CN106283877A - Polrvinyl chloride wallpaper with non-woven paper as base material of high flame retardant and preparation method thereof - Google Patents

Abstract

The invention discloses a highly flame-retardant polyvinyl chloride wallpaper with non-woven paper as the base material, which comprises a base material and a coating slurry, the base material is non-woven paper, and the coating slurry is PVC The paste, the coating dosage is 100-140g/m ² ; the PVC paste includes the following components: polyvinyl chloride resin PVC; liquid plasticizer cresyl diphenyl phosphate CDP; ammonium polyphosphate APP. The invention uses non-woven paper as the base material, uses lower-priced ammonium polyphosphate APP as the inorganic flame retardant, and uses cresyl diphenyl phosphate CDP as the liquid plasticizer to prepare low-cost, high-flame-retardant, PVC wallpaper based on non-woven paper with high smoke suppression and high mechanical properties.

Description

High flame-retardant polyvinyl chloride wallpaper based on non-woven paper and preparation method thereof

technical field

The invention relates to the field of wallpaper, in particular to a highly flame-retardant polyvinyl chloride wallpaper with non-woven paper as a base material and a preparation method thereof.

Background technique

China is the world's largest producer and consumer of wallpaper products, and the total sales of wallpaper products account for 29% of the world's consumption. Wallpaper products mainly include two categories: polyvinyl chloride wallpaper based on plant fiber paper and polyvinyl chloride wallpaper based on non-woven paper. In recent years, polyvinyl chloride wallpaper based on non-woven paper has become more and more popular among consumers due to its high mechanical strength and good corrosion resistance. In 2014, the domestic sales of PVC wallpaper based on non-woven paper increased by 58.8%, accounting for 47.9% of all wallpaper product sales, becoming one of the most important wallpaper products in my country. The national standard GB 8624-2012, which came into effect on October ₁ , 2013, stipulates that the combustion performance level of wallpaper products must reach B1 level, that is, the limiting oxygen index is ≥32. The limiting oxygen index of traditional polyvinyl chloride wallpaper products based on plant fiber paper is only about 21, which is a flammable material. The same is true for the polyvinyl chloride wallpaper based on non-woven paper that has emerged in recent years, which seriously threatens the safety of people's lives and property in a fire. Therefore, the research and development of flame-retardant polyvinyl chloride wallpaper based on non-woven paper that meets national standards is of great significance to the fire prevention, fire extinguishing and safe evacuation of interior wall decoration materials, as well as to increase the added value of wallpaper products. .

There are few reports on the flame retardant modification of PVC wallpaper based on non-woven paper. The flame retardant modification of traditional plant fiber paper-based PVC wallpaper mainly includes the flame retardant modification of paper-based materials and the flame retardant modification of polyvinyl chloride. Yang Shousheng mentioned in the paper "Development of Flame Retardant Base Paper for Wallpaper" published in the journal "New Building Materials" (2005, (7): 31-33) that using sepiolite, chlorinated paraffin, antimony trioxide and The plant fiber wallpaper base paper with certain flame retardant effect was prepared by mixing raw pulp and beating paper, but the product did not meet the national standard GB ^18585-2001 .

Contents of the invention

In order to solve the above-mentioned problems of high cost and insufficient flame retardant performance of the existing wallpaper, the present invention provides a non-woven paper-based polyester wallpaper with low cost and high flame retardant performance meeting the requirements of the national standard GB 8624-2012. Vinyl chloride wallpaper and its preparation method.

For this reason, inventor provides following technical scheme:

High flame-retardant polyvinyl chloride wallpaper based on non-woven paper, which includes a base material and a coating slurry, the base material is non-woven paper, and the coating slurry is polyvinyl chloride PVC paste , the coating dosage is 100-140g/m ² ; the polyvinyl chloride PVC paste includes the following components in parts by weight:

Polyvinyl chloride resin PVC 80-120 parts;

40-60 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 4.5-18 parts.

