阅读说明：本技术 一种含有无机金属离子的建筑板材及其制备方法 (Building board containing inorganic metal ions and preparation method thereof ) 是由 李毕忠 于 2021-04-26 设计创作，主要内容包括：本发明公开了一种含有无机金属离子的建筑板材,其制备原料以重量份计包括：PVC板材基材50-60份,增塑剂10-20份,抗菌剂2-5份,防腐剂0.01-0.1份,表面活性剂1-10份,涂料基料10-30份。本发明所述的含有无机金属离子的建筑板材,具有优良的抗菌,抗病毒的性能,并且使用的抗菌剂为多孔结构包覆的无机金属离子,杀菌功效释放稳定,具有缓释的效果,可以延长板材的抗菌,抗病毒时效,并且建筑板材具有优良的抗菌,抗病毒功效的同时还具有良好的力学性能,使用时间长。(The invention discloses a building board containing inorganic metal ions, which comprises the following preparation raw materials in parts by weight: 50-60 parts of PVC plate base material, 10-20 parts of plasticizer, 2-5 parts of antibacterial agent, 0.01-0.1 part of preservative, 1-10 parts of surfactant and 10-30 parts of coating base material. The building board containing inorganic metal ions has excellent antibacterial and antiviral properties, the used antibacterial agent is the inorganic metal ions coated by the porous structure, the antibacterial effect is stably released, the slow-release effect is achieved, the antibacterial and antiviral aging of the board can be prolonged, and the building board has excellent antibacterial and antiviral effects, good mechanical properties and long service time.)

1. A building board containing inorganic metal ions is characterized in that the preparation raw materials at least comprise: PVC plate base material, plasticizer, antibacterial agent, preservative and surfactant.

2. The building board containing inorganic metal ions as claimed in claim 1, wherein the preparation raw material comprises, in parts by weight: 50-60 parts of PVC plate base material, 10-20 parts of plasticizer, 2-5 parts of antibacterial agent, 0.01-0.1 part of preservative and 1-10 parts of surfactant.

3. The building board containing inorganic metal ions as claimed in claim 1, wherein the plasticizer is selected from one or more of fatty acid ester, aliphatic dibasic acid ester, polybasic alcohol acid, alkyl sulfonate and phthalate.

4. The inorganic metal ion-containing building board according to claim 1, wherein the antibacterial agent is a combination of an inorganic metal oxide and an inorganic porous material.

5. The building board containing inorganic metal ions according to claim 4, wherein the inorganic porous material is one selected from zeolite, activated carbon, insoluble phosphate, montmorillonite, tobermorite, and shell powder.

6. The building board containing inorganic metal ions as claimed in claim 4, wherein the inorganic metal oxide is selected from one or more of nano silver oxide, copper oxide, zinc oxide, aluminum oxide and titanium dioxide.

7. The building board containing inorganic metal ions according to claim 1, wherein the preservative is selected from one or more of organic acids, quaternary ammonium salts and peroxide preservatives.

8. The building board containing inorganic metal ions as claimed in claim 1, wherein the surfactant is selected from one or more of sodium sulfonate, sodium dodecylbenzenesulfonate and sodium stearate.

9. The inorganic metal ion-containing building board according to claim 1, wherein the weight ratio of the surfactant to the preservative is 1: (0.01-0.1).

10. A method of making a building board containing inorganic metal ions according to any one of claims 1 to 9, comprising the steps of:

(1) adding metal oxide and inorganic porous material into deionized water, mixing, stirring at constant temperature of 80-100 deg.C for 2-3h, oven drying, and grinding to obtain antibacterial agent powder;

(2) adding the plate base material, the plasticizer and the antibacterial agent powder into a high-speed stirrer according to the parts by weight, mixing and stirring, then adding the mixture into an internal mixer for mixing, wherein the mixing temperature is 110-145 ℃, adding the mixture into an open mill for plastication after mixing, and then pressing the mixture into sheets through two calenders;

(3) mixing a surfactant and a preservative, stirring in a high-speed mixer, and mixing and stirring for 1-2 hours to obtain the antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 30-60min at the temperature of 30-45 ℃ to finish the preparation.

Technical Field

The invention relates to a building board containing inorganic metal ions and a preparation method thereof, and mainly relates to the field of antibacterial and antiviral PVC boards.

