CN112299753A - Novel odor-removing antibacterial artificial stone and preparation method thereof - Google Patents
Novel odor-removing antibacterial artificial stone and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel odor-removing antibacterial artificial stone and a preparation method thereof, wherein the artificial stone comprises the following raw materials in parts by mass: 8-16 parts of resin, 55-65 parts of aggregate, 23-35 parts of filler and 1-2.5 parts of lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder; the aggregate comprises quartz aggregate and/or glass particles; the filling material comprises quartz powder and/or superfine quartz powder; the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder comprises quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: (1-3): (1-3): (0.1-0.5). The novel odor-removing antibacterial artificial stone has the advantages of good antibacterial effect, good weather resistance, difficult fading or discoloration, odor removal and harmful gas reduction. The preparation method of the novel odor-removing antibacterial artificial stone is simple in preparation process.
Description
Technical Field
The invention relates to the technical field of artificial stone production, in particular to a novel odor-removing antibacterial artificial stone and a preparation method thereof.
Background
The artificial stone is an artificial stone which is processed by taking quartz sand or added glass particles with a certain amount as aggregate, taking quartz powder as filler and taking unsaturated polyester resin as adhesive through the steps of vacuumizing, vibrating compaction, curing and the like, has hard texture and compact structure, and has the characteristics of wear resistance, pressure resistance, high temperature resistance, corrosion resistance, seepage prevention and the like which are incomparable with other decorative materials. The artificial stone is widely applied to public buildings such as hotels, restaurants, banks and the like, and is widely applied to the field of home decoration such as kitchen table boards, commode tables, kitchen and bathroom wall surfaces and the like.
When the artificial stone is used as the table top, food can be directly placed on the table top, and each part of a human body is easy to frequently contact with the artificial stone table top, so that the demand of people on the artificial stone product with the antibacterial function is increased. Traditional antibiotic rostone generally adopts silver ion as the antibacterial agent for the rostone also leads to artificial stone board face easily to be changeable colour because the easy oxidation of silver ion discolours when having had the antibacterial property, uses for a long time and produces the colour difference easily, becomes a big pain point of antibiotic rostone.
Disclosure of Invention
Aiming at the problems in the background art, the invention aims to provide a novel odor-removing antibacterial artificial stone which has good antibacterial effect and good weather resistance, is not easy to fade or discolor, can remove peculiar smell and reduce harmful gas, and solves the problems of poor weather resistance, easy discoloration and color difference in the use process of the traditional antibacterial artificial stone.
The invention also aims to provide a preparation method of the novel odor-removing antibacterial artificial stone, the preparation process is simple, the prepared artificial stone has good antibacterial property, is not easy to fade or change color, and the artificial stone with different textures and board effects can be prepared, so that the artificial stone has rich decorative effect and wide applicability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel odor-removing antibacterial artificial stone comprises the following raw materials in parts by mass: 8-16 parts of resin, 55-65 parts of aggregate, 23-35 parts of filler and 1-2.5 parts of lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
the aggregate comprises quartz aggregate and/or glass particles;
the filling material comprises quartz powder and/or superfine quartz powder;
the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder comprises quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: (1-3): (1-3): (0.1-0.5).
Preferably, in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder, the mesh number of the quartz powder is 100-200 meshes.
Preferably, the resin is any one of o-benzene type unsaturated polyester resin, m-benzene type unsaturated polyester resin, p-benzene type unsaturated polyester resin, vinyl resin or epoxy resin.
Preferably, the quartz aggregate is quartz mineral particles with the particle size of 2-120 meshes, and the glass particles are cullet with the particle size of 2-120 meshes;
in the filling material, the mesh number of the quartz powder is 325 meshes or 400 meshes, and the mesh number of the superfine quartz powder is 1000-2000 meshes.
Preferably, the raw materials further comprise 0.04-0.16 part of curing agent and 0.04-0.16 part of coupling agent according to the mass parts.
Preferably, the raw materials further comprise 0-2 parts by weight of pigment, wherein the pigment comprises one or more of titanium dioxide, iron oxide red pigment, iron oxide yellow pigment and iron oxide black pigment.
