CN100387644C - Antibiotic resin product and its producing method - Google Patents
Antibiotic resin product and its producing method Download PDFInfo
- Publication number
- CN100387644C CN100387644C CNB2004100033069A CN200410003306A CN100387644C CN 100387644 C CN100387644 C CN 100387644C CN B2004100033069 A CNB2004100033069 A CN B2004100033069A CN 200410003306 A CN200410003306 A CN 200410003306A CN 100387644 C CN100387644 C CN 100387644C
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- Prior art keywords
- glass powder
- antibiotic glass
- resin product
- antibiotic
- antibacterial
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- 230000003115 biocidal effect Effects 0.000 title claims description 225
- 238000000034 method Methods 0.000 title claims description 52
- 239000011521 glass Substances 0.000 claims abstract description 278
- 239000002245 particle Substances 0.000 claims abstract description 90
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 27
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 200
- 230000000844 anti-bacterial effect Effects 0.000 claims description 104
- 238000004519 manufacturing process Methods 0.000 claims description 30
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- 238000010309 melting process Methods 0.000 claims 2
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
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- 239000004615 ingredient Substances 0.000 description 3
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- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
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- 241000315672 SARS coronavirus Species 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000588722 Escherichia Species 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
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- 241000237502 Ostreidae Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
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- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention rleates to an antimicrobial resin product in which the antimicrobial glass scarcely turns yellow and has an excellent transparency and dispersibility and whose surface smoothness stays excellent, even when it is molded with an extrusion molding machine or the amount of the antimicrobial glass added is fluctuated and to the preparation thereof. The antimicrobial molding contains 0.1-10 wt.% antimicrobial glass to the total weight. The antimicrobial glass is polyhedral in shape, has an average volume particle size(D50)of 0.2-30 um and a specific surface area of 9,000-30,000 cm<2>/cm<3>, accordingly, an antimicrobial resin product with surface smoothness stays excellent can be obtained.
Description
Technical field
The present invention is relevant with antibacterial resin product and manufacture method thereof.Specifically, be exactly not to be subjected to the influence of building mortion kind, not to be subjected to what the influence of antibiotic glass powder addition, can both form the antibacterial resin product of smooth surface beauty.The present invention is relevant with this antibacterial resin product and manufacture method thereof.
Background technology
In recent years, in rosin productss such as material of construction, household appliances (televisor, computer, mobile phone, digital camera etc.) daily necessities, wrapping material or resin component, add the antibiotic glass powder, make it to have anti-microbial effect, the manufacture method that becomes the antibacterial resin product is adopted gradually.
As the antibiotic glass powder, the silver ions dissolution type bath of glass treatment agent of being showed just like Japanese kokai publication sho 62-210098 communique.Univalent silver ion content in this bath of glass treatment agent is converted into silver suboxide, just in the glass of 100 weight unit, contains the silver suboxide of 0.2 ~ 1.5 weight unit.B as glass ingredient
2O
3Content at 20 ~ 70 moles of %, be a kind of borosilicic acid salt antibiotic glass powder.Details are seen the example 2 and the example 3 of this patent gazette, and glass ingredient example 2 is: B
2O
320 ~ 30 moles of %, ZnO40 mole %, P
2O
530 ~ 40 moles of %.Example 3 is: in example 2 glass of 100 weight unit, add the Ag of 1 weight unit again
2O (calling special place document 1 in the following text).
In addition, on the Japanese kokai publication hei 1-313531 communique, the antibiotic glass powder is specifically by SiO in the antibacterial resin product
2, B
2O
3, P
2O
5Generate oxide compound and Na on network
2O, K
2Network filling oxide compounds such as O, CaO, ZnO constitute jointly.In the glass of 100 weight unit, the univalent silver ion content is converted into silver suboxide, and content is in 0.1 ~ 20 weight unit.Details are seen the example of this patent gazette, and glass ingredient is SiO
240 moles of %, B
2O
350 moles of %, Na
2O10 mole % in the glass of 100 weight unit, adds the Ag of 2 weight unit again
2O (calling patent documentation 2 in the following text).
The applicant of present patent application has also proposed the antibiotic glass powder of median size in 0.5 ~ 300 mu m range in addition, this antibiotic glass powder is not subjected to the influence of glass moiety, anti-sex change is good, be a kind of polyhedron-shaped, has deliquescent glass powder, its transparency height, favorable dispersity are applied in the resin and can cause the resin variable color, and manufacture also convenient.(referring to WO02-2879 communique (calling patent documentation 3 in the following text))
The antibiotic glass powder that patent documentation 1 is showed is as the B of glass
2O
3Content at 20 ~ 70 moles of %.But this kind antibiotic glass powder, estimation are them reckons without atomic shape, thereby this kind antibiotic glass powder is the gonorrhoea look, and easily cohesion lacks transparency, is applied in easily to cause the resin variable color in the resin, and also is not easy to be uniformly dispersed in resin.
When using this kind antibiotic glass powder production antibacterial resin product, the color of resin itself is changed, can make the transparent resin forfeiture transparency, and the antibacterial resin product surface be also uneven, lacks smoothness.
The antibiotic glass powder that patent documentation 2 is showed is with B
2O
3Be principal constituent, but the proportioning of network generation oxide compound and network filling oxide compound is not good, causes the glass melting time oversize, has influenced the anti-microbial property of antibiotic glass powder.
In addition, this antibiotic glass powder is not considered the shape of fine glass particle yet, thereby lacks the transparency and dispersed, and makes the resin variable color easily.The antibiotic glass powder of being showed with patent documentation 1 is the same, and practice easily makes the resin variable color in resin the time, and the rosin products surface also lacks smoothness.
The antibiotic glass powder that patent documentation 3 is showed, it also is the previous antibiotic glass powder that proposes of applicant, median size is in 0.5 ~ 300 mu m range, in practice, when for example on emission forming machine, being shaped, run into emission forming machine pressure inequality, when perhaps the glass powder addition is big, glass powder easily condenses, and protrudes in the rosin products surface, causes antibacterial resin product surface smoothness poor.
Summary of the invention
At above variety of problems, the applicant proposes shape, average volume particle diameter (D50), specific surface area and addition by control antibiotic glass powder through long term studies, can solve the problem that runs into when being shaped on emission forming machine.That is to say both to make emission forming machine that the pressure uneven phenomenon is arranged, perhaps the glass powder addition is bigger, and also can produce glass powder and be uniformly dispersed, the antibacterial resin product of smooth surface beauty, thus finished the present invention with flying colors.
The present invention adopts the antibiotic glass powder of anti-variable color, transparency height, favorable dispersity, manufactures the antibacterial resin product of smooth surface beauty by unique technological process, and is not subjected to building mortion kind and the bigger influence of antibiotic glass addition.Purpose of the present invention provides this antibacterial resin product and manufacture method thereof to society exactly.