Background

The building materials are various materials used in building engineering, and are classified into inorganic metal materials, non-metal materials, organic plant materials, synthetic polymer materials, and composite materials formed by compounding inorganic non-metal materials and organic materials. The synthetic polymer material comprises plastics, paint and asphalt material, and the PVC material in the plastics occupies most of the plastics. Along with the improvement of living standard, people attach more and more importance to safety and environmental protection, and hope to use PVC material with antibacterial and antiviral properties.

At present, the antibacterial and antiviral PVC plastic is added with an antibacterial agent to improve the antibacterial performance of the PVC plastic, but the used antibacterial agent is generally a single antibacterial agent, the antibacterial effect is single, the prepared PVC plastic has a good antibacterial effect at the beginning, but the antibacterial effect is reduced along with the prolonging of the use time, the antibacterial effect is reduced by using the silicate silver-loaded antibacterial component as the antibacterial agent in the patent of CN111777827A, the better antibacterial effect can be achieved at the initial stage of the preparation of the PVC material, but the antibacterial effect is gradually reduced along with the prolonging of the use time, and the long-time antibacterial effect cannot be achieved.

Disclosure of Invention

In order to improve the antibacterial and antiviral properties of the PVC board and prolong the antibacterial and antiviral time, the first aspect of the invention provides a building board containing inorganic metal ions, which is prepared from at least the following raw materials: PVC plate base material, plasticizer, antibacterial agent, preservative and surfactant.

As a preferred embodiment, the preparation raw materials comprise, in parts by weight: 50-60 parts of PVC plate base material, 10-20 parts of plasticizer, 2-5 parts of antibacterial agent, 0.01-0.1 part of preservative and 1-10 parts of surfactant.

As a preferred embodiment, the plasticizer is selected from one or more of fatty acid ester, aliphatic dibasic acid ester, polybasic alcohol acid, alkyl sulfonate and phthalate.

As a preferred embodiment, the antibacterial agent is a combination of an inorganic metal oxide and an inorganic porous material.

As a preferred embodiment, the inorganic porous material is one selected from the group consisting of zeolite, activated carbon, insoluble phosphate, montmorillonite, tobermorite, and shell powder.

As a preferred embodiment, the inorganic metal oxide is selected from one or a combination of several of nano silver oxide, copper oxide, zinc oxide, aluminum oxide and titanium dioxide.

In a preferred embodiment, the preservative is selected from one or a combination of organic acids, quaternary ammonium salts and peroxide preservatives.

In a preferred embodiment, the surfactant is selected from one or more of sodium sulfonate, sodium dodecyl benzene sulfonate and sodium stearate.

As a preferred embodiment, the weight ratio of the surfactant to the preservative is 1: (0.01-0.1).

In a second aspect, the present invention provides a method for preparing a building board containing inorganic metal ions, comprising the steps of:

(1) adding metal oxide and inorganic porous material into deionized water, mixing, stirring at constant temperature of 80-100 deg.C for 2-3h, oven drying, and grinding to obtain antibacterial agent powder;

(2) adding the plate base material, the plasticizer and the antibacterial agent powder into a high-speed stirrer according to the parts by weight, mixing and stirring, then adding the mixture into an internal mixer for mixing, wherein the mixing temperature is 110-145 ℃, adding the mixture into an open mill for plastication after mixing, and then pressing the mixture into sheets through two calenders;

(3) mixing a surfactant and a preservative, stirring in a high-speed mixer, and mixing and stirring for 1-2 hours to obtain the antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 30-60min at the temperature of 30-45 ℃ to finish the preparation.

Compared with the prior art, the invention has the following beneficial effects:

(1) the building board containing inorganic metal ions has antibacterial and antiviral properties, and can play a role in protecting the life safety of users when in use.

(2) According to the building board containing the inorganic metal ions, the mildew-proof coating is coated outside the board, so that the mildew-proof performance of the building board is greatly improved, and the service life of the building board can be effectively prolonged.

(3) According to the building board containing the inorganic metal ions, the antibacterial agent is the inorganic metal ions coated by the porous structure, the sterilization effect is stably released, the slow release effect is achieved, and the antibacterial and antiviral aging of the board can be prolonged.

