Artificial quartz stone plate and preparation method thereof

Abstract

The application discloses artificial quartz stone plate and a preparation method thereof. The artificial quartz stone plate comprises the following components: 10-25 parts of unsaturated polyester resin, 70-80 parts of quartz sand, 0.2-0.4 parts of a coupling agent, 0.1-0.15 parts of a curing agent, 0.5-0.9 parts of an accelerator, 0.5-2 parts of pigments and 3-10 parts of a composite antibacterial agent. The composite antibacterial agent is an organic antibacterial agent, which has excellent compatibility with the resin matrix material, can improve the mechanical properties of the quartz stone material, and on the other hand, the curing agent is added in batches, so that the suspended double bonds in the resin matrix and the composite antibacterial agent can fully contact and react, the molecular stability of the resin matrix and the composite antibacterial agent is further improved, and the quartz stone can have long-acting antibacterial ability and improved mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of quartz stone plate, in particular to a kind of artificial quartz stone plate and preparation method thereof. BACKGROUND

[0002] Quartz stone countertop is usually composed of more than 90% quartz sand and about 10% resin. Quartz sand provides hardness, and resin plays a bonding role and provides toughness. Because quartz stone has high hardness and high density, its surface hardness can reach Mohs hardness 6, close to diamond hardness, much higher than knives and other sharp tools used in the kitchen. Therefore, even if a hard object scratches the countertop, the countertop is not easily scratched and leaves marks.

[0003] Quartz stone countertops have a wide variety of colors and beautiful appearance, with good decorative properties. The pigments of quartz stone are mainly mineral materials, which have strong anti-fading ability. It is difficult to observe color changes with the naked eye after years of local contrast under strong sunlight. Basically, it can be considered as a non-fading material. In addition, it has excellent resistance to penetration, and it is not easy to appear yellow discoloration. Home countertops are objects that we must contact and use every day in our daily life, and they occupy a considerable area, such as kitchen countertops, washbasin, tea table, dining table, window sill, etc. Home countertops have both decorative properties and bearing functions, and their antibacterial cleaning is crucial to the indoor healthy environment.

[0004] Generally speaking, there are mainly two kinds of bacteria in the room, namely bacteria and fungi. If the home countertop is easy to absorb water, has many holes and gaps, and the stains are not cleaned in time, it is easy to breed pathogenic bacteria. Fungi, also known as mold, grow easily in water-accumulating countertops, which not only harms human health, but also affects the appearance and service life of the countertop; therefore, the antibacterial property of home countertops mainly needs to inhibit the breeding of bacteria and mold. At present, countertops mainly have quartz stone, natural marble and stainless steel. As we all know, natural marble has many holes and gaps, which is easy to hide dirt; stainless steel countertops are easy to scratch and have uneven holes, which makes cleaning difficult and leads to the breeding of bacteria. Artificial quartz stone countertops have incomparable advantages in antibacterial properties. There are existing technologies to give quartz stone antibacterial properties, such as CN111875294B discloses an antibacterial and mildew-proof quartz stone and a preparation method thereof. The technology can make the quartz stone have good antibacterial effect (antibacterial rate greater than 99%) and mildew-proof effect by adding a small amount of zirconium phosphate loaded with silver and zinc composite antibacterial agent (for example, the addition ratio is 0.125%), which helps to save costs and does not affect the physical properties of the quartz stone. However, the compatibility of the zirconium phosphate loaded with silver and zinc composite antibacterial agent and the system in the technology is poor, resulting in a complex preparation process and no improvement in the mechanical properties of the artificial quartz stone plate. Therefore, it is of great significance to provide an artificial quartz stone plate with excellent antibacterial properties and excellent mechanical properties. SUMMARY

[0005] The present application aims to provide a kind of artificial quartz plate and its preparation method, the quartz plate prepared by the present application has excellent antibacterial performance while its mechanical property is excellent, it has important significance to be applied in the field of home countertop.

[0006] One purpose of the present application is to provide a kind of artificial quartz plate, which is characterized by comprising the following components: unsaturated polyester resin 10-25 parts; Quartz sand 70-80 parts; Coupling agent 0.2-0.4 parts; Curing agent 0.1-0.15 parts; Promoter 0.5-0.9 parts; Pigment 0.5-2 parts; Composite antibacterial agent 3-10 parts.

[0007] Further, the unsaturated polyester resin is a combination of one or more of epoxy resin, phenolic resin or polyurethane.