A preparation method of a novel odor-removing antibacterial artificial stone is used for preparing the novel odor-removing antibacterial artificial stone and comprises the following steps:
(1) preparing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: carrying out dry ball milling on quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide for 1-4 h to prepare lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
(2) dispersing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: stirring resin and keeping the stirring state, adding the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder into the resin, adding a curing agent and a coupling agent, and keeping the stirring state for more than 0.5h to obtain a resin primary mixed material;
(3) mixing materials: mixing and uniformly stirring the resin primary mixed material, the aggregate and the filler to obtain a mixed material;
(4) material distribution: blanking the mixture into a material distribution frame;
(5) pressing: vacuumizing and pressing the mixture in the material distribution frame to obtain a blank body;
(6) and (3) curing: curing the blank and then demoulding;
(7) and (3) post-treatment: carrying out post-treatment on the blank after curing treatment, wherein the post-treatment adopts one or more of polishing treatment, crystal face treatment and special-shaped processing treatment to prepare the novel odor-removing antibacterial artificial stone;
the pigment is added in the step (2) by mixing with the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder and the resin and/or in the step (3) by mixing with the resin primary mixture, the aggregate and the filler and uniformly stirring, or in the step (4) by spraying the powder to a cloth frame.
Preferably, in the step (3), the process of mixing and uniformly stirring the resin primary mixture, the aggregate and the filler specifically comprises: and sequentially adding the aggregate, the superfine quartz powder in the filler, the resin primary mixture and the quartz powder in the filler into a stirrer to be mixed and stirred uniformly, and stirring the added raw materials uniformly before adding the raw materials each time.
Preferably, in the step (6), the curing temperature of the curing treatment is 80-110 ℃, and the curing time is 50-120 min.
Preferably, in the step (7), the special-shaped processing treatment is one or more of chamfering, rounding, perforating, sand blasting, abrasive brushing, profiling and engraving processing.
Compared with the prior art, the invention has the following beneficial effects:
1. by adding the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder and adopting a lanthanum oxide-cerium oxide-silver oxide composite system, silver ions can be released by silver oxide under the action of water to contact with bacteria, cell walls and cell membranes of the bacteria are damaged, the bacteria are inactivated, and the lanthanum oxide and the cerium oxide can release ultra-far infrared THz electromagnetic waves which are between microwaves and infrared radiation, have low photon energy and good biocompatibility and are harmless to a human body. Compared with infrared light, the ultra-far infrared THz electromagnetic wave has strong transmission and better penetrating power, and can enable oxygen molecules (O) in the air2) The active oxygen is excited, and the moisture on the table top and in the air is excited to become hydroxyl radicals, so that a hydroxyl radical ground state (active oxygen) is generated, a peptide chain in bacterial protein can be broken, the structure of the bacterial protein is damaged, and the bacteria lose activity;
2. in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder, the lanthanum oxide and the cerium oxide can release ultra-far infrared THz electromagnetic waves, and oxygen molecules (O) in the air can be generated2) Activated into active oxygen and water on the table top and in the air intoHydroxyl radical to generate hydroxyl radical ground state (active oxygen) to break down C-H and N-H in main pollutants such as formaldehyde, toluene, ammonia and hydrogen sulfide in air, so as to continuously decompose and convert these harmful substances into carbon dioxide (CO) in air2) With water (H)2O), can play a role in removing odor and reducing harmful gases for a long time;
3. because the whole system adopts the combination of resin and aggregate and filler, the aggregate plays the skeleton support effect, owing to pile up between the aggregate and form the space, through filler packing space has guaranteed the packing compactness, makes lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder can combine in the raw materials of rostone closely, keeps antibacterial property better.
Detailed Description
A novel odor-removing antibacterial artificial stone comprises the following raw materials in parts by mass: 8-16 parts of resin, 55-65 parts of aggregate, 23-35 parts of filler and 1-2.5 parts of lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
the aggregate comprises quartz aggregate and/or glass particles;
the filling material comprises quartz powder and/or superfine quartz powder;
the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder comprises quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: (1-3): (1-3): (0.1-0.5).
