阅读说明：本技术 一种钙锌稳定剂及其在spc地板基材生产中的应用 (Calcium-zinc stabilizer and application thereof in SPC floor base material production ) 是由 徐吉军 刘森林 董峰 于 2021-10-09 设计创作，主要内容包括：本发明涉及SPC地板技术领域,具体涉及一种钙锌稳定剂及其在SPC地板基材生产中的应用。原料以质量份数计包括,硬脂酸60～80份、纳米氧化锌5～8份、硬脂酸钙2～5份、水滑石2～4份、单甘脂5～10份、聚乙烯蜡5～10份、季戊四醇2～5份、轻质碳酸钙5～10份。本发明提供的钙锌稳定剂具有润滑性能高、塑化速度快等优点,大大降低了加工助剂的使用量,同时,在SPC地板基材加工过程高效稳定、节能降耗、产能提升。(The invention relates to the technical field of SPC floors, in particular to a calcium-zinc stabilizer and application thereof in SPC floor substrate production. The raw materials comprise, by mass, 60-80 parts of stearic acid, 5-8 parts of nano zinc oxide, 2-5 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of monoglyceride, 5-10 parts of polyethylene wax, 2-5 parts of pentaerythritol and 5-10 parts of light calcium carbonate. The calcium-zinc stabilizer provided by the invention has the advantages of high lubricating property, high plasticizing speed and the like, greatly reduces the using amount of a processing aid, and meanwhile, is efficient and stable in the SPC floor base material processing process, saves energy, reduces consumption and improves the productivity.)

1. The calcium-zinc stabilizer is characterized by comprising, by mass, 60-80 parts of stearic acid, 5-8 parts of nano zinc oxide, 2-5 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of monoglyceride, 5-10 parts of polyethylene wax, 2-5 parts of pentaerythritol and 5-10 parts of hydrotalcite.

2. The calcium zinc stabilizer according to claim 1, which comprises 1 to 2 parts of a mildewcide;

or, 1-5 parts of ultraviolet resistant absorbent.

3. A process for preparing the Ca-Zn stabilizer according to claim 1, which comprises melting stearic acid, adding nano zinc oxide, reacting, adding calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol and light calcium carbonate, and stirring.

4. The method for preparing the calcium zinc stabilizer according to claim 3, wherein the reaction temperature is 115-120 ℃;

or heating stearic acid to 70-75 ℃, heating to 115-120 ℃ to completely melt, and then adding nano zinc oxide to react.

5. The method for preparing a calcium-zinc stabilizer according to claim 3, wherein the calcium stearate, the hydrotalcite, the monoglyceride, the polyethylene wax, the pentaerythritol, and the light calcium carbonate are added, and then the mixture is heated to 120 to 130 ℃ and stirred.

6. The method for preparing a calcium-zinc stabilizer according to claim 3, wherein the calcium stearate, the hydrotalcite, the monoglyceride, the polyethylene wax, the pentaerythritol and the light calcium carbonate are added and stirred uniformly, and then the mildew preventive and/or the ultraviolet-resistant absorbent are added and stirred uniformly.

7. Use of a calcium zinc stabilizer according to claim 1 or 2 in the production of SPC floor substrates.

8. An SPC floor substrate is characterized by comprising, by mass, 50 parts of PVC, 150-175 parts of calcium powder, 30-50 parts of a return material, 4-5 parts of a stabilizer, 1.7-2.0 parts of a lubricant and 2-3.5 parts of a processing aid; wherein the stabilizer is the calcium zinc stabilizer.

9. An SPC floor substrate according to claim 8, wherein the lubricants are an internal lubricant and an external lubricant; preferably, the mass ratio of the inner lubricant to the outer lubricant is 0.7-0.8: 1.0-1.2.

10. An SPC flooring substrate as claimed in claim 8, wherein the processing aids comprise a plasticizer and an impact modifier.

Technical Field

The invention relates to the technical field of SPC floors, in particular to a calcium-zinc stabilizer and application thereof in SPC floor substrate production.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

SPC (SPC) stone Plastic composite floor is a novel environment-friendly floor newly developed in recent years, and has the characteristics of no formaldehyde, mildew resistance, moisture resistance, fire resistance, insect resistance, simplicity in installation, recycling and the like. The main raw material of the SPC floor is polyvinyl chloride resin, an SPC base material is extruded by combining an extruder with a T-shaped die, and a PVC wear-resistant layer, a PVC color film and the SPC base material are respectively heated, laminated and embossed at one time by using a three-roll or four-roll calender, so that the SPC floor is completely produced without using glue in the production process.