The method according to this invention is made polyhedron with the shape of antibiotic glass powder, and addition is controlled in (with respect to overall weight) 0.1 ~ 10 weight % scope, average volume particle diameter (D50) is controlled in 0.2 ~ 30 mu m range, specific surface area is controlled at 9,000 ~ 30,000cm
2/ cm
3In the scope, can solve above variety of problems.
Antibacterial resin product of the present invention is controlled at antibiotic glass powder 90% particle volume diameter (D90) in 1 ~ 50 mu m range when producing, and the ratio of D90/D50 is controlled in 2.5 ~ 4 scopes, and effect is comparatively desirable.
Antibacterial resin product of the present invention is when producing, and with the antibiotic glass powder, particle diameter is in actual the containing than being controlled at below (with respect to entire amount) 10 volume % more than the 50 μ m, and effect is comparatively desirable.
Antibacterial resin product of the present invention is when producing, and with the antibiotic glass powder, particle diameter is in actual the containing than being controlled at below (with respect to entire amount) 5 volume % below the 0.1 μ m, and effect is comparatively desirable.
The antibiotic branch product of the present invention is when producing, and the size-grade distribution of antibiotic glass powder should have first peak value and second peak value, and effect is comparatively desirable like this.
Antibacterial resin product of the present invention is when producing, and the dissolution rate that has the metal ion of anti-microbial effect in the antibiotic glass powder should be controlled in 1 ~ 100 μ g/hr scope, and effect is comparatively desirable like this.
Another form of the present invention, in the antibacterial resin product, the content of polyhedron-shaped antibiotic glass powder is controlled at the manufacture method in (with respect to whole total amount) 0.1 ~ 10 weight unit % scope.Manufacture method of the present invention comprises fusion, cooling pulverizing, these three technological processs of hybrid shaping.
(A) fusion: will contain the frit fusion of stripping property antibacterial metal ions, and make it to become the technological process that glass melts liquid.
(B) cooling is pulverized: glass is melted liquid cool off in water, fine powder is broken again after the coarse reduction, makes the polyhedron that is shaped as of antibiotic glass powder, and in average volume particle diameter (D50) control 0.2 ~ 30 mu m range, specific surface area is controlled at 9,000 ~ 30,000cm
2/ cm
3Process for making in the scope.
(C) hybrid shaping: with polyhedron-shaped antibiotic glass powder homodisperse in resin, be shaped, become the technological process of an antibacterial resin product by needed shape.
The manufacture method of antibacterial resin product of the present invention is when implementing, wherein shredding unit uses jaw crusher, electronic runner milling, motorized pulleys, oscillating mill, ball mill, simpson mill, jet mill etc. in (B) cooling disintegrating process, and effect is comparatively desirable.
Particularly use jaw crusher earlier antibiotic glass to be crushed to about average volume particle diameter (D50) 5mm, with electronic runner milling or motorized pulleys antibiotic glass is crushed to about average volume particle diameter (D50) 1mm again, then be crushed to specified average volume particle diameter (D50), specific surface area and polyhedron-shaped with the glass powder of jet mill about again with 1mm, such processing method, effect is even more ideal.
The manufacture method of antibacterial resin product of the present invention is when implementing, wherein building mortion uses emission forming device, SMC (Sheet Molding Compoud) compression molding device, BMC (BulkMolding Compoud) compression molding device and press molding equipment in (C) hybrid shaping technology, and effect is comparatively desirable.
According to antibacterial resin product of the present invention, the addition of antibiotic glass powder is controlled in the scope of specified amount, be controlled at the shape of antibiotic glass powder simultaneously, average volume particle diameter (D50), specific surface area, can produce anti-variable color, transparency height, antibiotic glass powder is uniformly dispersed, the antibacterial resin product of smooth surface beauty, and be not subjected to the restriction of building mortion kind.
According to antibacterial resin product of the present invention, the antibiotic glass powder is worked as in 90% particle volume diameter (D90) the control specialized range, and the ratio of D90/D50 also is controlled in the specialized range, can make the dispersiveness of antibiotic glass powder better, both make the ejaculation pressure of emission forming device that some variations take place, and also can produce ganoid antibacterial resin product.
According to antibacterial resin product of the present invention, with actual contain than be controlled at prescribed value below of particle diameter more than 50 μ m of antibiotic glass powder, can make the dispersiveness of discoloration-resistant, the transparency and antibiotic glass powder of antibacterial resin product better, the surface is also Paint Gloss, and produces the restriction that also is not subjected to the building mortion kind.
According to antibacterial resin product of the present invention, with actual contain than be controlled at prescribed value below of particle diameter below 0.1 μ m of antibiotic glass powder, can make the dispersiveness of discoloration-resistant, the transparency and antibiotic glass powder of antibacterial resin product better, the surface is also Paint Gloss, and produces the restriction that also is not subjected to the building mortion kind.
According to antibacterial resin product of the present invention, the size-grade distribution of employed antibiotic glass powder has plural peak value, can make the dispersiveness of discoloration-resistant, the transparency and antibiotic glass powder of antibacterial resin product better, the surface is Paint Gloss, and produces the restriction that also is not subjected to the building mortion kind.
According to the manufacture method of antibacterial resin product of the present invention, the addition of antibiotic glass powder is controlled in the specified amount scope, be controlled at shape, average volume particle diameter (D50) and the specific surface area of antibiotic glass powder simultaneously.Use such antibiotic glass powder, can produce discoloration-resistant, the transparency well, the antibiotic glass powder is uniformly dispersed, the antibacterial resin product of smooth surface beauty, and produce the restriction that is not subjected to the building mortion kind.
The manufacture method of antibacterial resin product according to the present invention, in (B) cooling disintegrating process, use specified shredding unit, can make the dispersiveness of discoloration-resistant, the transparency and antibiotic glass powder of antibacterial resin product better, the surface is also Paint Gloss, and produces the restriction that is not subjected to the building mortion kind.
According to the manufacture method of antibacterial resin product of the present invention, in (C) hybrid shaping technology, use corresponding building mortion, can produce effectively that discoloration-resistant, the transparency are good, the antibiotic glass powder is uniformly dispersed ganoid antibacterial resin product.
Description of drawings
Fig. 1 is the particle size distribution figure of the antibiotic glass powder of example 1;
Fig. 2 is the particle size distribution figure of the antibiotic glass powder of example 2;
Fig. 3 is the particle size distribution figure of the antibiotic glass powder of example 3;
Fig. 4 a-c is antibacterial resin cosmetics containers and bottle cap;
Fig. 5 is the explanatory view of antibacterial resin suction pumps;
Fig. 6 is antibiotic Flesible plastic container;
Fig. 7 is antibacterial resin bucket and drinking device.