According to the traditional antibacterial artificial stone, silver ions are used as a main antibacterial carrier, and the addition amount of silver oxide (or silver compounds existing in other forms) reaches 0.06-0.25% of the whole system, so that the influence of the oxidative discoloration of silver materials on the color change of the surface of the artificial stone exceeds the acceptable degree of human sense;
according to the invention, the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is added, and a lanthanum oxide-cerium oxide-silver oxide composite system is adopted, wherein the silver oxide can be released under the action of waterSilver ions are released to contact with bacteria to destroy cell walls and cell membranes of the bacteria to inactivate the bacteria, the lanthanum oxide and the cerium oxide can release ultra-far infrared THz electromagnetic waves which are between microwaves and infrared radiation, photon energy is low, biocompatibility is good, and the nano-silver-containing nano-silver oxide is harmless to human bodies. Compared with infrared light, the ultra-far infrared THz electromagnetic wave has strong transmission and better penetrating power, and can enable oxygen molecules (O) in the air2) The active oxygen is excited, and the moisture on the table top and in the air is excited to become hydroxyl radicals, so that a hydroxyl radical ground state (active oxygen) is generated, a peptide chain in bacterial protein can be broken, the structure of the bacterial protein is damaged, and the bacteria lose activity;
in addition, the lanthanum oxide and the cerium oxide can release ultra-far infrared THz electromagnetic waves, and can enable oxygen molecules (O) in the air2) Excited into active oxygen, and excite the water on the table top and in the air into hydroxyl radicals, thereby generating hydroxyl radical ground state (active oxygen), and the carbon-hydrogen (C-H) and the nitrogen-H in the main pollutants such as formaldehyde, toluene, ammonia, hydrogen sulfide and the like in the air can be broken and split, thereby continuously decomposing and converting the harmful substances into carbon dioxide (CO) in the air2) With water (H)2O), can play a role in removing odor and reducing harmful gases for a long time;
because whole system adopts the combination of resin with aggregate and stopping, the aggregate plays the skeleton support effect, owing to pile up between the aggregate and form the space, through the filler fills the space, has guaranteed the packing compactness degree, makes lanthanum oxide-cerium oxide-silver oxide composite modification quartz powder can combine closely in the raw materials of rostone, keeps antibacterial property better, if the additive amount of aggregate, filler or resin is too much or too little, will lead to filling closely inadequately, makes lanthanum oxide-cerium oxide-silver oxide composite modification quartz powder can't combine closely in the raw materials of rostone, and the antibacterial property of the rostone who makes is poor.
According to the novel odor-removing antibacterial artificial stone, the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is introduced, so that the problems of poor weather resistance, easy color change and color difference in the using process of the traditional antibacterial artificial stone are solved while the antibacterial performance of the traditional silver antibacterial material is kept, and meanwhile, the novel odor-removing antibacterial artificial stone has a new function of removing harmful and unpleasant gases such as hydrogen sulfide, formaldehyde, benzene, ammonia and the like, and can remove peculiar smell and reduce harmful gases. In addition, the radioactivity index of the novel odor-removing antibacterial artificial stone reaches national standard A class (no use occasion), the half lethal concentration LD50 is more than 5000mg/kg (no toxicity), and the use performance is good.
Preferably, the addition amount of the filler and the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is 25-32 parts by weight.
The aggregate can play the skeleton support effect in the system, the aggregate is owing to pile up, forms the space between the granule, through adding the stopping is right the aggregate piles up the space that forms and packs, and will lanthanum oxide-cerium oxide-silver oxide composite modification quartz powder closely combines in the raw materials of rostone, when the stopping with the additive amount of lanthanum oxide-cerium oxide-silver oxide composite modification quartz powder is 25 ~ 32, the packing compactness is high, and the associativity of lanthanum oxide-cerium oxide-silver oxide composite modification quartz powder and the raw materials of rostone is good, the antibiotic effect of novel antibiotic rostone is good.
Preferably, in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder, the mesh number of the quartz powder is 100-200 meshes.