The production of SPC substrates is a key process for stone plastic flooring. The production formula mainly comprises: polyvinyl chloride resin, natural calcium powder, a calcium zinc stabilizer, a lubricant, a processing aid and the like, wherein the calcium zinc stabilizer is a key raw material in the production process. Because PVC processing defect is not high temperature resistance, hydrogen chloride gas is released in the heating extrusion process, and the small molecule gas can cause the violent decomposition of PVC to influence each physical property of PVC, in order to reduce the decomposition of PVC, a proper amount of stabilizer is usually added in the processing process to overcome the decomposition of PVC resin. Most of the traditional stabilizers are lead salt stabilizers, and because the contained heavy metals such as lead, cadmium and the like are harmful to the environment and human bodies, the traditional stabilizers are forbidden or replaced gradually. The calcium zinc stabilizer is used as an environment-friendly product and is widely accepted and used more and more, and with the continuous progress of the technology in recent years and the continuous improvement of the cost performance, the calcium zinc stabilizer can replace a lead salt stabilizer in the manufacture of a whole series of products. However, the inventors have found through practical production that the existing calcium zinc stabilizers have a problem of poor plasticizing ability, and thus more processing aids are required to be added to increase the plasticizing ability of SPC substrate preparation.

Disclosure of Invention

In order to solve the defects of the prior art, the invention aims to provide a calcium-zinc stabilizer and application thereof in SPC floor base material production.

In order to achieve the purpose, the technical scheme of the invention is as follows:

on the one hand, the calcium-zinc stabilizer comprises, by mass, 60-80 parts of stearic acid, 5-8 parts of nano zinc oxide, 2-5 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of monoglyceride, 5-10 parts of polyethylene wax, 2-5 parts of pentaerythritol and 5-10 parts of hydrotalcite.

The nano zinc oxide is used for reacting with partial stearic acid to generate zinc stearate, and is used for ensuring the initial coloring of the product; the calcium stearate is used for long-term heat resistance and plasticizing promotion; the monoglyceride and the polyethylene wax play a role in internal and external lubrication, and the hydrotalcite mainly plays a role in prolonging heat resistance in the whole processing process; in conclusion, zinc stearate ensures initial coloring, calcium stearate promotes plasticization, monoglyceride solves friction between material molecules, PE wax solves friction between materials and a charging barrel screw and a die, and hydrotalcite plays a role in inhibiting PVC decomposition. The light calcium carbonate has the functions of promoting plasticization and reducing density in the using process.

On the other hand, the preparation method of the calcium-zinc stabilizer comprises the steps of melting stearic acid, adding nano zinc oxide for reaction, adding calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol and light calcium carbonate, and uniformly stirring to obtain the calcium-zinc stabilizer.

In a third aspect, the use of a calcium zinc stabilizer as described above in the production of SPC flooring substrates.

The SPC floor base material comprises, by mass, 50 parts of PVC, 150-175 parts of calcium powder, 30-50 parts of return materials, 4-5 parts of stabilizing agents, 1.7-2.0 parts of lubricating agents and 2-3.5 parts of processing aids; wherein the stabilizer is the calcium zinc stabilizer.

The invention has the beneficial effects that:

1. the calcium-zinc stabilizer provided by the invention has the advantages of excellent thermal stability, long thermal stability time, good initial coloring, large lubrication, suitability for preparation of SPC floor base materials with high calcium powder adding proportion, and great reduction of production instability behaviors such as mold removal and machine halt.

2. The calcium zinc stabilizer provided by the invention has the advantages that the plasticization is more thorough in the process of preparing the SPC floor base material, the product quality is more excellent, the production temperature can be effectively reduced, the possibility of high-temperature paste is prevented, the extrusion speed is faster, the possibility of adjustment is provided, the production efficiency is improved, and the production cost is reduced.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

FIG. 1 shows the results of rheological measurements of the Ca-Zn stabilizer prepared in example 1 of the present invention, wherein a is the temperature curve of the Ca-Zn stabilizer of example 1, b is the temperature curve of the commercially available Ca-Zn stabilizer, c is the torque curve of the Ca-Zn stabilizer of example 1, and d is the torque curve of the commercially available Ca-Zn stabilizer;

FIG. 2 is a photograph of a sample block of example 1 of the present invention after rheology, wherein a is the calcium zinc stabilizer of example 1 and b is a commercially available calcium zinc stabilizer;

FIG. 3 is a picture of Congo red test of example 1 according to the present invention performed for 25 minutes, wherein a is the Ca-Zn stabilizer prepared in example 1 and b is a commercially available Ca-Zn stabilizer;

FIG. 4 is a 35 minute picture of Congo red test of example 1 of the present invention, wherein a is the Ca-Zn stabilizer prepared in example 1 and b is the commercially available Ca-Zn stabilizer.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

In the production process of SPC floor base materials, calcium powder needs to be added as much as possible in order to reduce the cost, and the calcium powder is increased, so that the processing and production are difficult. In order to solve the problem, the invention researches a plurality of commercially available calcium zinc stabilizers, however, the existing commercially available calcium zinc stabilizers used for producing SPC floor base materials have the problem of excessive addition of processing aids. In view of the problem of poor plasticizing capacity of the conventional calcium-zinc stabilizer, the invention provides a calcium-zinc stabilizer and application thereof in SPC floor substrate production.