Specific implementation method
First example
First example is also promptly with respect to overall weight, the content of antibiotic glass powder in 0.1 ~ 10 weight % scope, and this antibiotic glass powder be shaped as polyhedron, average volume particle diameter (D50) is in 0.2 ~ 30 mu m range, specific surface area is 9,000 ~ 30,000cm
2/ cm
3Antibacterial resin product in the scope.
Below with regard to the shape of the employed antibiotic glass powder of antibacterial resin product of first example, the style of average volume particle diameter, specific surface area, glass composition, resin, antibacterial resin product etc. specifies.
1, the shape of antibiotic glass powder
The antibiotic glass powder is a polyhedron, also promptly has a plurality of angles and face.For example form polyhedron by 6 ~ 10 bodies, but a said here polyhedral key character be do not comprise spherical and granular.Flakey, acicular antibiotic glass powder when injection molding, stop up lance head easily in addition, so also do not belong in the polyhedron scope.
Different with the antibiotic glass powder of shape such as spherical, after polyhedral antibiotic glass powder was subjected to light, light passed through to a certain direction easily, can prevent light phenomenon at random.Thereby the polyhedron-shaped transparency that can improve the antibiotic glass powder.
Polyhedron-shaped antibiotic glass powder not only disperses than being easier in resin, and when being shaped on emission forming device, has the feature that distributes by certain orientation.Thereby use polyhedron-shaped antibiotic glass powder, and manufacture the antibacterial resin product, powder is uniformly dispersed in resin easily, and can prevent light phenomenon at random, has the higher transparency.
Moreover polyhedron-shaped antibiotic glass powder is not easy cohesion in production, the use, thus when pulverizing, just more convenient to the control of median size, when on emission forming device, being shaped, also easy homodisperse.
In addition, the antibiotic glass powder that uses in the antibiotic glass product, its powder shape can also be other shapes except that above-mentioned polyhedron.For example, make the aggegation of a part of antibiotic glass micropartical, attached to polyhedron-shaped particle surface.Also can use the antibiotic glass micropartical separately.
And, can also cover the antibiotic glass particle with inorganic particles or organism particle.For example use coupling agent, the organism particle is covered be fixed on polyhedron antibiotic glass particle surface.Perhaps, about 400 ~ 800 ℃, it is being melted at the antibiotic glass particle surface inorganic particles and the heating of antibiotic glass mix particles.
Such structure can be controlled antibacterial metal ions with comparalive ease, and for example the dissolution rate of silver ions is also helpful to the dispersiveness that improves the antibiotic glass powder.
Antibiotic glass particle of the present invention is the polyhedron particle, and the motion that other cover particle is subjected to polyhedron-shaped restriction, thereby can cover evenly.
First example, and in the example that will address later, the amount of polyhedron glass powder might not leave no choice but be controlled at 100 weight %, also can suitably contain the antibiotic glass powder of some other shapes in the antibiotic glass powder.But this moment, the content of polyhedron antibiotic glass powder should be more than 80 weight %.Its reason is the content such as the less than 80 weight % of polyhedron antibiotic glass powder, and the antibiotic glass powder is dispersed just poor in resin, and transparency is also low.So consider the dispersiveness and the transparency, the content of polyhedron antibiotic glass powder is comparatively ideal more than 90 weight %, and is then even more ideal more than 95 weight %.
2, the size-grade distribution of antibiotic glass powder
1., average volume particle diameter (D50)
One of feature of antibiotic glass powder is that average volume particle diameter (D50) is in 0.2 ~ 30 mu m range.Its entire amount that is defined as antibiotic glass powder cumulative volume is as 100% o'clock, cumulative volume be 50% o'clock particle diameter just as D50 (μ m), D50 is controlled in the specialized range.
The reason that D50 is controlled in 0.2 ~ 30 mu m range is: as D50 during less than 0.2 μ m, the antibiotic glass powder is the blending dispersion difficulty in resin, and is easy to generate light phenomenon at random, influences transparency.And as D50 during greater than 30 μ m, the antibiotic glass powder is equally also difficulty of blending dispersion in resin.And when being shaped on emission forming device, compacting pressure is as changing, and then the antibacterial resin product surface will be uneven, lacks smoothness.
In sum, it is comparatively ideal that the D50 of antibiotic glass powder is controlled in 0.5 ~ 20 mu m range, is controlled in 1 ~ 10 mu m range then even more ideal.
The average volume particle diameter of antibiotic glass powder (D50), and 90% particle volume diameter (D90) that will address later on, perhaps other specifies the actual ratio that contains of the antibiotic glass powder of particle diameter, and available laser type particle size distribution device, decanter type particle size distribution device carry out the size-grade distribution measuring and calculating.Also can be according to the electron photomicrograph of antibiotic glass powder, after making image and handling, calculate its size-grade distribution.
2., average volume particle diameter (with the relation of D90)
90% particle volume diameter (D90) that is associated with average volume particle diameter (D50) should be controlled in 1 ~ 50 mu m range, and the ratio of D90/D50 should be controlled in 2.5 ~ 4 scopes.Its reason be the ratio of D90/D50 as less than 2.5, the antibiotic glass powder is blending dispersion difficulty just in resin, easily produces light phenomenon at random, causes transparency low.And when the ratio of D920/D50 greater than 4, antibiotic glass powder blending dispersion difficulty in resin, and antibacterial resin product surface smoothness is also poor.
Thereby it is comparatively ideal that the ratio of the D90/D50 of antibiotic glass powder is controlled in 2.6 ~ 3.8 scopes, is controlled in 2.8 ~ 3.6 scopes then even more ideal.
Fig. 1 ~ Fig. 3 is the particle size distribution figure of antibiotic glass powder, and D90 is in 1 ~ 50 mu m range, and the ratio of D90/D50 is in 2.7 ~ 3.6 scopes.
3., the actual ratio that contains
The actual ratio that contains of the antibiotic glass powder of particle diameter more than 50 μ m with respect to entire amount, should be controlled at below the 10 volume %.
Its reason is that particle diameter is excessive, the condensation nucleus when easily becoming cohesion.Thereby the actual of antibiotic glass powder of excessive particle diameter contained than being controlled at below the prescribed value, help improving the dispersiveness of antibiotic glass powder, avoid stopping up the lance head of building mortion, make the smooth beauty of antibacterial resin product surface.
The actual ratio that contains of the antibiotic glass powder of particle diameter below 0.1 μ m with respect to entire amount, should be controlled at below the 5 volume %.