Preferably, the PVC paste of the present invention comprises the following components in parts by weight:

Polyvinyl chloride resin PVC 90-110 parts;

45-55 parts of liquid plasticizer toluene diphenyl phosphate CDP;

Ammonium polyphosphate APP 6-10 parts.

More preferably, the PVC paste of the present invention comprises the following components in parts by weight:

100 parts of polyvinyl chloride resin PVC;

50 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 7.5 parts.

Further, the PVC paste of the present invention also includes the following components in parts by weight:

The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion.

The invention also discloses a method for preparing a highly flame-retardant polyvinyl chloride wallpaper with non-woven paper as the base material, which includes the following steps:

Step 1: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 2: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain a PVC paste;

Step 3: apply the PVC paste on the surface of the non-woven paper base material by rotary screen printing, solidify and shape after drying, and obtain the non-woven paper-based polyvinyl chloride wallpaper with high flame retardancy.

Further, the preparation method of the high flame-retardant polyvinyl chloride wallpaper based on non-woven paper according to the present invention specifically includes the following steps:

Step 1: Add polyvinyl chloride resin PVC, auxiliary plasticizer epoxy soybean oil ESO, potassium-zinc composite heat stabilizer, viscosity reducer D40 solvent oil to the liquid plasticizer cresyl diphenyl phosphate CDP, and stir at high speed Obtain PVC premix after mixing;

Step 2: Add ammonium polyphosphate APP, titanium dioxide TiO ₂ , foaming agent azodicarbonamide ADC, and foaming aid zinc oxide ZnO to the PVC premix, and stir and mix at high speed to obtain PVC paste;

Step 3: apply the PVC paste on the surface of the non-woven paper base material by rotary screen printing, foam molding after drying, and obtain the non-woven paper-based polyvinyl chloride wallpaper with high flame retardancy;

Wherein, the parts by weight of each auxiliary material component are:

The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion.

Preferably, in the step 3, the mesh of the rotary screen is 50-100 mesh.

Preferably, in the step 3, after the PVC paste is coated on the surface of the non-woven paper substrate by rotary screen printing, it is dried at 180-250° C. for 0.5-1.5 min to solidify and form.

The invention uses non-woven paper as the base material, adds inorganic flame retardant ammonium polyphosphate APP and flame-retardant plasticizer cresyl diphenyl phosphate CDP to polyvinyl chloride resin to prepare polychloride with non-woven paper as the base material. vinyl wallpaper. Because the inorganic flame retardant ammonium polyphosphate APP can improve the flame retardancy and thermal stability of PVC wallpaper, and the plasticizer cresyl diphenyl phosphate CDP can help improve the flame retardancy of PVC wallpaper, and the two The cost of raw materials is relatively low, therefore, the non-woven paper-based polyvinyl chloride wallpaper prepared by the present invention has low cost, high flame retardancy, high smoke suppression and high mechanical properties.

The limit oxygen index of the polyvinyl chloride wallpaper based on non-woven paper prepared by the invention can reach 33.8 after flame-retardant modification, which is 57.2% higher than that of the prior art; the maximum smoke density is 9.8%, which is 9.8% higher than that of the prior art. The reduction is 35.1%; the transverse and longitudinal wet tensile strengths reach 1.21 and 1.24kN·m ^-1 respectively, which are 7.1% and 7.8% higher than the prior art. The polyvinyl chloride wallpaper prepared with the non-woven paper as the base material meets the flame-retardant requirement of B1-grade material limit oxygen index ≥ 32 in the national standard GB 8624-2012.