The invention provides a calcium-zinc stabilizer, which comprises, by mass, 60-80 parts of stearic acid, 5-8 parts of nano-zinc oxide, 2-5 parts of calcium stearate, 2-4 parts of hydrotalcite, 5-10 parts of monoglyceride, 5-10 parts of polyethylene wax, 2-5 parts of pentaerythritol and 5-10 parts of light calcium carbonate.

In some examples of this embodiment, the mildew inhibitor is 1-2 parts.

Some examples of this embodiment include 1-5 parts of the UV absorber.

The invention also provides a preparation method of the calcium zinc stabilizer, which comprises the steps of melting stearic acid, adding nano zinc oxide for reaction, adding calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol and light calcium carbonate, and uniformly stirring to obtain the calcium zinc stabilizer.

In some examples of this embodiment, the reaction temperature is 115-120 ℃.

In some examples of the embodiment, stearic acid is heated to 70-75 ℃, then heated to 115-120 ℃ to be completely melted, and then added with nano zinc oxide for reaction.

In some examples of this embodiment, calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol, and precipitated calcium carbonate are added, and then the mixture is heated to 120 to 130 ℃, followed by stirring.

In some examples of this embodiment, the calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol, and light calcium carbonate are added and stirred uniformly, and then the anti-mildew agent and/or the anti-uv absorber are added and stirred uniformly.

The preferred preparation method of the invention comprises the following steps:

1. and (3) starting steam, preheating the reaction kettle to 70-75 ℃, and keeping the temperature for 20-40 minutes to ensure that the temperature of the reaction kettle is uniform.

2. And opening the stirrer, slowly adding stearic acid, stirring and slowly dissolving, heating to 115-120 ℃ for complete melting, adding zinc oxide, stirring and reacting for 20-40 minutes, and finishing the reaction.

3. Heating to 120-130 ℃ (ensuring that the calcium stearate is melted), adding calcium stearate, hydrotalcite, monoglyceride, polyethylene wax, pentaerythritol and light calcium carbonate in sequence, and stirring for 20-40 minutes (keeping at 120-130 ℃).

4. Adding the mildew preventive and the ultraviolet-resistant absorbent and stirring (keeping the temperature at 120-130 ℃) for 10-20 minutes.

5. Discharging the materials, cooling by a double-roller tablet press, and tabletting.

In a third embodiment of the present invention, there is provided a use of the above calcium zinc stabilizer in the production of SPC floor substrates.

The invention provides a fourth embodiment of the invention, which provides an SPC floor substrate, wherein the raw materials comprise, by mass, 50 parts of PVC, 150-175 parts of calcium powder, 30-50 parts of a return material, 4-5 parts of a stabilizer, 1.7-2.0 parts of a lubricant and 2-3.5 parts of a processing aid; wherein the stabilizer is the calcium zinc stabilizer.

In some examples of this embodiment, the lubricant is an internal lubricant and an external lubricant. The internal lubricant includes G60, etc. The external lubricant includes PE wax and the like. The mass optimal ratio of the internal lubricant to the external lubricant is 0.7-0.8: 1.0-1.2.

In some embodiments of this embodiment, the processing aid comprises a plasticizer and an impact modifier. Preferably a mixture of chlorinated polyvinyl chloride (abbreviated as CPE) and ACR resin (abbreviated as ACR). CPE not only can be used as a plasticizer, but also can be mutually fused with PVC, and has phase separation phenomenon, and the CPE is in a plastic alloy state containing elastomer particles after mixing, so that the impact resistance of the PVC is improved. The mechanical property of the SPC floor base material can be improved after the CPE is matched with the ACR.

In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.

Example 1

The preparation method of the calcium-zinc stabilizer comprises the following steps:

1. and starting steam, preheating the reaction kettle to 70 ℃, and keeping the temperature for 30 minutes to ensure that the temperature of the reaction kettle is uniform.

2. And opening the stirrer, slowly adding 70 parts by mass of stearic acid, stirring and slowly dissolving, heating to 115 ℃ for full melting, adding 6 parts by mass of nano zinc oxide, stirring and reacting for 30 minutes, and finishing the reaction.

3. 4 parts by mass of calcium stearate, 3 parts by mass of hydrotalcite, 8 parts by mass of monoglyceride, 7 parts by mass of polyethylene wax, 3 parts by mass of pentaerythritol, and 6 parts by mass of light calcium carbonate were successively added, and stirred for 30 minutes (held at 125 ℃).

4. Adding 1 part by mass of mildew preventive and 3 parts by mass of ultraviolet-resistant absorbent and stirring for 15 minutes.