The aggregate can play the skeleton support effect in the system, the aggregate is owing to pile up, forms the space between the granule, through adding the filler is right the aggregate piles up the space that forms and fills, and will among the compound modified quartz powder of lanthanum oxide-cerium oxide-silver oxide, the mesh number of quartz powder is 100 ~ 200 mesh, makes lanthanum oxide-cerium oxide-silver oxide compound modified quartz powder can the zonulae occludens in the raw materials of rostone, in addition, will quartz powder, nanometer lanthanum oxide, nanometer cerium oxide and nanometer silver oxide mix, because the mesh number is 100 ~ 200 mesh the surface of quartz powder has sharp, sharp-pointed edges and corners, utilizes these edges and corners to in mixing process to nanometer lanthanum oxide, nanometer cerium oxide and nanometer silver oxide break up, make nanometer lanthanum oxide, nanometer, The nano cerium oxide and the nano silver oxide can be dispersed and adsorbed on the surface of the quartz powder, so that the dispersion uniformity of the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide is improved.
Specifically, the resin is any one of o-benzene type unsaturated polyester resin, m-benzene type unsaturated polyester resin, p-benzene type unsaturated polyester resin, vinyl resin or epoxy resin.
Through adopting resin with aggregate and stopping cooperate, the artificial stone that obtains through curing forming's compressive strength is high, and the durability is good, and performance is good.
Preferably, the quartz aggregate is quartz mineral particles with the particle size of 2-120 meshes, and the glass particles are cullet with the particle size of 2-120 meshes;
in the filling material, the mesh number of the quartz powder is 325 meshes or 400 meshes, and the mesh number of the superfine quartz powder is 1000-2000 meshes.
The quartz aggregate is one or more of quartz mineral particles with the particle size of 2-4 meshes, 4-6 meshes, 6-8 meshes, 8-16 meshes, 16-26 meshes, 26-40 meshes, 40-70 meshes, 70-100 meshes and 70-120 meshes; the glass particles are one or more of cullet with the particle size of 2-4 meshes, 4-6 meshes, 6-8 meshes, 8-16 meshes, 16-26 meshes, 26-40 meshes, 40-70 meshes, 70-100 meshes and 70-120 meshes.
The aggregate is quartz aggregate and/or glass particles, so that a skeleton supporting effect can be achieved in a system, the strength of the novel odor-removing antibacterial artificial stone is guaranteed, and the filling compactness of the novel odor-removing antibacterial artificial stone can be improved by matching with the resin and the filler, so that the light-weight high-strength using effect is achieved;
in addition, the aggregate is piled up, gaps are formed among particles, and the filler is added, is quartz powder and superfine quartz powder and can be filled among the gaps formed by the aggregate or coated on the surface of the aggregate. A large number of practices prove that the filling compactness is highest when the mesh number of the quartz powder in the filler is 325 meshes or 400 meshes, a small number of gaps still exist after the quartz powder is used for filling the gaps formed among the aggregates, and in order to achieve the optimal filling compactness, the gaps left after the quartz powder is filled are refilled by the superfine quartz powder, so that the filling compactness is ensured, the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder can be tightly combined in raw materials of the artificial stone, the obtained artificial stone has a good antibacterial effect, and the effects of removing peculiar smell and reducing harmful gases are good.
Further, the raw materials further comprise 0.04-0.16 part of curing agent and 0.04-0.16 part of coupling agent by weight.
The curing agent and the coupling agent are conventional curing agents and coupling agents.
By adding the coupling agent, the coupling agent can be combined with the resin, the aggregate or the filler, the dispersibility of the raw materials is improved, and by adding the curing agent, the raw materials are mixed and cured and formed, so that the novel odor-removing antibacterial artificial stone is high in compressive strength and good in service performance.
Further, the raw materials further comprise 0-2 parts by weight of pigment, wherein the pigment comprises one or more of titanium dioxide, iron oxide red pigment, iron oxide yellow pigment and iron oxide black pigment.
According to the face effect needs of rostone, when the face of the rostone of preparation needs to have the colour effect, through adding effect such as red, yellow or grey black can be adjusted out to the pigment, make adopt novel decoration effect of removing the antibiotic rostone of flavor abundanter, more pleasing to the eye.