Description of drawings

Below in conjunction with accompanying drawing and specific embodiment the present invention will be described in further detail:

Fig. 1 is the detection result figure of the limit oxygen index value of the polyvinyl chloride wallpaper with non-woven paper as base material prepared with reference to Examples 1-16;

Fig. 2 is the thermogravimetric analysis chart of three kinds of inorganic flame retardants;

Fig. 3 is the thermogravimetric analysis figure of the polyvinyl chloride wallpaper that does not add ammonium polyphosphate APP and adds the polyvinyl chloride wallpaper that adds ammonium polyphosphate APP to non-woven paper as base material;

Fig. 4 is the simulated combustion test comparison chart of polyvinyl chloride wallpaper with non-woven paper as the base material prepared without adding ammonium polyphosphate APP and adding ammonium polyphosphate APP (A is the polyvinyl chloride wallpaper without adding flame retardant ; B is the polyvinyl chloride wallpaper with 5% APP added);

Fig. 5 is a comparison chart of the detection results of the limiting oxygen index value of polyvinyl chloride wallpaper based on non-woven paper prepared with reference to Examples 17-19 and Example 1 of the present invention;

Fig. 6 is that two kinds of liquid plasticizers dioctyl phthalate DOP and cresyl diphenyl phosphate CDP carry out thermogravimetric analysis figure;

Fig. 7 is a comparison diagram of the smoke density measurement of polyvinyl chloride wallpaper with non-woven paper as the base material prepared by referring to Example 17 and Example 1 of the present invention;

Fig. 8 is a graph showing the detection results of the limiting oxygen index of the polyvinyl chloride wallpaper with non-woven paper as the base material prepared in Examples 2-6 of the present invention.

detailed description

In order to describe in detail the technical content, structural features, achieved objectives and effects of the present invention, the following will be described in detail in conjunction with the embodiments.

High flame-retardant polyvinyl chloride wallpaper based on non-woven paper, which includes a base material and a coating slurry, the base material is non-woven paper, the coating slurry is PVC paste, the The coating dosage is 100-140g/m ² ; the PVC paste includes the following components in parts by weight:

Polyvinyl chloride resin PVC 80-120 parts;

40-60 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 4.5-18 parts.

The invention also discloses a method for preparing a highly flame-retardant polyvinyl chloride wallpaper with non-woven paper as the base material, which includes the following steps:

Step 1: take each component by formula;

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste on the surface of the non-woven paper substrate by 50-100 mesh rotary screen printing, the coating amount is 100-140g/m ² , dry at 180-250°C for 0.5-1.5min to solidify molding to obtain the high flame-retardant polyvinyl chloride wallpaper with non-woven paper as the base material.

In the prior art, the polyvinyl chloride wallpaper based on non-woven paper generally adopts Al(OH) ₃ and Mg(OH) ₂ as inorganic flame retardants; adopts dioctyl phthalate DOP as liquid plasticizer . In order to better illustrate the non-woven paper-based polyvinyl chloride wallpaper prepared by the present invention, the following reference examples are performed according to the prior art. Referring to Examples 1-5, only adding inorganic flame retardant Al(OH) ₃ prepares polyvinyl chloride wallpaper with non-woven paper as the base material. Reference examples 6-10 are only adding inorganic flame retardant Mg (OH) ₂ Preparation of polyvinyl chloride wallpaper with non-woven paper as the base material; Reference examples 11-15 are only adding inorganic flame retardant ammonium polyphosphate APP Preparation of polyvinyl chloride wallpaper based on non-woven paper; reference example 16 is to prepare polyvinyl chloride wallpaper based on non-woven paper without adding any inorganic flame retardant. Reference Example 17 is to use dioctyl phthalate DOP as a liquid plasticizer, and no inorganic flame retardant ammonium polyphosphate APP is added to prepare polyvinyl chloride wallpaper with non-woven paper as the base material; Reference Example 18 is Polyvinyl chloride wallpaper based on non-woven paper was prepared by using dioctyl phthalate DOP as liquid plasticizer and adding inorganic flame retardant ammonium polyphosphate APP. Reference Example 19 is to use cresyl diphenyl phosphate CDP as a liquid plasticizer without adding the inorganic flame retardant ammonium polyphosphate APP to prepare polyvinyl chloride wallpaper with non-woven paper as the base material.