Its reason is that particle diameter is too small, easily cohesion around condensation nucleus.Thereby the actual of antibiotic glass powder that will cross small particle size contain than being controlled at below the prescribed value, helps improving the dispersiveness of antibiotic glass powder, avoids stopping up the lance head of building mortion, makes antibiotic glass powder-product smooth surface beauty.
Fig. 1 ~ Fig. 3 is the particle size distribution figure of antibiotic glass powder, actual the contain ratio of particle diameter more than 50 μ m, and particle diameter contains than being respectively below the 10 volume % and below the 5 volume % actual below the 0.1 μ m.
4., plural peak value
It is comparatively desirable that the antibacterial resin product according to the present invention, antibiotic glass powder use size-grade distribution have the antibiotic glass powder effect of plural peak value.As Fig. 2, shown in Figure 3, the antibiotic glass powder that size-grade distribution has first peak value, second peak value is comparatively ideal.
Its reason is the antibiotic glass powder of this structure, the glass particle of the glass particle of first peak value and second peak value can evenly closely mix, thereby make the antibiotic glass powder have splendid anti-microbial property and dispersing property, can not be subjected to the influence of building mortion kind, produce ganoid antibacterial resin product.
Size-grade distribution has plural peak value, then size-grade distribution self amplitude is wider, but by adjusting the specific surface area of antibiotic glass powder, the actual ratio that contains of specified particle diameter, can not be subjected to the influence of building mortion kind equally, produce ganoid antibacterial resin product, and the utilization of antibiotic glass powder in production reality also becomes convenient.
3, the specific surface area of antibiotic glass powder
One of feature of antibiotic glass powder, promptly specific surface area should be controlled at 9,000 ~ 30,000cm
2/ cm
3In the scope.
Its reason is a specific surface area less than 9,000cm
2/ cm
3The time, the blending dispersion of antibiotic glass powder in resin is poor, the practice difficulty, and the product surface after being shaped is rough.Surpass 30 and work as specific surface area, 000cm
2/ cm
3The time, particle diameter is too small, easily produces light phenomenon at random, influences transparency.
So specific surface area (cm of antibiotic glass powder
2/ cm
3), can calculate according to the particle size distribution result.Suppose that glass powder is spherical, according to take off data, can calculate unit volume (cm
3) surface-area (cm
2).
4, the glass moiety (1) of antibiotic glass powder
The glass moiety of antibiotic glass powder has Ag
2O, ZnO, CaO, B
2O
3And P
2O
5, and when being 100 weight % with overall weight, Ag
2The content of O in 0.2 ~ 5 weight % scope, the content of ZnO in 1 ~ 50 weight % scope, the content of CaO in 0.1 ~ 15 weight % scope, B
2O
3Content in 0.1 ~ 15 weight % scope, P
2O
5Content in 30 ~ 80 weight % scopes.
The weight ratio of ZnO/CaO should be controlled in 1.1 ~ 15 scopes.
①、Ag
2O
Ag
2O has the material of anti-microbial effect as in the glass formula 1, is necessary moiety.Contain Ag in the glass
2O, when glass dissolved, the Ag ion can play long-term anti-microbial effect with the slowly stripping of certain speed.
Ag
2It is comparatively ideal that the content of O is controlled in 0.2 ~ 5 weight % scope, and its reason is Ag
2It is not enough that the content of O such as less than 0.2 weight, the anti-microbial property of that antibiotic glass powder just seem, and will obtain the antibacterial effect of regulation, just must heavy addition antibiotic glass powder.On the other hand, work as Ag
2When the content of O surpassed 5 weight, the antibiotic glass powder just was easy to variable color, and cost is also high, and is economical inadequately.
②、ZnO
In glass formula 1, ZnO is necessary moiety.In the network-like molecular structure of antibiotic glass, ZnO plays a part the filling oxide compound.ZnO can not only prevent variable color, and can improve the anti-microbial property of antibiotic glass.
The content of ZnO with respect to overall weight, should be controlled in 2 ~ 60 weight % scopes.Its reason is content such as less than 2 weight of ZnO, will be difficult to the effect of bringing into play anti-variable color and improving anti-microbial property.And when the content of ZnO surpassed 60 weight %, the transparency of antibiotic glass was just very low, and lacked due physical strength.
The content of ZnO, the content that should take all factors into consideration CaO decides.Specifically, the weight ratio of ZnO/CaO should be controlled in 1.1 ~ 15 scopes.Its reason be the weight ratio of ZnO/CaO as less than 1.1, the anti-color changeable effect of antibiotic glass is not good.And when the weight ratio of ZnO/CaO greater than 15 the time, antibiotic glass can become oyster white, devitrification.
③、CaO
In glass formula 1, CaO is necessary moiety, is basic network filling oxide compound.In producing antibiotic glass powder process, can play the effect that reduces melt temperature, and, bring into play the effect of anti-variable color with ZnO.
The content of CaO with respect to overall weight, is controlled in 0.1 ~ 15 weight % scope more satisfactory.Its reason is content such as the less than 0.1 weight % of CaO, can't bring into play the effect of anti-variable color and reduction melt temperature.And when the content of CaO surpasses 15 weight %, can reduce the transparency of antibiotic glass on the contrary.
④、B
2O
3
In glass formula 1, B
2O
3Being necessary moiety, is basic network filling oxide compound.In the present invention, also with the improvement of the antibiotic glass transparency, Ag ion homogeneous stripping property is relevant.
B
2O
3Content, with respect to overall weight, be controlled in 0.1 ~ 15 weight % scope more satisfactory.Its reason is B
2O
3Content such as less than 0.1 weight %, antibiotic glass transparent low, Ag ionic homogeneous stripping property physical strength inequality.And work as B
2O
3Content when surpassing 15 weight %, antibiotic glass is easy to change, and lacks physical strength.
⑤、P
2O
5
In glass formula 1, P
2O
5Being necessary moiety, is basic network filling oxide compound.In the present invention, also with the improvement of the antibiotic glass transparency, Ag ion homogeneous stripping property is relevant.
P
2O
5Content, with respect to overall weight, be controlled in 30 ~ 80 weight % scopes more satisfactory.Its reason is P
2O
5Content such as less than 30 weight %, antibiotic glass transparent low, Ag ionic homogeneous stripping property physical strength inequality.And work as P
2O
5Content when surpassing 80 weight %, antibiotic glass is easy to change, and lacks physical strength.
6., other composition
In glass formula 1, can also add some other composition, for example CeO
2, MgO, Na
2O, Al
2O
3, K
2O, SiO
2, BaO etc., the addition of these compositions is wanted suitably not exceed purpose scope of the present invention, becomes the glass of other purposes.