5. Discharging the materials, performing tabletting molding by a double-roller cooling tabletting machine to obtain the calcium zinc stabilizer.

The calcium-zinc stabilizer prepared in this example and a commercially available calcium-zinc stabilizer were tested by a happ rheometer, and the test conditions and the test results are shown in table 1 and table 2, respectively. Among them, the commercially available calcium-zinc stabilizer is the one having the best plasticizing effect selected by examination of a plurality of commercially available calcium-zinc stabilizers (CZ-4, hereinafter, commercially available calcium-zinc stabilizers are all the commercially available calcium-zinc stabilizers).

TABLE 1 examination conditions

TABLE 2 test results

The result shows that the calcium-zinc stabilizer provided by the embodiment is plasticized more quickly, so that during production, the plasticized state can be achieved more easily, a solid foundation is laid for realizing production at a lower temperature, and a bedding is laid for stably starting up for a long time.

The photo of the sample block after the rheology is shown in fig. 2, the calcium zinc stabilizer prepared in this example has better plasticization, more round appearance, unchanged blocking color and long thermal stability time, while the calcium zinc stabilizer sold in the market has poor molding and plasticizing performance and has no plasticizing effect.

Congo red experiments were performed on the calcium zinc stabilizer prepared in this example and a commercially available calcium zinc stabilizer under the following experimental conditions: 50 g of PVC and 2.5 g of calcium zinc stabilizer are subjected to oil bath at the constant temperature of 200 ℃.

At 25 minutes, the test material of the commercial calcium zinc stabilizer discolored and decomposed, and the congo red test paper discolored, as shown in fig. 3. At 35 minutes, the test charge of the Ca-Zn stabilizer prepared in this example discolored and decomposed, as shown in FIG. 4. The stability of the calcium zinc stabilizer prepared in this example is demonstrated by the current commercial calcium zinc stabilizer.

The raw materials for the preparation of SPC flooring substrates using this example are shown in Table 3.

TABLE 3 raw material tables (parts by mass)

The calcium zinc stabilizer adopted by the SPC floor base material 1 is a commercially available calcium zinc stabilizer, and the calcium zinc stabilizer adopted by the SPC floor base material 2 is the calcium zinc stabilizer prepared in this example.

The mechanical properties of the SPC floor base material prepared by the method are as follows:

the results show that the calcium zinc stabilizer prepared in this example can greatly reduce the addition amount of the processing aid (CPE + ACR).

Example 2

The preparation method of the calcium-zinc stabilizer comprises the following steps:

1. and starting steam, preheating the reaction kettle to 75 ℃, and keeping the temperature for 30 minutes to ensure that the temperature of the reaction kettle is uniform.

2. And opening the stirrer, slowly adding 80 parts by mass of stearic acid, stirring and slowly dissolving, heating to 120 ℃ for full melting, adding 8 parts by mass of nano zinc oxide, stirring and reacting for 30 minutes, and finishing the reaction.

3.5 parts by mass of calcium stearate, 4 parts by mass of hydrotalcite, 5 parts by mass of monoglyceride, 6 parts by mass of polyethylene wax, 2 parts by mass of pentaerythritol, and 6 parts by mass of light calcium carbonate were successively added, and stirred for 30 minutes (kept at 130 ℃).

4. Adding 2 parts by mass of mildew preventive and 4 parts by mass of ultraviolet-resistant absorbent and stirring for 15 minutes.

5. Discharging the materials, performing tabletting molding by a double-roller cooling tabletting machine to obtain the calcium zinc stabilizer.

Example 3

The preparation method of the calcium-zinc stabilizer comprises the following steps:

1. and starting steam, preheating the reaction kettle to 72 ℃, and keeping the temperature for 30 minutes to ensure that the temperature of the reaction kettle is uniform.

2. And opening the stirrer, slowly adding 60 parts by mass of stearic acid, stirring and slowly dissolving, heating to 115 ℃ for full melting, adding 5 parts by mass of nano zinc oxide, stirring and reacting for 30 minutes, and finishing the reaction.

3. 2 parts by mass of calcium stearate, 2 parts by mass of hydrotalcite, 10 parts by mass of monoglyceride, 10 parts by mass of polyethylene wax, 5 parts by mass of pentaerythritol, and 9 parts by mass of light calcium carbonate were successively added, and stirred for 30 minutes (kept at 130 ℃).

4. Adding 1 part by mass of mildew preventive and 5 parts by mass of ultraviolet-resistant absorbent and stirring for 15 minutes.

5. Discharging the materials, performing tabletting molding by a double-roller cooling tabletting machine to obtain the calcium zinc stabilizer.

The properties of the calcium zinc stabilizers prepared in examples 2-3 are similar to those of the calcium zinc stabilizer prepared in example 1.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.