Referring to Example 1

Step 1: take each component by formula;

100 parts of polyvinyl chloride resin PVC;

Dioctyl phthalate DOP 50 parts;

Inorganic flame retardant Al(OH) ₃ 7.5 parts;

Step 2: adding polyvinyl chloride paste resin PVC into dioctyl phthalate DOP, and stirring at a speed of 400 r/min to obtain a PVC premix;

Step 3: Add inorganic flame retardant Al(OH) ₃ to the PVC premix, and then stir at a speed of 1000r/min until evenly stirred to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Referring to Example 2-5

With reference to Examples 2-5, adjust the addition of the inorganic flame retardant Al(OH) ₃ , and all the other operations are the same as in Reference Example 1. In the reference example 2, the addition of the inorganic flame retardant Al (OH) ₃ is 1% of the PVC premix weight, which is 1.5 parts; in the reference example 3, the addition of the inorganic flame retardant Al (OH) ₃ Be 3% of PVC premix weight, be 4.5 parts; Referring to Example 4, the addition of inorganic flame retardant Al (OH) is ₈ % of PVC premix weight, be 12 parts; Referring to Example 5 Among them, the addition of inorganic flame retardant Al (OH) ₃ is 10% of the PVC premix weight, is 15 parts.

Referring to Example 6

Step 1: take each component by formula;

100 parts of polyvinyl chloride resin PVC;

Dioctyl phthalate DOP 50 parts;

Inorganic flame retardant Mg(OH) ₂ 7.5 parts;

Step 2: adding polyvinyl chloride paste resin PVC into dioctyl phthalate DOP, and stirring at a speed of 400 r/min to obtain a PVC premix;

Step 3: Add inorganic flame retardant Mg(OH) ₂ to the PVC premix, and then stir at a speed of 1000r/min until evenly stirred to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Referring to Examples 7-10

Referring to Examples 7-10 to adjust the addition of inorganic flame retardant Mg (OH) ₂ , all the other operations are the same as in Reference Example 6. With reference to Example 7, the addition of inorganic flame retardant Mg (OH) ₂ is 1% of the PVC premix weight, which is 1.5 parts; in reference to Example 8, the addition of inorganic flame retardant Mg (OH) ₂ It is 3% of the PVC premix weight, which is 4.5 parts; with reference to Example 9, the addition of inorganic flame retardant Mg(OH) is ₈ % of the PVC premix weight, which is 12 parts; with reference to Example 10 Among them, the addition of inorganic flame retardant Mg(OH) ₂ is 10% of the PVC premix weight, which is 15 parts.

Referring to Example 11

Step 1: take each component by formula;

100 parts of polyvinyl chloride resin PVC;

7.5 parts of inorganic flame retardant ammonium polyphosphate APP;

Dioctyl phthalate DOP 50 parts;

Step 2: adding polyvinyl chloride paste resin PVC into dioctyl phthalate DOP, and stirring at a speed of 400 r/min to obtain a PVC premix;

Step 3: Add inorganic flame retardant ammonium polyphosphate APP to the PVC premix, and then stir at a speed of 1000r/min until evenly stirred to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Referring to Example 12-15

Refer to Examples 12-15 to adjust the addition amount of the inorganic flame retardant ammonium polyphosphate APP, and the rest of the operations are the same as in Reference Example 11. In the reference example 12, the addition of the inorganic flame retardant ammonium polyphosphate APP is 1% of the weight of the PVC premix, which is 1.5 parts; in the reference example 13, the addition of the inorganic flame retardant ammonium polyphosphate APP It is 3% of the weight of the PVC premix, which is 4.5 parts; referring to Example 14, the addition of the inorganic flame retardant ammonium polyphosphate APP is 8% of the weight of the PVC premix, which is 12 parts; referring to Example 15 Among them, the addition amount of the inorganic flame retardant ammonium polyphosphate APP is 10% of the weight of the PVC premix, which is 15 parts.