5, the glass moiety (2) of antibiotic glass powder
The glass moiety (2) of antibiotic glass powder then is not contain ZnO, mainly contains Ag
2O, CaO, B
2O
3And P
2O
5When being 100 weight % with overall weight, Ag
2The content of O is at content 15 ~ 50 weight %, the B of 0.2 ~ 5 weight %, CaO
2O
3Content at 0.1 ~ 15 weight %, P
2O
5Content 30 ~ 80 weight % scopes in, and CaO/Ag
2The weight ratio of O should be controlled in 5 ~ 15 scopes.
①、Ag
2O
About Ag
2O is identical with prescription 1, and content also is with respect to overall weight, is controlled in 0.2 ~ 5 weight % scope more satisfactory.
②、CaO
CaO is a network filling oxide compound basic in the antibiotic glass, can play and reduce melt temperature and anti-variable color effect.
Here the content of CaO with respect to overall weight, is controlled in 15 ~ 50 weight % scopes more satisfactory.Its reason be CaO contain quantity not sufficient 15 weight %, because of not containing ZnO in this prescription, so can't bring into play anti-variable color and reduce the effect of melt temperature.
And when the content of CaO surpassed 50 weight %, it is very low that the transparency of antibiotic glass becomes on the contrary.
The content of CaO is taken all factors into consideration Ag
2The content of O decides better, specifically, and CaO/Ag
2The weight ratio of O is controlled in 5 ~ 15 scopes more satisfactory.
3., B
2O
3And P
2O
5
B
2O
3And P
2O
5Identical with prescription 1.
4., other composition
CeO
2, MgO, Na
2O, Al
2O
3, K
2O, SiO
2, BaO etc., all identical with prescription 1.
6, surface treatment
At the antibiotic glass powder surface, carry out surface treatment with coupling agent, effect is more satisfactory.
After coupling agent treatment, the antibiotic glass powder can have better discoloration-resistant, the transparency and dispersed, can not be subjected to the influence of building mortion kind, produces surface antibacterial resin product Paint Gloss.
Spendable coupling agent has silane coupling agent, aluminum coupling agent, titanium coupling agent etc.At polyhedron antibiotic glass powder, use the silane coupling agent better effects if.
The usage quantity of silane coupling agent, the polyhedron antibiotic glass powder usage quantity of per 100 weight unit is controlled in 0.01 ~ 30 weight unit scope, and effect is more satisfactory.
7, dissolution rate
In the antibiotic glass powder, the dissolution rate of antibacterial metal ions is controlled in 1 ~ 100 μ g/hr scope more satisfactory.
Its reason be the dissolution rate of antibacterial metal ions as less than 1 μ g/hr, do not have anti-microbial effect.And when the dissolution rate of antibacterial metal ions during greater than 100 μ g/hr, the antibiotic time length is short, and the addition of antibiotic glass powder is big in other words, and the antibacterial resin transparency of products is low.
Thereby comprehensive germ resistance and transparent good recipe face factor, the dissolution rate of antibacterial metal ions is controlled in 5 ~ 80 μ g/hr scopes then even more ideal.
8, resin
The antibacterial resin product earlier with antibiotic glass powder and mixed with resin, is mixed into comparatively ideal of antibacterial resin when being shaped.
Suitable resin has polyvinyl resin, acrylic resin, poly-carbon resin, polystyrene resin, polyvinyl chloride (PVC) RESINS, acrylic resin, Resins, epoxy, polyurethane resin, melamine resin, resol or the like.
When selecting resin, select for use light transmission rate more satisfactory at 50 ~ 100% resin, the selective light transmitance is then better at 80 ~ 100% resin.
Light transmission rate (%)=through light quantity/incident light quantity * 100
Can measure with absorption photometric instrument and quantorecorder by light quantity and incident light quantity.
The addition of antibiotic glass powder, with respect to overall weight, being controlled in 0.1 ~ 10 weight % scope is one of its key character.
Its reason is the addition such as the less than 0.1 weight % of antibiotic glass powder, and the anti-microbial property of antibacterial resin product is low.And when the addition of antibiotic glass powder surpassed 10 weight %, the bad mechanical strength of antibacterial resin product was difficult to mix, and transparency of products is also low.
So from factors such as balanced anti-microbial property and physical strengths, it is comparatively ideal that the addition of antibiotic glass powder is controlled in (with respect to overall weight) 0.5 ~ 8 weight % scope, is controlled in 1 ~ 5 weight % scope then even more ideal.
9, antibacterial resin product
There is no particular restriction for the style of antibacterial resin product, both can use the resin that contains the antibiotic glass powder, and directly shaping becomes the antibacterial resin product; Also can will contain the resin of antibiotic glass powder, processing makes it to become antimicrobial product on the rosin products surface.In a word, can adopt corresponding working method, produce various antibacterial resin products according to concrete purposes.
For example, as the example that Fig. 4, Fig. 5, Fig. 6, Fig. 7 exemplified, Fig. 4 is typical resin cosmetics containers, and bottle 10 and bottle cap 12 all are the antibacterial resin products.Suction pumps 20 among Fig. 5, the Flesible plastic container 30 among Fig. 6, the bucket 40 among Fig. 7 and drinking device 41 all are the antibacterial resin containers.
The 2nd example
The 2nd example also is the manufacture method of antibacterial resin product, and it comprises fusion, cooling pulverizing, these three technological processs of hybrid shaping.
1., the mixing engineering of frit and fusion engineering (technological process A)
With Ag
2O, ZnO, CaO, B
2O
3, P
2O
5Deng frit (antibiotic glass prescription 1) and Ag
2O, CaO, B
2O
3, P
2O
5Deng frit (the antibiotic glass prescription 2 that does not contain ZnO), behind the correct weighing, mix respectively.Mixing can be used mixed stirring devices such as omnipotent stirrer, the defeated and dispersed machine of aluminium magnetic, ball mill, turbine mixer.Use omnipotent stirrer, machine speed is set at 250rpm, time set is 10 ~ 180 minutes, and mixed effect is comparatively desirable.
Then the antibiotic glass raw material that uniform mixing is finished drops into fusion in the glass melting furnace, and melt temperature is set at 1100 ~ 1500 ℃, and the fusion time is set at 1 ~ 8 hour, and the fusion effect is comparatively desirable, and production efficiency is also high, and antibiotic glass devitrification not.
2., the comminution engineering of antibiotic glass (technological process B)
Glass metal cooling is pulverized, be ground into polyhedron-shapedly, median size is the technological process in specialized range also.
Concrete grammar is first coarse reduction (comprising cooling pulverizing in the water), then moderate pulverizing, fine pulverizing again, and this method can be produced the antibiotic glass powder of various particle diameters with raising the efficiency.According to the purposes difference, the requirement to the median size of antibiotic glass powder in actual the use is different, so after antibiotic glass is pulverized, can carry out stage treatment, to adapt to different requirements.