(4) According to the building board containing inorganic metal ions, the use ratio of the PVC board base material to the antibacterial agent is optimized, so that the board has excellent antibacterial and antiviral properties, and meanwhile, the good mechanical properties are kept.

Detailed Description

In order to improve the antibacterial and antiviral properties of the PVC board and prolong the antibacterial and antiviral time, the first aspect of the invention provides a building board containing inorganic metal ions, which is prepared from at least the following raw materials: PVC plate base material, plasticizer, antibacterial agent, preservative and surfactant.

As a preferred embodiment, the preparation raw materials comprise, in parts by weight: 50-60 parts of PVC plate base material, 10-20 parts of plasticizer, 2-5 parts of antibacterial agent, 0.01-0.1 part of preservative and 1-10 parts of surfactant.

As a preferred embodiment, the plasticizer is selected from one or more of fatty acid ester, aliphatic dibasic acid ester, polybasic alcohol acid, alkyl sulfonate and phthalate.

As a preferred embodiment, the antibacterial agent is a combination of an inorganic metal oxide and an inorganic porous material.

As a preferred embodiment, the inorganic porous material is one selected from the group consisting of zeolite, activated carbon, insoluble phosphate, montmorillonite, tobermorite, and shell powder.

As a preferred embodiment, the inorganic metal oxide is selected from one or a combination of several of nano silver oxide, copper oxide, zinc oxide, aluminum oxide and titanium dioxide.

It is further preferred that the inorganic metal oxide is a combination of nano silver oxide and zinc oxide.

Further preferably, the weight ratio of the nano silver oxide to the zinc oxide is 1: (1-2).

The inorganic metal oxide is selected from the compound of zinc oxide and nano silver oxide, and the weight ratio of the zinc oxide to the nano silver oxide is 1: (1-2). The zinc oxide can absorb the energy of light in the environment, valence electrons are excited to jump, oxygen and water molecules on the surface of the zinc oxide and in the surrounding environment are activated, superoxide anions and hydroxyl free radicals with strong redox capability are formed, and the superoxide anions and the hydroxyl free radicals can react with glucoside, unsaturated fatty acid and protein in microbial cells to destroy the normal structure of the microbes, so that the microbes die. When trace heavy metal ions contact with the microbial membrane, the metal ions and the microbial membrane are tightly combined due to coulomb attraction, the metal ions can penetrate through the microbial membrane to enter the body of the microbe, and the anions and sulfydryl on proteins in the microbe body undergo chemical reaction to cause protein solidification, so that the disturbance of a system in the microbe body is caused to cause the death of the microbe. The nano silver oxide and the zinc oxide have a synergistic effect, and the addition of the zinc oxide can improve the photocatalytic effect of the nano silver oxide, so that superoxide anions and hydroxyl radicals with strong redox capability can be generated on the surface of the nano silver oxide, and the antibacterial capability of the compound composition is improved. And the applicant finds that when the weight ratio of the zinc oxide to the nano silver oxide is 1: (1-2), the bacteriostatic effect is the best, and the probable reason is presumably that the nano silver oxide can release part of silver ions to contact with microorganisms to play a certain bactericidal effect, and the low-concentration metal oxide has a slow-release effect in the subsequent stage, so that the bacteriostatic effect can be maintained for a long time.

In a preferred embodiment, the preservative is selected from one or a combination of organic acids, quaternary ammonium salts and peroxide preservatives.

In a preferred embodiment, the surfactant is selected from one or more of sodium sulfonate, sodium dodecyl benzene sulfonate and sodium stearate.

As a preferred embodiment, the weight ratio of the surfactant to the preservative is 1: (0.01-0.1).