Referring to Example 16

Step 1: Weigh the components according to the formula:

100 parts of polyvinyl chloride resin PVC;

Dioctyl phthalate DOP 50 parts;

Heavy calcium carbonate CaCO ₃ 55 parts;

Step 2: Add polyvinyl chloride paste resin PVC to dioctyl phthalate DOP, and stir at a speed of 400 r/min to obtain a PVC premix.

Step 3: Add heavy calcium carbonate CaCO ₃ to the PVC premix, and stir at a speed of 1000 r/min until the PVC paste is evenly stirred to obtain PVC paste.

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

The limit oxygen index values were detected for the polyvinyl chloride wallpaper based on non-woven paper prepared in the above reference examples 1-16. Among them, the determination method of the limiting oxygen index value refers to the combustion sample of the non-self-supporting material (Class V) standard in the national standard GB/T2406.2-2009, and the JF-3 oxygen index measuring instrument is used to measure the combustion of the 80mm sample The minimum oxygen concentration required. Three parallel tests were carried out for each sample, and the average value was taken as the limiting oxygen index value of the sample. All limit oxygen index value detection tests of the present invention adopt this method.

See Figure 1 for the testing results of the limiting oxygen index of the polyvinyl chloride wallpaper based on non-woven paper prepared with reference to Examples 1-16. It can be seen from Figure 1 that the polyvinyl chloride wallpaper with non-woven paper as the base material prepared by referring to Example 16 was prepared without adding the inorganic flame retardant ammonium polyphosphate APP and the liquid plasticizer toluene diphenyl phosphate CDP before modification. The limiting oxygen index of the material is only 21.5, which is far lower than the requirement of the national standard GB 8624-2012 that the limiting oxygen index _of B1 grade materials is ≥ 32. With the continuous increase of the addition of the three inorganic flame retardants Al(OH) ₃ , Mg(OH) ₂ and ammonium polyphosphate APP, the limiting oxygen index of the prepared PVC wallpaper based on non-woven paper was average. Upward trend. When the addition of ammonium polyphosphate APP reached 10%, the limiting oxygen index of the prepared polyvinyl chloride wallpaper based on non-woven paper reached 27.3, which was 27.0% higher than that before modification. The limiting oxygen index of polyvinyl chloride wallpaper modified by adding ammonium polyphosphate APP is always higher than that of polyvinyl chloride wallpaper modified by adding Al(OH) ₃ and Mg(OH) ₂ . This shows that the present invention can better improve the flame retardancy of polyvinyl chloride wallpaper by adding ammonium polyphosphate APP. When the addition of ammonium polyphosphate APP exceeds 5%, the limit oxygen index of the polyvinyl chloride wallpaper does not increase significantly. Therefore, from the perspective of cost, the addition of ammonium polyphosphate APP is preferably 5%.

Three kinds of inorganic flame retardants Al(OH) ₃ , Mg(OH) ₂ and ammonium polyphosphate APP were analyzed by thermogravimetric analysis. The specific analysis method is: use the STA449F3 thermogravimetric analyzer (Germany Netzsch Instrument Manufacturing Co., Ltd.) to test the thermal mass loss of the three inorganic flame retardants. The test atmosphere is oxygen, the reference substance is Al ₂ O ₃ , the temperature rise range is 25-800°C, the temperature rise rate is 10°C·min ^-1 , and the temperature at which the mass loss of PVC wallpaper reaches 1% after heat treatment is taken as the initial heat decomposition temperature. All thermogravimetric analysis tests of the present invention all adopt this method.