2.-1 coarse reduction
So-called coarse reduction also is about to antibiotic glass and is ground into the particle of median size about 10mm.Breaking method generally is that glass metal is injected flowing water, and glass melts the liquid explosion of catching a cold, and is ground into small-particle.
Antibiotic glass after the coarse reduction is acerous bulk, can confirm by electron micrograph.
2.-2 moderate is pulverized
So-called moderate is pulverized, and is exactly with the antibiotic glass particle of median size about 10mm, is ground into the particulate of median size about 1mm.Concrete grammar is to use earlier jaw crusher, with median size is antibiotic glass particle about 10mm, is ground into median size and is the particle about 5mm, uses electronic runner milling or motorized pulleys again, with median size is particle about 5mm, be ground into median size and be about 1mm particulate.Carry out moderate so stage by stage and pulverize, can control the median size of antibiotic glass powder in the crushing process effectively.
Antibiotic glass powder after moderate is pulverized is the polyhedron that the angle is arranged, and can confirm by electron photomicrograph.
2.-3 wash pulverizing
Fine powder is broken to be exactly particulate after moderate is pulverized, further is ground into median size and is the micropartical about 0.1 ~ 30 μ m.Broken electronic runner milling, motorized pulleys, oscillating mill, edge mill, the jet mills etc. of using of fine powder wherein use the jet mill effect best.Jet mill is state-of-the art pulverizer, has the automatic screening function, can prevent to produce the powder of small particle size, can effectively control the particle diameter of antibiotic glass powder.Spraying pressure is controlled at 0.59 ~ 1.18Mpa (6 ~ 12kg f/cm
2) in the scope, effect is more satisfactory.
Many after antibiotic glass powder after fine powder is broken, its polyhedral angle are pulverized than moderate, average volume particle diameter (D50), specific surface area are controlled also than being easier to, and these can confirm by electron photomicrograph and size-grade distribution result.
3., the manufacturing of antibacterial resin product (technological process C)
With polyhedron antibiotic glass powder, mix with the branch particle, after being uniformly dispersed, shape by desired shape, become the manufacturing process process of antibacterial resin product.
Blending means can adopt the method for mixing, and under room temperature (25 ℃) condition, stirs 1 ~ 20 minute, and stirrer can use turbine mixer.
Building mortion can use emission forming device, SMC (Sheet Molding Compoud) compression molding device, BMC (Bulk Molding Compoud) compression molding device, press molding equipment etc.
[example]
Below the invention will be further described by example.Example is that a part of the present invention is given an example, and practical application of the present invention surely not is confined to example.
[example 1]
1, fusion
The overall weight of antibiotic glass powder (antibiotic glass prescription 1) is as 100 weight %, P
2O
5Be that 50 weight %, CaO are 5 weight %, Na
2O is 1.5 weight %, B
2O
3Be 10 weight %, Ag
2O is 3 weight %, CeO
2Be that 0.5 weight %, ZnO are 30 weight %.Each raw material is dropped in the omnipotent stirrer, mix.The stirrer machine speed is 250rpm, churning time 30 minutes.Drop into fusion in the glass melting furnace after mixing again, melt temperature is 1280 ℃, and the fusion time is 3.5 hours, makes the antibiotic glass raw material be fused into glass and melts liquid.
2, cooling is pulverized
From glass melting, take out glass and melt liquid, pour in 25 ℃ the flowing water and cool off.Glass melts the liquid explosion of catching a cold in water, become the glass particle of median size about 10mm.The glass particle of this moment is observed in microscopically, can see that this particle is frangible, and acerous no face.
Then use jaw crusher to pulverize, machine speed 120rpm, glass particle enters jaw crusher from top to bottom from funneling feeding box, is ground into the particulate about median size 5mm.
Then pulverize with motorized pulleys, cylinder gap 1mm, machine speed 30rpm after the pulverizing once, arrives 0.25mm with gap adjustment again, and machine speed 30rpm carries out secondary and pulverizes.
Antibiotic glass powder after secondary is pulverized is to have the angle that the polyhedron-shaped of face arranged.
Use jet mill to carry out fine pulverization process at last, spraying pressure is 0.78Mpa, and the input amount of antibiotic glass powder is 5kg/hr, and forming average volume particle diameter (D50) at last is 2.6 μ m, and specific surface area is 26000cm
2/ cm
3The antibiotic glass powder.
Antibiotic glass powder after fine powder is broken through electron microscope observation, can confirm that the above micropartical of 95 weight % is to have the angle that the polyhedron of face is arranged.
3, the manufacturing of antibacterial resin product
With polyhedron antibiotic glass powder and polypropylene (PP) mixed with resin, the addition of powder is 3 weight %, 25kg/10min under the room temperature.The shaping forming temperature is 190 ℃ on emission forming machine subsequently, and specific product is antibacterial resin Container for cosmetics and bottle cap, sees Fig. 4 (a) (b).
4, to antibiotic glass powder and antibacterial resin product evaluation
To antibiotic glass powder and antibacterial resin product, do the and the following evaluation.
1., the transparency
To the transparency of antibiotic glass powder, use microscope, evaluate by following standard.
Excellent: water white transparency
Very: a part is opaque
In: a part of adularescent sense
Difference: be white in color fully
2., coherency
To the surface of antibiotic glass powder (polyhedron particle), use microscope, carry out the coherency evaluation by following standard.
Excellent: as not have minuteness particle around the surface and adhere to
Very: have minuteness particle to adhere to slightly around the surface
In: there is a small amount of minuteness particle to adhere to around the surface
Difference: have a large amount of minuteness particles to adhere to around the surface
3., Ag ionic stripping property
100g antibiotic glass powder impregnation in 500ml distilled water (20 ℃), is used bobbing machine vibration 1 hour.With centrifugal separator far away the Ag ion of separating out is separated from solution then, used filter paper (5C) to filter again, as test sample.Ag ion in the test sample is measured with ICP Emission Spectrophotometer method, further calculates Ag ionic stripping quantity (mg/kg conversion) again.
4., discoloration-resistant
With UV irradiation equipment to antibiotic glass powder prolonged exposure (the reflection shield temperature: 63 ℃, illumination: 300 ~ 700nm, 255w/m
2), behind the irradiation certain hour, use microscope, by following standard, the discoloration-resistant of antibiotic glass powder is evaluated.Evaluation result sees Table 1.
Excellent: prolonged exposure was still water white after 100 hours
Very: prolonged exposure is after 50 hours, and is still water white
Excellent: prolonged exposure is after 10 hours, and is still water white
Excellent: prolonged exposure is after 10 hours, and glass colour changes
5., anti-microbial property is estimated 1, is estimated 2
The antibiotic glass powder is joined in polypropylene (PP) resin, and addition 0.2 weight % mixes the back and is shaped on forming mill, makes the sheet material of thick 2mm, long 50mm, wide 50mm, as the anti-microbial property test sample.
