbial property detects

Use inhibition zone method that the timber of embodiment and reference examples is carried out antibiotic property test, wherein bacterium Planting is escherichia coli, and concrete detection method is as follows:

The timber of embodiment 1-3 Yu reference examples is cut into wood particle, a size of 5mm cube, Then to its sterilization treatment, irradiate 0.5 the most again under uviol lamp and be as a child individually placed to scribble greatly In the agar plates of enterobacteria, subsequently culture dish is positioned in incubator, under the conditions of 37 DEG C 24 hours, finally measure antibacterial circle diameter.Test result is shown in Table 2.

The antibiotic property of table 2 timber and anti-ultraviolet property

Embodiment	Embodiment 1	Embodiment 2	Embodiment 2	Reference examples
					Antibacterial circle diameter (mm)	9.0	12.8	13.2	—
ΔE*	9.53	6.67	6.98	20.22

Test result indicate that: along with the increase of nano oxidized Zn content, the antibiotic property of timber is obviously enhanced. Test example 5 anti-ultraviolet property detects

Sample is positioned in ultraviolet case, under ultra violet lamp, by measuring sample surfaces face The complexion changedization assessment sample resistivity to ultraviolet.Wherein, colour measurement equipment is used (Dataflash 110Datacolor) test sample becomes through 6 weeks ultra-vioket radiation rear surface lightness Changing (Δ L*), red green degree change (Δ a*), champac colourity change (Δ b*), according to as follows Formula calculates color and changes (Δ E*):

${\mathrm{\ΔE}}^{*}=\sqrt{{\left({\mathrm{\ΔL}}^{*}\right)}^2+{\left({\mathrm{\Δa}}^{*}\right)}^2+{\left({\mathrm{\Δb}}^{*}\right)}^2}$

Test result is listed in table 2.

Result shows: compared with reference examples, and the wood color through impregnation process changes less, Along with the increase of zinc salt concentration, nano zine oxide load capacity increases, and the color change of timber is also got over Little, illustrate that the anti-uv-ray of timber gradually strengthens.

Although, describe the present invention above by embodiment, but those skilled in the art It will be appreciated that on the premise of without departing from present invention spirit and essence, the improvement that the present invention is done And modification, all should belong in protection scope of the present invention.

Claims (8)

1. antibacterial, the preparation method of uvioresistant timber, it is characterised in that include depending on Secondary timber pickling liquid A and timber pickling liquid B carries out impregnation process, described timber to timber Impregnation liquid A is the aqueous solution of zinc salt, and described timber pickling liquid B is the aqueous solution of alkali.

Preparation method the most according to claim 1, it is characterised in that described timber soaks Stain liquid A is the aqueous solution of the zinc salt of concentration 0.2-1.0mol/L, described zinc salt be zinc nitrate, One or more in zinc chloride, zinc sulfate, zinc citrate.

Preparation method the most according to claim 1, it is characterised in that described timber soaks Stain liquid B is the aqueous solution of the alkali of concentration 0.2-0.8mol/L, and described alkali is ammonia or hydroxide Sodium.

4. according to the arbitrary described preparation method of claim 1-3, it is characterised in that include Step:

1) processing timber with timber pickling liquid A, treatment temperature is 10-30 DEG C, prior to vacuum Impregnation process 10-30 minute under the conditions of 0.08-0.10MPa, impregnates 30-120 under normal pressure Minute；

2) timber is carried out impregnation process, in temperature 10-30 DEG C condition with timber pickling liquid B Lower fully reaction 12-60 hour.

3) by step 2) process after timber carry out cold drying process, dry temperature is 50-80 DEG C, the time is 60-80 hour.

Preparation method the most according to claim 4, it is characterised in that step 2) in, With timber pickling liquid B, timber is carried out impregnation process, under the conditions of temperature 20-30 DEG C fully React 30-50 hour.

Preparation method the most according to claim 4, it is characterised in that described step 2) In, it is soaked in water after impregnation process or rinses timber, until the water soaked or the water outlet of flushing For neutrality.

Preparation method the most according to claim 4, it is characterised in that described step 3) In, the temperature being dried is 55-70 DEG C, and the time is 70-75 hour.

8. the material that the arbitrary described preparation method of claim 1-7 prepares.