[0008] Further, the quartz sand is composed of quartz sand 6-8 mesh, quartz sand 8-16 mesh, quartz sand 24-40 mesh and quartz sand 40-70 mesh, and the ratio of the above four particle sizes is 3:4:4:16.

[0009] Further, the coupling agent in the present application is selected from at least one of γ-aminopropyl triethoxysilane, vinyl triethoxysilane or vinyl trimethoxysilane.

[0010] Further, the curing agent in the present application is selected from one or more of tert-butyl peroxy(2-ethylhexanoate), methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide or fatty polyamine. The curing agent added in the present application is used to promote the curing of unsaturated polyester resin on the one hand, and on the other hand, it can be used as an initiator for the secondary initiation of double bonds suspended in the composite antibacterial agent, which can promote the further crosslinking of unsaturated polyester resin and composite antibacterial agent.

[0011] Further, the promoter in the present application is one or several of triethanolamine, hexenyl bis-stearamide or stannous octoate.

[0012] Further, the pigment in the present application is a combination of one or both of iron yellow and iron red;

[0013] Further, the preparation method of the composite antibacterial agent in the present application is as follows:

[0014] 1) adding triallyl isocyanurate, acrylic acid, divinyl benzene with a mass ratio of 1:(2-4):1 into polyvinyl alcohol aqueous solution, adding a 5% sodium chloride solution, mixing uniformly, adding a solution of toluene and liquid wax with a ratio of 2:3 as a pore-forming agent, stirring at a speed of 300 r / min, increasing the temperature of the system to 45℃ and keeping for 1 hour, adding azobisdimethylvaleronitrile, and reacting at a temperature of 50-53℃ under stirring for 2-3 hours.

[0015] 2) naturally cooling the product after the reaction of step 1) to room temperature, adding into ethanol, centrifuging, washing and drying the precipitate to obtain a low-crosslinked polymer;

[0016] 3) dispersing the low-crosslinked polymer obtained in step 2) into a silver nitrate solution, stirring and adsorbing for 1-1.5 hours, centrifuging, and drying the precipitate to obtain a composite antibacterial agent.

[0017] In the present application, toluene and liquid wax are used as pore-forming agents. After the polymerization starts, the generated polymer chains are dissolved in the mixed system composed of monomers and pore-forming agents. When the polymer chains gradually increase, they are separated from the mixed system, and phase separation occurs. The initially separated polymers form microgel nuclei, and the microgel nuclei aggregate into microspheres. With the continuous polymerization reaction, the microgel nuclei and the microspheres are connected together, and the presence of poor solvents is finally retained in the pores between the nuclei and the microspheres. When the pore-forming agents are removed, the space left is the pore. In the present application, the combination of good solvents and poor solvents makes the polymer pore size and uniformity excellent. On the one hand, the appropriate pore size is conducive to the loading of silver ions, and on the other hand, the uniform distribution of the pore structure can adsorb organic matter and silver ions, which is conducive to the bacteriostatic effect of silver ions.

[0018] In the present application, azobisdimethylvaleronitrile is used. On the one hand, azobisdimethylvaleronitrile has a low initiation temperature and high initiation efficiency, which can make the crosslinking reaction proceed rapidly and form more short-chain structures of the polymer. On the other hand, with the increase of the crosslinking reaction rate, more suspended double bonds exist in the crosslinked material due to the steric hindrance of the polymer and other reasons in the polymerization process, which is conducive to the subsequent reaction with unsaturated resins, improves the bonding ability of the composite antibacterial agent and the resin matrix, and further improves the long-acting antibacterial ability of the antibacterial agent.

[0019] Another object of the present application is to provide a preparation method of artificial quartz stone slabs, which comprises the following steps:

[0020] 1) mixing the composite antibacterial agent and one-third of the curing agent and toluene according to the above ratio, swelling sufficiently to obtain a swollen composite antibacterial agent;

[0021] 2) mixing the swelling composite antibacterial agent, unsaturated polyester resin and quartz sand, coupling agent, accelerator, pigment and remaining curing agent obtained in step 1) according to the aforementioned proportion;

[0022] 3) cloth to the mold, form loose blank;

[0023] 4) vibration pressing;

[0024] 5) curing, obtaining artificial stone plate finished product.

[0025] The present application mixes and swells the composite antibacterial agent and the curing agent in toluene in advance before preparing artificial quartz stone, since the composite antibacterial agent has formed a slightly crosslinked structure during preparation, part of the unreacted double bonds are hidden inside the crosslinked structure, the present application uses toluene to pre-swelling the composite antibacterial agent, which can make the suspended double bond fully exposed, facilitate the full contact of the composite antibacterial agent and the curing agent, in the subsequent heating and curing process, the suspended double bond in the composite antibacterial agent will further crosslink under the action of the curing agent, the bacteriostatic agent is grafted into the resin matrix, giving the artificial quartz stone more long-acting antibacterial effect.