Simultaneously, test organisms is cultivated on the agar plate culture plate, 35 ℃ of culture temperature, incubation time 24 hours, nutrient solution concentration 1/500 (Eiken Chemical's system), in the nutrient solution after the cultivation, the test organisms number should be controlled at 1 * 10 ℃ of FU/ml.
Test organisms adopts representative streptococcus aureus (Staphy lococus aureus IFO
#12732) and intestinal bacteria (Escherichia Coji ATCC
#8739) two kinds of bacterium.Respectively get the 0.5ml nutrient solution and drop on the test sample, be covered with film, place the constant temperature wet tank to cultivate, under the condition that humidity 95%, temperature are 35 ℃, cultivated 24 hours, calculate the test organisms number (growth colony) on the test sample afterwards again.
Do not contain polypropylene (PP) resin of antibiotic glass powder, make test sample plate equally, with same nutrient solution, same cultural method is cultivated, and calculates the test organisms number (growth colony) on the test sample plate that does not contain the antibiotic glass powder afterwards.
Compare the test organisms number (growth colony) on two test sample plate, can draw the anti-microbial property of antibacterial resin print.
Antibiotic evaluation 1 is the test result of streptococcus aureus, and antibiotic evaluation 2 is colibacillary test results.
The anti-microbial property judgement criteria is as follows:
Excellent: contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours/do not contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours is less than 1/10000
Very: contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours/do not contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours is between 1/10000 ~ 1/1000
In: contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours/do not contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours is between 1/1000 ~ 1/100
Difference: contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours/do not contain on the test sample plate of antibiotic glass powder, the bacterium number after the cultivation in 24 hours is greater than 1/100
6., surface smoothing
Use the surface smoothness survey meter, the surface of antibiotic rosin products is measured,, surperficial smoothness is estimated by following standard.
Excellent: surfaceness is below 1 μ m
Very: surfaceness is below 10 μ m
In: surfaceness is below 50 μ m
Difference: surfaceness is more than 50 μ m
[example 2]
Example 2 adopts the antibiotic glass powder (antibiotic glass fill a prescription 1) identical with example 1, and when different is last fine powder was broken, the input amount of antibiotic glass powder changed 50kg/hr into, and the average volume particle diameter that is shaped at last (D50) is 13.4 μ m, and specific surface area is 9800cm
2/ cm
3Polyhedron antibiotic glass powder, and the identical manufacture method of employing and example 1 is made the antibacterial resin product, and product is estimated.
[example 3]
Example 3 adopts the antibiotic glass powder (antibiotic glass fill a prescription 1) identical with example 1, and when different is last fine powder was broken, the input amount of antibiotic glass powder changed 30kg/hr into, and the average volume particle diameter that is shaped at last (D50) is 10.9 μ m, and specific surface area is 19700cm
2/ cm
3Polyhedron antibiotic glass powder, and the identical manufacture method of employing and example 1 is made the antibacterial resin product, and product is estimated.
[example 4]
4 of examples have only been done change to the antibiotic glass moiety, and manufacture method and example 1 are identical, and the antibacterial resin product of manufacturing is estimated.
This routine antibiotic glass prescription is as follows:
With respect to overall weight, P
2O
5Content be that the content of 59.6 weight %, CaO is 26.3 weight %, Na
2The content of O is 0.6 weight %, B
2O
3Content be 10 weight %, Ag
2The content of O is 3 weight %, CeO
2Content be 0.5 weight %.
This routine antibiotic glass powder is similarly polyhedron-shaped, and average volume particle diameter (D50) is 2.6 μ m, and specific surface area is 25000cm
2/ cm
3
[comparative example 1]
Comparative example 1 adopts the antibiotic glass powder (antibiotic glass fill a prescription 1) identical with example 1, but the average volume particle diameter of powder (D50) difference.The average volume particle diameter (D50) of the antibiotic glass powder of comparative example 1 is 35 μ m, and specific surface area is 8000cm
2/ cm
3, make the antibacterial resin product equally, and product estimated.
[comparative example 2]
Comparative example 2 adopts the antibiotic glass powder (antibiotic glass prescription 1) identical with example 1, but when fine powder is broken at last, use be not jet mill, but ball mill.After fine powder is broken, handle with flame method again, at last the antibiotic glass powder of Xing Chenging be shaped as spherically, average volume particle diameter (D50) is 35 μ m, specific surface area is 4000cm
2/ cm
3, make the antibacterial resin product equally, and product estimated.
[table 1]
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | |
| Glass formula | 1 | 1 | 1 | 1 | 1 | 1 |
| Ag 2O content (wt%) | 3 | 3 | 3 | 3 | 3 | 3 |
| D50(μm) | 2.6 | 13.4 | 10.9 | 2.6 | 35 | 35 |
| D90(μm) | 7.1 | 44.8 | 34.2 | 7.0 | 102 | 83 |
| D90/D50 | 2.7 | 3.3 | 3.1 | 2.7 | 2.9 | 2.4 |
| Shape | Polyhedron | Polyhedron | Polyhedron | Polyhedron | Polyhedron | Spherical |
| Specific surface area (cm 2/cm 3) | 26000 | 9800 | 19700 | 26000 | 8000 | 4000 |
| The transparency | Excellent | Very | Excellent | Excellent | Very | In |
| Coherency | Very | Very | Excellent | Excellent | In | Difference |
| Ag stripping quantity (mg/kg) | 4320 | 2180 | 2360 | 1260 | 415 | 208 |
| Discoloration-resistant | Excellent | Very | Excellent | Excellent | In | In |
| Antibiotic evaluation 1 | Excellent | Very | Excellent | Excellent | Very | Very |
| Antibiotic evaluation 2 | Excellent | Very | Excellent | Excellent | Very | Very |
| Surface smoothing | Excellent | Very | Very | Excellent | In | Difference |
[application on the industry]
As described above, as long as antibiotic resin product of the present invention, by the shape of control antibiotic glass powder, average volume particle diameter (D50), specific area and addition just can improve discoloration-resistant, the transparency, the dispersiveness of antibiotic glass powder. During hybrid shaping, can not be subjected to the impact of building mortion kind, also not be subjected to the impact of antibiotic glass powder addition size, produce the antibiotic resin product of smooth surface beauty.
By manufacture method of the present invention, shape, average volume particle diameter (D50), specific area, the addition of antibiotic glass powder are controlled in the prescribed limit, just can manufacture expeditiously the antibiotic resin product of smooth surface beauty, and not be subjected to the impact of building mortion kind and addition size.