A preparation method of a novel odor-removing antibacterial artificial stone is used for preparing the novel odor-removing antibacterial artificial stone and comprises the following steps:
(1) preparing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: carrying out dry ball milling on quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide for 1-4 h to prepare lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
(2) dispersing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: stirring resin and keeping the stirring state, adding the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder into the resin, adding a curing agent and a coupling agent, and keeping the stirring state for more than 0.5h to obtain a resin primary mixed material;
(3) mixing materials: mixing and uniformly stirring the resin primary mixed material, the aggregate and the filler to obtain a mixed material;
(4) material distribution: blanking the mixture into a material distribution frame;
(5) pressing: vacuumizing and pressing the mixture in the material distribution frame to obtain a blank body;
(6) and (3) curing: curing the blank and then demoulding;
(7) and (3) post-treatment: carrying out post-treatment on the blank after curing treatment, wherein the post-treatment adopts one or more of polishing treatment, crystal face treatment and special-shaped processing treatment to prepare the novel odor-removing antibacterial artificial stone;
the pigment is added in the step (2) by mixing with the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder and the resin and/or in the step (3) by mixing with the resin primary mixture, the aggregate and the filler and uniformly stirring, or in the step (4) by spraying the powder to a cloth frame.
Because the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder adopts nano lanthanum oxide, nano cerium oxide and nano silver oxide, the nano metal oxide has small particle size and large specific surface area, ions of the nano metal oxide are close to the surface of the particles, and the nano metal oxide can generate strong charge adsorption effect on substances close to the surfaces of the particles, so after the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide are mixed and ball-milled with large-size quartz powder (100-200 meshes are about 0.075 mm-0.15 mm), the nano metal oxide can be firmly adsorbed on the surfaces of the quartz particles, and the coated lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is formed;
in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder, the quartz powder can help the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide to disperse and prevent the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide from reuniting again, if the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide are directly added into a system, self-reuniting is easy to occur, the nano cerium oxide and the nano silver oxide cannot be uniformly dispersed in the whole product system, so that the prepared artificial stone has an antibacterial effect locally, has no antibacterial effect locally, and cannot meet the use requirement;
in addition, because the usage amount of the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is small, in the step (2), the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is firstly added into the resin, and the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder can be better dispersed in the whole system by virtue of the fluidity and the stirring process of the resin;
the pigment can be added in the step (2) and/or the step (3) or the step (4) according to different plate surface texture patterns. When preparing a uniform line plate, adding the pigment in the step (2) and/or the step (3) to form lines uniformly distributed on the whole body; when a product with local lines is prepared, the pigment is added in the step (4), and the pigment is directly added at the local part needing the lines;
the preparation method of the novel odor-removing antibacterial artificial stone is simple in preparation process, the prepared artificial stone is good in antibacterial property, not prone to fading or discoloring, the artificial stone with different textures and board effects can be prepared, the decoration effect is rich, and the applicability is wide.
Preferably, in the step (5), the vacuum degree of the vacuum pumping reaches-96 kPa or above, and the swing frequency of the pressing head is 3000-4500 Hz.
The vacuum degree of the vacuumizing and the swing frequency of the pressing head are set, so that the vacuumizing effect and the pressing effect of the mixture in the cloth frame are guaranteed, the density and the strength of the novel odor removal antibacterial artificial stone are improved, and the air hole defects are reduced.
Preferably, in the step (3), the process of mixing and uniformly stirring the resin primary mixture, the aggregate and the filler specifically comprises: and sequentially adding the aggregate, the superfine quartz powder in the filler, the resin primary mixture and the quartz powder in the filler into a stirrer to be mixed and stirred uniformly, and stirring the added raw materials uniformly before adding the raw materials each time.
The aggregate, the superfine quartz powder in the filler, the resin primary mixture and the quartz powder in the filler are sequentially added into a stirrer to be mixed and uniformly stirred, so that the resin primary mixture can be well dispersed in the whole system, the raw materials in the whole system are good in combination, the filling compactness is high, the added raw materials are required to be uniformly stirred before each raw material is added, and the dispersion uniformity of the raw materials in the whole system is ensured.
Preferably, in the step (6), the curing temperature of the curing treatment is 80-110 ℃, and the curing time is 50-120 min.
Through the control of the curing temperature and the curing time of the curing treatment in the step (6), the curing effect of the blank is ensured, the situation that the product is cracked due to overhigh curing temperature is avoided, or the situation that the curing is incomplete due to too low curing temperature and too short curing time is avoided, and the using effect of the novel odor removal antibacterial artificial stone is ensured.