[0026] The beneficial effects of the present application are:

[0027] 1、The present application polymerizes divinylbenzene, acrylic acid and crosslinking agent, and simultaneously adds compounded solvent in the system, so that the obtained matrix material has microporous structure, the microporous structure has appropriate pore size and uniform distribution, can adsorb organic matter and bacteria, in addition, since a specific type of crosslinking agent is selected, the molecular chain is long, the bacteriostatic agent molecular chain has a certain flexibility, can play the role of matrix resin in addition to the antibacterial effect, can give the quartz stone plate excellent mechanical properties.

[0028] 2、The present application uses the above-mentioned material as the matrix, loads silver ions in the matrix material, gives the matrix material antibacterial properties, in addition, since the matrix material has the adsorption capacity of the microporous structure, the combination between the matrix material and the silver ions can be strengthened, the release time of the silver ions is prolonged, the antibacterial agent has long-lasting antibacterial properties.

[0029] 3、The base material is formed by free radical polymerization between polystyrene and acrylic acid and a crosslinking agent, due to the increase in the reaction steric hindrance of the molecular chain in the free radical polymerization process, a part of the double bonds in the base material is not completely reacted, in the preparation process of the quartz stone, the composite antibacterial agent and part of the curing agent are pre-swollen in the solvent, then the resin and the curing agent are added, under the action of the curing agent, the double bonds which are not completely reacted are secondarily initiated, and then participate in the crosslinking reaction of the resin, that is, the composite antibacterial agent is combined into the resin matrix, and the remaining suspended double bonds of the antibacterial agent are consumed, which can further improve the stability of the composite antibacterial agent, and can give the quartz stone plate more durable antibacterial performance. DETAILED DESCRIPTION

[0030] The embodiments of the present application are described in detail below, the following examples are exemplary, and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0031] In addition, the terms "first", "second" are only for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined with "first", "second" can explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "a plurality of" is at least two, such as two, three, etc., unless otherwise specifically limited.

[0032] It should be noted that the composite antibacterial agent in the embodiments of the present application is prepared by the following method: triallyl isocyanurate, acrylic acid and divinylbenzene with a mass ratio of 1:(2-4):1 are added to a polyvinyl alcohol aqueous solution, and a 5% mass concentration sodium chloride solution is added, then a solution of toluene and liquid wax with a ratio of 2:3 is added as a pore former, stirring at a speed of 300 r / min, the system temperature is raised to 45 DEG C for 1 hour, azobisdimethyl isopropyl cyanide is added, and the reaction is carried out at a temperature of 50-53 DEG C under stirring conditions for 2-3 h. The product is naturally cooled to room temperature, added to ethanol, centrifuged, washed and dried, and a low crosslinked polymer is obtained; the low crosslinked polymer is dispersed into a silver nitrate solution, stirred and adsorbed for 1-1.5 h, then centrifuged, and the precipitate is dried to obtain the composite antibacterial agent.

[0033] Example 1

[0034] An artificial quartz stone plate, the raw materials of which include the following components in parts by weight: unsaturated polyester resin 10 parts; quartz sand 80 parts; gamma-aminopropyl triethoxysilane 0.2 parts; dibenzoyl peroxide 0.1 parts; hexenyl bis-stearamide 0.5 parts; iron yellow 0.5 parts; composite antibacterial agent 8.7 parts. The quartz sand includes particle sizes of 6-8 mesh, 8-16 mesh, 24-40 mesh and 40-70 mesh in a ratio of 3:4:4:16.

[0035] The artificial quartz plate is made by the following process: the composite antibacterial agent and one third of the curing agent and toluene are mixed according to the above-mentioned proportion, and the composite antibacterial agent is fully swelled; the swelled composite antibacterial agent, the unsaturated polyester resin, the quartz sand, the coupling agent, the accelerator, the pigment and the remaining curing agent are mixed according to the above-mentioned proportion; the mixed material is laid into a mold to form a loose blank; the loose blank is vibrated and pressed to obtain a compact blank; and the compact blank is heated and cured to obtain the artificial quartz plate product.