Antibiotic resin product of the present invention also has certain deactivation to SARS virus in addition. When for example SARS virus is attached to the antibiotic resin product surface, can be by effectively deactivation.
Claims (9)
1. antibacterial resin product, the glass powder that contains the stripping property antibacterial metal ions with anti-microbial effect is blended in the resin, reshaping becomes the antibacterial resin product with anti-microbial effect, with respect to overall weight, the content of glass powder that contains the stripping property antibacterial metal ions is in 0.1 ~ 10 weight % scope, and this contain the stripping property antibacterial metal ions glass powder be shaped as polyhedron, D50 represents average volume particle diameter, D50 is in 0.2 ~ 30 mu m range, specific surface area is 9,000 ~ 30,000cm
2/ cm
3In the scope.
2. antibacterial resin product as claimed in claim 1 is characterized in that, this D90 represents to contain the particle volume diameter of the glass powder 90 percent of stripping property antibacterial metal ions, and D90 is in 1 ~ 50 mu m range, and the rate value of D90/D50 is in 2.5 ~ 4 scopes.
3. antibacterial resin product as claimed in claim 1 or 2 is characterized in that, with respect to entire amount, particle diameter contains than below 10 volume % the actual of the glass powder that contains the stripping property antibacterial metal ions more than the 50 μ m.
4. antibacterial resin product as claimed in claim 1 or 2 is characterized in that, with respect to entire amount, particle diameter contains than below 5 volume % the actual of the glass powder that contains the stripping property antibacterial metal ions more than the 0.1 μ m.
5. antibacterial resin product as claimed in claim 1 or 2 is characterized in that, the size-grade distribution that contains the glass powder of stripping property antibacterial metal ions has first peak value and second peak value.
6. antibacterial resin product as claimed in claim 1 or 2 is characterized in that, the dissolution rate that contains the metal ion with anti-microbial effect that contains in the glass powder of stripping property antibacterial metal ions is in 1 ~ 100 μ g/hr scope.
7. make the antibacterial resin method for product for one kind, make by containing the atomic glass powder that contains the stripping property antibacterial metal ions of polyhedron-shaped antibiotic glass, this glass powder that contains the stripping property antibacterial metal ions with respect to overall weight content in 0.1 ~ 10 weight % scope, described following (A) ~ (C) three technological processs that comprise: promptly comprise melting process, process, these three technological processs of hybrid shaping process were pulverized in cooling: wherein
(A) melting process: will contain the frit fusion of stripping property antibacterial metal ions, and make it to become the technological process that glass melts liquid;
(B) cooling crushing process: glass is melted liquid cool off in water, fine powder is broken again after the coarse reduction, makes the polyhedron that is shaped as of the glass powder that contains the stripping property antibacterial metal ions, and specific surface area is 9,000 ~ 30,000cm
2/ cm
3Process for making in the scope;
(C) hybrid shaping process: with the polyhedron-shaped glass powder that contains stripping property antibacterial metal ions homodisperse in resin, be shaped, become the technological process of an antibacterial resin product by needed shape.
8. antibacterial resin Manufacturing Method of Products as claimed in claim 7, it is characterized in that employed shredding unit can be one of jaw crusher, electronic runner milling, motorized pulleys, oscillating mill, ball mill, edge mill, jet mill in the described cooling disintegrating process.
9. as claim 7 or 8 described antibacterial resin Manufacturing Method of Products, it is characterized in that, the building mortion that uses in the described hybrid shaping technology can be emission forming device, one of tabular film plastics compression molding device, block film plastics compression molding device, press molding equipment.
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|---|---|---|---|
| JP2003382892 | 2003-11-12 | ||
| JP2003382892A JP4387163B2 (en) | 2003-11-12 | 2003-11-12 | Antibacterial molded article and manufacturing method thereof |
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|---|---|
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| CN100387644C true CN100387644C (en) | 2008-05-14 |
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| JP5388326B2 (en) * | 2008-05-12 | 2014-01-15 | 住化スタイロンポリカーボネート株式会社 | Transparent thermoplastic resin composition having excellent antibacterial properties and molded article comprising the same |
| US10131574B2 (en) | 2013-06-17 | 2018-11-20 | Corning Incorporated | Antimicrobial glass articles and methods of making and using same |
| CN113317324B (en) * | 2021-05-26 | 2022-05-17 | 晋大纳米科技（厦门）有限公司 | Glass silver-zinc-loaded antibacterial agent and preparation method thereof |
| CN113462157B (en) * | 2021-07-21 | 2023-09-26 | 马鞍山东毅新材料科技有限公司 | High-temperature-resistant polyimide display panel film and production process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002037643A (en) * | 2000-07-24 | 2002-02-06 | Nippon Electric Glass Co Ltd | Antimicrobial glass and its resin components |
| JP2002047359A (en) * | 2000-08-01 | 2002-02-12 | C I Kasei Co Ltd | Antibiotic polystylene heat shrinkable film |
| US6410633B1 (en) * | 1997-08-20 | 2002-06-25 | Nippon Electric Glass Co., Ltd. | Antibacterial glass and resin composite comprising the same |
| WO2003018499A2 (en) * | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial powdered glass and use thereof |
| WO2003085051A1 (en) * | 2002-04-05 | 2003-10-16 | Kanebo, Ltd. | Antibacterial glass composition, antibacterial resin composition and process for producing the same |
| CN1452602A (en) * | 2000-09-29 | 2003-10-29 | 兴亚硝子株式会社 | Antibacterial glass and method for production thereof |
-
2003
- 2003-11-12 JP JP2003382892A patent/JP4387163B2/en not_active Expired - Lifetime
-
2004
- 2004-01-19 CN CNB2004100033069A patent/CN100387644C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6410633B1 (en) * | 1997-08-20 | 2002-06-25 | Nippon Electric Glass Co., Ltd. | Antibacterial glass and resin composite comprising the same |
| JP2002037643A (en) * | 2000-07-24 | 2002-02-06 | Nippon Electric Glass Co Ltd | Antimicrobial glass and its resin components |
| JP2002047359A (en) * | 2000-08-01 | 2002-02-12 | C I Kasei Co Ltd | Antibiotic polystylene heat shrinkable film |
| CN1452602A (en) * | 2000-09-29 | 2003-10-29 | 兴亚硝子株式会社 | Antibacterial glass and method for production thereof |
| WO2003018499A2 (en) * | 2001-08-22 | 2003-03-06 | Schott Glas | Antimicrobial powdered glass and use thereof |
| WO2003085051A1 (en) * | 2002-04-05 | 2003-10-16 | Kanebo, Ltd. | Antibacterial glass composition, antibacterial resin composition and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005146058A (en) | 2005-06-09 |
| CN1616527A (en) | 2005-05-18 |
| JP4387163B2 (en) | 2009-12-16 |
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