Specifically, in the step (7), the special-shaped processing treatment is one or more of chamfering, rounding, perforating, sand blasting, grinding and brushing, profiling and engraving.
Through to after-treatment is carried out to the body after curing treatment, special-shaped processing can make the novel antibiotic rostone of removing the flavor obtain different shape effects to improved the richness of decorating, the effect is pleasing to the eye.
Preferably, after the special-shaped processing treatment in the step (7) is completed, a polishing machine and/or waterproof abrasive paper is/are adopted to polish and polish the part of the artificial stone, which needs polishing.
And (7) after the special-shaped processing treatment is finished, grinding and polishing are carried out on the part of the artificial stone needing polishing, so that the surface smoothness of the product can be improved, and the surface texture is good.
The technical solution of the present invention is further explained by the following embodiments.
In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Examples 1 to 5
A novel odor-removing antibacterial artificial stone is prepared by preparing raw materials according to the raw material formula shown in Table 1 for later use, and is prepared according to the following steps:
(1) preparing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: putting quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide into a ball mill, and performing dry ball milling for 3 hours to prepare lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
(2) dispersing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: adding resin into a stirring barrel, stirring the resin and keeping the stirring state, adding the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder and the pigment into the resin, adding a curing agent and a coupling agent, and keeping the stirring state for 1h to obtain a resin primary mixed material;
(3) mixing materials: sequentially adding the aggregate, the superfine quartz powder in the filler, the resin primary mixture and the quartz powder in the filler into a stirrer in sequence, uniformly stirring, and uniformly stirring the added raw materials before adding the raw materials each time to obtain a mixture;
(4) material distribution: blanking the mixture into a material distribution frame;
(5) pressing: vacuumizing the mixture in the material distribution frame by using vacuumizing equipment (the vacuum degree of vacuumizing reaches-96 kPa), and starting pressing equipment for pressing (the swing frequency of a pressing head is 3500Hz) to obtain a blank;
(6) and (3) curing: sending the blank into curing equipment for curing treatment (the curing temperature is 100 ℃, the curing time is 90min), and then demolding;
(7) and (3) post-treatment: and polishing the blank after curing to obtain the novel odor-removing antibacterial artificial stone.
TABLE 1 raw Material formulation composition
Wherein the resin is vinyl resin, the curing agent is methyl ethyl ketone peroxide, and the coupling agent is silane coupling agent;
the quartz aggregate is quartz mineral particles with the particle size of 70-100 meshes and 70-120 meshes, and the glass particles are cullet with the particle size of 70-100 meshes and 70-120 meshes;
the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is prepared from quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: 2: 2: 0.3, the mesh number of the quartz powder in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is 100-200 meshes;
the mesh number of the quartz powder in the filling material is 325 meshes, and the mesh number of the superfine quartz powder is 1000-2000 meshes;
the colored pigment is iron red pigment.
Example 6
Compared with the embodiment 5, the raw materials of the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder are quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: 1: 1: 0.1, and the formula and the preparation method of the other raw materials are consistent with those of the example 5, so that the novel odor-removing antibacterial artificial stone is prepared.
Example 7
Compared with the embodiment 5, the raw materials of the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder are quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: 3: 3: 0.5, and the formula and the preparation method of the other raw materials are consistent with those of the example 5, so that the novel odor-removing antibacterial artificial stone is prepared.
Comparative example 1
Compared with the artificial stone prepared in the embodiment 5, the addition amount of the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is 4 parts, and the formula and the preparation method of the other raw materials are the same as those of the embodiment 5, so that the artificial stone is prepared.
Comparative example 2
Compared with the embodiment 5, the mesh number of the quartz powder in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is 40-70 meshes, and the formula and the preparation method of the rest raw materials are the same as those in the embodiment 5, so that the antibacterial artificial stone is prepared.
Comparative example 3
Compared with the embodiment 5, the mesh number of the quartz powder in the filling material is 200 meshes, and the formula and the preparation method of the other raw materials are the same as those of the embodiment 5, so that the antibacterial artificial stone is prepared.