[0036] Example 2

[0037] An artificial quartz plate, the raw materials of which include the following components in parts by weight: unsaturated polyester resin 15 parts; quartz sand 78 parts; tert-butyl peroxy(2-ethylhexanoate) 0.3 parts; dibenzoyl peroxide 0.15 parts; triethanolamine 0.8 parts; iron yellow 1 part; and composite antibacterial agent 4.75 parts. The quartz sand includes particle sizes of 6-8 mesh, 8-16 mesh, 24-40 mesh and 40-70 mesh in a proportion of 3:4:4:16.

[0038] The artificial quartz plate is made by the following process: the composite antibacterial agent and one third of the curing agent and toluene are mixed according to the above-mentioned proportion, and the composite antibacterial agent is fully swelled; the swelled composite antibacterial agent, the unsaturated polyester resin, the quartz sand, the coupling agent, the accelerator, the pigment and the remaining curing agent are mixed according to the above-mentioned proportion; the mixed material is laid into a mold to form a loose blank; the loose blank is vibrated and pressed to obtain a compact blank; and the compact blank is heated and cured to obtain the artificial quartz plate product.

[0039] Example 3

[0040] An artificial quartz plate, the raw materials of which include the following components in parts by weight: unsaturated polyester resin 20 parts; quartz sand 75 parts; vinyl trimethoxysilane 0.4 parts; dibenzoyl peroxide 0.1 parts; hexenyl bis-stearamide 0.5 parts; iron red 1 part; and composite antibacterial agent 3 parts. The quartz sand includes particle sizes of 6-8 mesh, 8-16 mesh, 24-40 mesh and 40-70 mesh in a proportion of 3:4:4:16.

[0041] The artificial quartz plate is made by the following process: the composite antibacterial agent and one third of the curing agent and toluene are mixed according to the above-mentioned proportion, and the composite antibacterial agent is fully swelled; the swelled composite antibacterial agent, the unsaturated polyester resin, the quartz sand, the coupling agent, the accelerator, the pigment and the remaining curing agent are mixed according to the above-mentioned proportion; the mixed material is laid into a mold to form a loose blank; the loose blank is vibrated and pressed to obtain a compact blank; and the compact blank is heated and cured to obtain the artificial quartz plate product.

[0042] Example 4

[0043] The artificial quartz stone plate is prepared from the following components in parts by weight: 10 parts of unsaturated polyester resin; 80 parts of quartz sand; 0.3 parts of gamma-aminopropyl triethoxysilane; 0.15 parts of dibenzoyl peroxide; 0.5 parts of hexenyl bis-stearamide; 0.5 parts of iron yellow; and 9.55 parts of composite antibacterial agent. The quartz sand includes particles with sizes of 6-8 mesh, 8-16 mesh, 24-40 mesh and 40-70 mesh in a ratio of 3:4:4:16.

[0044] The artificial quartz stone plate is prepared from the following components in parts by weight: 10 parts of unsaturated polyester resin; 80 parts of quartz sand; 0.3 parts of gamma-aminopropyl triethoxysilane; 0.15 parts of dibenzoyl peroxide; 0.5 parts of hexenyl bis-stearamide; 0.5 parts of iron yellow; and 9.55 parts of composite antibacterial agent. The quartz sand includes particles with sizes of 6-8 mesh, 8-16 mesh, 24-40 mesh and 40-70 mesh in a ratio of 3:4:4:16.

[0045] Characterization of antibacterial performance of the quartz stone plates prepared in Examples 1-4

[0046] The antibacterial performance is tested according to the Standard Test Method for Determining the Antibacterial Activity of Antimicrobial Agents in Polymeric or Hydrophobic Materials, ASTM E2180-2012. The comparative example in the table is a quartz stone plate without the addition of antibacterial agent, and the other parameters are the same as those in Example 1. The results are shown in Table 1.

[0047] Table 1 Characterization of antibacterial performance of the quartz stone plates prepared in Examples 1-4

[0048]

[0049]

[0050] It can be seen from the antibacterial performance characterization test that the quartz stone plates prepared in Examples 1-4 have excellent antibacterial performance. With the increase of the composite antibacterial agent, the antibacterial performance is improved to a certain extent, and the 48h antibacterial rate is about 98%, which has a long-lasting antibacterial performance. This is due to the special structure of the composite antibacterial agent in the present application. On the one hand, the porous structure simultaneously loads silver ions, so that the antibacterial agent has excellent antibacterial performance. On the other hand, the interface reaction between the composite antibacterial agent and the resin matrix improves the stability of the composite antibacterial agent in the system, and the migration and precipitation of the antibacterial agent are not easy, thereby having excellent long-acting antibacterial performance.