Further preferably, the weight ratio of the surfactant to the preservative is 1: (0.01-0.05). More preferably 1: 0.025.

the preservative contains certain polar groups, has higher surface energy and stronger van der waals force among particles, has a tendency of easy aggregation when being directly used as a filler of a coating, has poor dispersion stability in the coating, can influence the mechanical property of the coating, and needs to be modified by adding a surfactant to coat the surface of the preservative in order to weaken the van der waals force and enhance the stability of the coating. The applicant has found that when the weight ratio of surfactant to preservative is 1: (0.01-0.05), the antibacterial and antiviral performance of the obtained material is best, and presumably, the surfactant can be uniformly coated on the surface of the antibacterial agent under the condition of optimal mixing ratio of the surfactant and the antibacterial agent, so that the friction force in motion is reduced, the viscosity is reduced, the stability and the mechanical property of the coating are improved, and the coating achieves the long-acting and stable antibacterial and antiviral efficacy. When the usage amount of the surfactant is small, the surface coating is incomplete, and the effect of combining the antibacterial agent and the surfactant is not achieved; when the usage amount of the surfactant exceeds the optimal usage amount, more than one layer of the surfactant may be coated on the surface of the antibacterial agent, so that a phenomenon of multi-layer coating is caused, the preservative is changed from hydrophobicity to hydrophilicity and is not easy to dissolve in the coating, and the friction force of the antibacterial agent is increased, so that the viscosity is increased, and the stability of the coating is not facilitated.

As a preferred embodiment, the weight ratio of the antibacterial agent to the PVC plate substrate is 1: (10-30).

The weight ratio of the antibacterial agent to the PVC plate base material is 1: (10-30) the building board has better antibacterial and antiviral properties, and the antibacterial agent has better slow release property and can keep a longer antibacterial effect. When the weight parts of the antibacterial agent and the PVC plate base material are not in the optimal weight part range, the antibacterial agent can agglomerate, the granularity of the antibacterial agent is increased, the specific surface area is reduced, the antibacterial and antiviral effects of the antibacterial agent are reduced, the mechanical property of the PVC building plate is reduced due to excessive use of the antibacterial agent, and the service time of the plate is shortened.

As a preferred embodiment, the preparation raw materials also comprise a coating base material, wherein the coating base material is epoxy resin and the weight portion is 10-30 portions.

In a second aspect, the present invention provides a method for preparing a building board containing inorganic metal ions, comprising the steps of:

(1) adding metal oxide and inorganic porous material into deionized water, mixing, stirring at constant temperature of 80-100 deg.C for 2-3h, oven drying, and grinding to obtain antibacterial agent powder;

(2) adding the plate base material, the plasticizer and the antibacterial agent powder into a high-speed stirrer according to the parts by weight, mixing and stirring, then adding the mixture into an internal mixer for mixing, wherein the mixing temperature is 110-145 ℃, adding the mixture into an open mill for plastication after mixing, and then pressing the mixture into sheets through two calenders;

(3) mixing a surfactant, a preservative and a coating base material, stirring in a high-speed mixer, and mixing and stirring for 1-2 hours to obtain the antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 30-60min at the temperature of 30-45 ℃ to finish the preparation.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the starting materials used are all commercially available, unless otherwise specified.

Example 1

A building board containing inorganic metal ions is prepared from the following raw materials in parts by weight: 55 parts of PVC sheet base material, 15 parts of dibutyl phthalate, 2.5 parts of zeolite, 1.48 parts of nano silver oxide, 1 part of zinc oxide, 0.1 part of potassium sorbate, 4 parts of sodium dodecyl benzene sulfonate and 20 parts of epoxy resin.

The PVC board substrate is purchased from Sichuan plastic Co Ltd, and has the model of PA 66-101L.

The epoxy resin is purchased from ba ling petrochemical company ltd, and has a CAS number of 388-19-7.

The zeolite was purchased from Xinyang heavy-duty mining material plants.

A method for preparing a building board containing inorganic metal ions comprises the following steps: the preparation method comprises the following steps of (by weight portion),

(1) adding nano silver oxide, zinc oxide and zeolite into deionized water, mixing, stirring at 90 ℃ for 2.5h, performing suction filtration, washing, drying and grinding to obtain antibacterial agent powder;

(2) adding the PVC plate base material, dibutyl phthalate and the antibacterial agent powder obtained in the step one into a high-speed stirrer according to the weight part, mixing and stirring, then adding the mixture into an internal mixer for mixing, wherein the mixing temperature is 125 ℃, adding the mixture into an open mill for plastication after mixing, and then pressing the mixture into sheets through two calenders;

(3) mixing sodium dodecyl benzene sulfonate and potassium sorbate, adding the mixture into epoxy resin, stirring the mixture in a high-speed mixer at a high speed for 1.5 hours to prepare an antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 45min at 40 ℃ to finish the preparation.