Comparative example 4
The antibacterial artificial stone is prepared from the following raw materials in parts by weight:
13 parts of vinyl resin, 60 parts of quartz aggregate (specifically quartz mineral particles with the particle sizes of 70-100 meshes and 70-120 meshes), 27 parts of quartz powder (with the mesh number of 325 meshes), 0.2 part of nano silver oxide, 1.3 parts of curing agent (specifically methyl ethyl ketone peroxide) and 1.5 parts of coupling agent (specifically silane coupling agent);
the preparation method comprises the following steps:
(1) mixing raw materials: putting the raw materials into a stirrer according to the formula amount, and uniformly mixing and stirring to obtain a mixture;
(3) material distribution: blanking the mixture into a material distribution frame;
(4) pressing: vacuumizing the mixture in the material distribution frame by using vacuumizing equipment (the vacuum degree of vacuumizing reaches-96 kPa), and starting pressing equipment for pressing (the swing frequency of a pressing head is 3500Hz) to obtain a blank;
(5) and (3) curing: sending the blank into curing equipment for curing treatment (the curing temperature is 100 ℃, the curing time is 90min), and then demolding;
(6) and (3) post-treatment: and polishing the blank subjected to curing treatment to obtain the antibacterial artificial stone.
And (3) performance testing:
(1) and (3) testing the antibacterial rate: the antibacterial rate is determined according to the test method of JC/T897-2014 antibacterial ceramic product antibacterial performance.
(2) Weather resistance test (color change value Δ E): the samples are measured by adopting the artificial climate resistance of GB/T35157-2017 resin type synthetic stone plate 6.4.7.1, wherein the color difference and the visual relation (color change value delta E) in the test result are as follows: 0 to 0.5 (slight color difference, minimal feeling); 0.5-1.5 (small color difference, slight feeling); l.5-3 (small color difference, obvious feeling); 3-6 (large chromatic aberration, obvious feeling); more than 6 (large chromatic aberration, strong feeling);
the test results are shown in the following table:
from the test results, the novel odor-removing antibacterial artificial stone prepared in the embodiments 1 to 7 has a good antibacterial effect, the tested color change values delta E are all less than 0.5, only small color difference exists, the antibacterial performance of the artificial stone is ensured, meanwhile, the situation that the artificial stone is discolored due to the fact that a large amount of silver oxide is added independently is avoided, meanwhile, the novel odor-removing antibacterial artificial stone prepared in the embodiments 1 to 7 has a removal effect on formaldehyde, ammonia, benzene and hydrogen sulfide gas, and is excellent in service performance, and in addition, the embodiments 1 to 7 can meet the water absorption rate, pollution resistance, chemical corrosion resistance, Mohs hardness, linear expansion coefficient, aging resistance, wear resistance, high temperature resistance, bending strength, compression strength and falling ball impact resistance of the industrial standard JG/T463 2014 artificial quartz stone slab for building decoration, The requirements of freeze-thaw resistance and heavy metal content;
in comparative example 1, the addition amount of lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is too large, so that the color change value delta E of the antibacterial artificial stone is larger than 0.5, slight color difference can be felt, and the using effect of the antibacterial artificial stone is influenced;
comparative example 2 since the mesh number of the quartz powder in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is too small and the particles are too large, when the quartz powder, the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide are mixed, the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide are not easily scattered, so that the nano lanthanum oxide, the nano cerium oxide and the nano silver oxide are poor in dispersion uniformity in the whole system, and the antibacterial effect and the harmful gas removal effect of the antibacterial artificial stone are affected;
the quartz powder in the filler of the comparative example 3 has too small mesh number and too large particles, and is filled in the aggregate, so that the filling compactness is reduced, the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder cannot be tightly combined in the raw materials of the artificial stone, and the antibacterial effect and the harmful gas removal effect of the antibacterial artificial stone are influenced;
comparative example 4 through directly adding nanometer silver oxide to the raw materials, and the addition amount is big, and although antibiotic effect is good, the color change value delta E through the test is greater than 2, and the colour difference sensation is obvious, uses for a long time and discolours easily, and is not pleasing to the eye, has seriously influenced antibiotic rostone's result of use.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A novel odor-removing antibacterial artificial stone is characterized by comprising the following raw materials in parts by mass: 8-16 parts of resin, 55-65 parts of aggregate, 23-35 parts of filler and 1-2.5 parts of lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
the aggregate comprises quartz aggregate and/or glass particles;
the filling material comprises quartz powder and/or superfine quartz powder;
the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder comprises quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide, wherein the mass ratio of the quartz powder to the nano lanthanum oxide to the nano cerium oxide to the nano silver oxide is 100: (1-3): (1-3): (0.1-0.5).