[0051] Mechanical property characterization of artificial quartz stone prepared in examples 1-4: it should be noted that the mechanical properties of the artificial quartz stone plate described in the present application are tested according to the method for testing synthetic stone in GBT35160.2-2017, and the Mohs hardness is measured by a Mohs hardness tester, and the results are shown in table 2:

[0052] Table 2 mechanical property characterization of artificial quartz stone prepared in examples 1-4

[0053]

[0054] From the mechanical property characterization data, it can be seen that the mechanical properties of the quartz stone prepared in examples 1-4 are excellent, on the one hand, the composite antibacterial agent used in the present application is an organic antibacterial agent, which has excellent compatibility with the resin matrix material, and can improve the mechanical properties of the quartz stone material, on the other hand, the curing agent is added in batches in the present application, which can make the double bonds in the resin matrix and the composite antibacterial agent fully contact and react, further improve the molecular stability of the resin matrix and the composite antibacterial agent, and make the quartz stone have excellent long-acting antibacterial ability and its mechanical properties are also improved.

[0055] It is obvious for those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, from any point of view, the examples should be regarded as exemplary and non-limiting, the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

Claims

1. An artificial quartz slab, characterized by The composition comprises the following components: unsaturated polyester resin 10-25 parts, quartz sand 70-80 parts, coupling agent 0.2-0.4 parts, curing agent 0.1-0.15 parts, accelerator 0.5-0.9 parts, pigment 0.5-2 parts, and composite antibacterial agent 3-10 parts; The preparation method of the composite antibacterial agent is as follows: 1) triallyl isocyanurate, acrylic acid, and divinylbenzene with a mass ratio of 1:(2-4):1 are added into a polyvinyl alcohol aqueous solution, a 5% sodium chloride solution is added, and the mixture is uniformly mixed, then a solution of toluene: liquid wax with a ratio of 2:3 is added as a pore-forming agent, stirring is carried out at a speed of 300 r / min, the system temperature is raised to 45℃ and kept for 1 hour, azobisdimethylvaleronitrile is added, and the temperature is raised to 50-53℃, and the reaction is carried out under stirring for 2-3 hours; 2) the product after the reaction in step 1) is naturally cooled to room temperature, added into ethanol, centrifuged, and the precipitate is washed and dried to obtain a low-crosslinked polymer; 3) the low-crosslinked polymer obtained in step 2) is dispersed into a silver nitrate solution, stirred and adsorbed for 1-1.5 hours, centrifuged, and the precipitate is dried to obtain the composite antibacterial agent.

2. The artificial quartz slab of claim 1, wherein, The unsaturated polyester resin is a combination of one or more of epoxy resin, phenolic resin, or polyurethane.

3. The artificial quartz slab of claim 1, wherein, The quartz sand is composed of four particle sizes of quartz sand 6-8 mesh, quartz sand 8-16 mesh, quartz sand 24-40 mesh, and quartz sand 40-70 mesh, and the ratio of the above four particle sizes of quartz sand is 3:4:4:

16.

4. The artificial quartz slab of claim 1, wherein, The coupling agent is selected from at least one of γ-aminopropyl triethoxysilane, vinyl triethoxysilane, or vinyl trimethoxysilane.

5. The artificial quartz slab of claim 1, wherein, The curing agent is selected from one or more of tert-butyl peroxy(2-ethylhexanoate), methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, dibenzoyl peroxide, or fatty polyamine.

6. The artificial quartz slab of claim 1, wherein, The accelerator is one or more of triethanolamine, hexenyl bis-stearamide, or stannous octoate.

7. The artificial quartz slab of claim 1, wherein, The pigment is a combination of one or both of iron yellow and iron red.

8. A method of producing the quartz stone slab according to any one of claims 1 to 7, characterized in that The method comprises the following steps: 1) the composite antibacterial agent, one-third of the curing agent, and toluene are mixed according to the above ratio, and the composite antibacterial agent is fully swelled to obtain a swelled composite antibacterial agent; 2) the swelled composite antibacterial agent obtained in step 1), the unsaturated polyester resin, and the quartz sand, coupling agent, accelerator, pigment, and the remaining curing agent are mixed according to the above ratio; 3) the mixture is laid into a mold to form a loose blank; 4) the blank is vibrated and pressed; 5) the blank is cured to obtain a finished artificial stone plate.

9. The method of claim 8, wherein, The amount of toluene in step 1) is determined according to the amount sufficient to swell the composite antibacterial agent.

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