Example 2

A building board containing inorganic metal ions is prepared from the following raw materials in parts by weight: 50 parts of PVC plate base material, 10 parts of epoxy fatty acid methyl ester, 1 part of tobermorite, 0.5 part of nano zinc oxide, 0.725 part of titanium dioxide, 0.06 part of dodecyl trimethyl ammonium chloride, 6 parts of sodium sulfonate and 10 parts of epoxy resin.

The PVC board substrate is purchased from Sichuan plastic Co Ltd, and has the model of PA 66-101L.

The epoxy resin is purchased from ba ling petrochemical company ltd, and has a CAS number of 388-19-7.

The tobermorite was purchased from west asia chemical technology ltd.

A method for preparing a building board containing inorganic metal ions comprises the following steps: the preparation method comprises the following steps of (by weight portion),

(1) adding nano zinc oxide, titanium dioxide and tobermorite into deionized water, mixing, stirring for 3h at 80 ℃, performing suction filtration, washing, drying and grinding to obtain antibacterial agent powder;

(2) adding the PVC plate base material, epoxy fatty acid methyl ester and the antibacterial agent powder obtained in the step one into a high-speed stirrer according to parts by weight, mixing and stirring, then adding into an internal mixer for mixing, wherein the mixing temperature is 120 ℃, adding into an open mill for plastication after mixing, and then pressing into sheets through two calenders;

(3) mixing sodium sulfonate and dodecyl trimethyl ammonium chloride, adding into epoxy resin, stirring at high speed in a high-speed mixer for 1h to obtain antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 60min at the temperature of 30 ℃ to finish the preparation.

Example 3

A building board containing inorganic metal ions is prepared from the following raw materials in parts by weight: 60 parts of PVC plate base material, 20 parts of dipentaerythritol ester, 1.5 parts of shell powder, 1 part of nano silver oxide, 0.69 part of copper oxide, 0.8 part of ethylene oxide, 8 parts of sodium stearate and 30 parts of epoxy resin.

The PVC board substrate is purchased from Sichuan plastic Co Ltd, and has the model of PA 66-101L.

The epoxy resin is purchased from ba ling petrochemical company ltd, and has a CAS number of 388-19-7.

The shell powder is purchased from Xinxin oyster shell factories.

A method for preparing a building board containing inorganic metal ions comprises the following steps: the preparation method comprises the following steps of (by weight portion),

(1) adding nano silver oxide, copper oxide and shell powder into deionized water, mixing, stirring for 2h at 100 ℃, performing suction filtration, washing, drying and grinding to obtain antibacterial agent powder;

(2) adding the PVC plate base material, dipentaerythritol ester and the antibacterial agent powder obtained in the first step into a high-speed stirrer according to parts by weight, mixing and stirring, then adding the mixture into an internal mixer for mixing, wherein the mixing temperature is 140 ℃, and after mixing, adding the mixture into an open mill for plastication, and then pressing the mixture into sheets through two calenders;

(3) mixing sodium stearate and ethylene oxide, adding into epoxy resin, stirring at high speed in a high-speed mixer for 1h to obtain the antibacterial coating;

(4) and (4) coating the prepared antibacterial coating on the upper surface and the lower surface of the sheet prepared in the step (II), and baking for 30min at 45 ℃ to finish the preparation.

Comparative example 1

The building board containing inorganic metal ions and the preparation method thereof have the same specific steps as example 1, and are different from the specific steps of 2.5 parts of nano silver and 0 part of zinc oxide.

Comparative example 2:

the specific steps of a building board containing inorganic metal ions are the same as example 1, except that 5 parts of zinc oxide is used.

Comparative example 3:

the specific steps of a building board containing inorganic metal ions are the same as example 1, except that 1 part of potassium sorbate is used.

And (3) performance testing:

1. and (3) testing antibacterial performance: the test was carried out according to the GB/T31402-2015 standard.

2. And (3) testing the mildew resistance grade: the test is carried out according to the GB/T24128-2009 standard.

3. And (3) testing antiviral performance: the test was carried out according to ISO21702-2019 standard.

The examples and comparative examples were tested according to the above criteria and the results are shown in table 1.

TABLE 1