2. The artificial stone for removing odor and resisting bacteria as claimed in claim 1, wherein the mesh number of the quartz powder in the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder is 100-200 meshes.
3. A novel artificial stone for removing odor and resisting bacteria according to claim 1, wherein the resin is any one of o-benzene type unsaturated polyester resin, m-benzene type unsaturated polyester resin, p-benzene type unsaturated polyester resin, vinyl resin or epoxy resin.
4. The artificial stone for removing odor and resisting bacteria as claimed in claim 1, wherein the quartz aggregate is quartz mineral particles with a particle size of 2-120 meshes, and the glass particles are cullet with a particle size of 2-120 meshes;
in the filling material, the mesh number of the quartz powder is 325 meshes or 400 meshes, and the mesh number of the superfine quartz powder is 1000-2000 meshes.
5. The novel odor-removing antibacterial artificial stone according to claim 1, wherein the raw materials further comprise 0.04-0.16 parts of a curing agent and 0.04-0.16 parts of a coupling agent by weight.
6. The novel odor-removing antibacterial artificial stone according to claim 1, wherein the raw materials further comprise 0-2 parts by weight of pigment, wherein the pigment comprises one or more of titanium dioxide, iron red pigment, iron yellow pigment and iron black pigment.
7. A method for preparing a novel odor-removing antibacterial artificial stone, which is used for preparing the novel odor-removing antibacterial artificial stone as claimed in any one of claims 1 to 6, and comprises the following steps:
(1) preparing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: carrying out dry ball milling on quartz powder, nano lanthanum oxide, nano cerium oxide and nano silver oxide for 1-4 h to prepare lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder;
(2) dispersing lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder: stirring resin and keeping the stirring state, adding the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder into the resin, adding a curing agent and a coupling agent, and keeping the stirring state for more than 0.5h to obtain a resin primary mixed material;
(3) mixing materials: mixing and uniformly stirring the resin primary mixed material, the aggregate and the filler to obtain a mixed material;
(4) material distribution: blanking the mixture into a material distribution frame;
(5) pressing: vacuumizing and pressing the mixture in the material distribution frame to obtain a blank body;
(6) and (3) curing: curing the blank and then demoulding;
(7) and (3) post-treatment: carrying out post-treatment on the blank after curing treatment, wherein the post-treatment adopts one or more of polishing treatment, crystal face treatment and special-shaped processing treatment to prepare the novel odor-removing antibacterial artificial stone;
the pigment is added in the step (2) by mixing with the lanthanum oxide-cerium oxide-silver oxide composite modified quartz powder and the resin and/or in the step (3) by mixing with the resin primary mixture, the aggregate and the filler and uniformly stirring, or in the step (4) by spraying the powder to a cloth frame.
8. The method for preparing artificial stone with odor removing and antibacterial effects as claimed in claim 7, wherein in the step (3), the process of mixing and stirring the resin primary mixture, the aggregate and the filler is specifically as follows: and sequentially adding the aggregate, the superfine quartz powder in the filler, the resin primary mixture and the quartz powder in the filler into a stirrer to be mixed and stirred uniformly, and stirring the added raw materials uniformly before adding the raw materials each time.
9. The preparation method of the novel artificial stone with odor removal and antibiosis functions as claimed in claim 7, wherein in the step (6), the curing temperature of the curing treatment is 80-110 ℃, and the curing time is 50-120 min.
10. The method for preparing artificial stone with odor removing and antibacterial effects as claimed in claim 7, wherein in the step (7), the special-shaped processing is one or more of chamfering, rounding, perforating, sand blasting, grinding and brushing, profiling and engraving.
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