The thermogravimetric analysis results of inorganic flame retardants Al(OH) ₃ , Mg(OH) ₂ and ammonium polyphosphate APP are shown in Figure 2. It can be seen from Figure 2 that the initial thermal decomposition temperatures of Al(OH) ₃ , Mg(OH) ₂ and ammonium polyphosphate APP are 227, 200 and 250°C, respectively, and the thermal stability of ammonium polyphosphate APP is the best. The flame retardant mechanism of Al(OH) ₃ and Mg(OH) ₂ is similar. It starts to pyrolyze after 200°C, and gradually loses crystal water to become metal oxides Al ₂ O ₃ and MgO. At the same time, the released water vapor can play a role The function of diluting oxygen and absorbing the radiant energy in the flame reduces the flame temperature on the surface of PVC and slows down the pyrolysis speed of PVC. Ammonium polyphosphate APP begins to lose weight rapidly after 250°C, and releases a large amount of CO ₂ and NH ₃ gases. These gases are not easy to burn and can play a role in isolating O ₂ . As the temperature rises further, ammonium polyphosphate APP gradually pyrolyzes to generate P ₂ O ₅ and P ₂ O ₃ , covering the surface of PVC to form a physical insulation layer. The heat insulation layer can inhibit the generation of flammable gas, and can also prevent further oxidation and thermal decomposition of PVC.

Using the same thermogravimetric analysis method as above to modify the polyvinyl chloride wallpaper without adding ammonium polyphosphate APP in reference example 16 and the non-woven paper based on non-woven paper prepared by adding ammonium polyphosphate APP in reference example 11 The polyvinyl chloride wallpaper was analyzed by thermogravimetric analysis, and the analysis results are shown in Figure 3.

It can be seen from Figure 3 that the thermal weight loss process of PVC wallpaper based on non-woven paper can be divided into two stages. The first stage is 220-300°C, the thermal weight loss rate is faster, this stage shows the reaction of rapid mass reduction after PVC removes HCl; the second stage is 300-800°C, the thermal weight loss rate is slower, this stage is PVC Changes in the structure of conjugated polyenes and the combustion decomposition process of carbon-containing compounds. Referring to Example 11, after modification by adding 5% ammonium polyphosphate APP, the thermal decomposition rate of the polyvinyl chloride wallpaper after 250° C. is always lower than that of the material before modification. The temperature of this demarcation point is consistent with the initial decomposition temperature of ammonium polyphosphate APP, indicating that the thermal decomposition of ammonium polyphosphate APP improves the thermal stability of polyvinyl chloride wallpaper based on non-woven paper.

The polyvinyl chloride wallpaper based on non-woven paper modified with reference to Example 16 without adding ammonium polyphosphate APP and the polyvinyl chloride wallpaper based on non-woven paper prepared in Reference Example 11 were simulated combustion According to the test, the photos of the external appearance of the reference example 16 and reference example 11 after simulating combustion at 300°C for 1-6 minutes are shown in Fig. 4 . The specific test method is as follows: cut the prepared polyvinyl chloride wallpaper into a square with a side length of 2 cm, put it into a SX2-5-12 box-type resistance furnace (Shanghai Boxun Industrial Co., Ltd. Medical Equipment Factory) for simulated combustion at different times, and observe The appearance of the material after simulated combustion. The atmosphere in the furnace is air, the temperature is set at 300°C, and the simulated combustion time is 1-6min.

As can be seen from Fig. 4, the polyvinyl chloride wallpaper with non-woven paper as the base material before modification in reference to Example 16 has obvious surface carbonization phenomenon after simulating combustion for 2 minutes; as time increases, the polyvinyl chloride wallpaper surface The carbonization became more and more obvious; the PVC wallpaper began to show serious curling phenomenon after 5 minutes of simulated burning. With reference to Example 11, after adding 5% ammonium polyphosphate APP modified polyvinyl chloride wallpaper with non-woven paper as the base material, obvious surface carbonization occurs after 4 minutes of simulated combustion; Good dimensional stability was maintained within 6 min. This shows that the addition of ammonium polyphosphate APP of the present invention can delay the carbonization time of the surface of polyvinyl chloride wallpaper, thereby improving the dimensional stability, thermal stability and flame retardancy of polyvinyl chloride wallpaper based on non-woven paper.

Referring to Example 17

Step 1: Weigh each component according to the formula:

100 parts of polyvinyl chloride resin PVC;

Liquid plasticizer dioctyl phthalate DOP 50 parts;

Heavy calcium carbonate CaCO ₃ 55 parts;

Step 2: adding polyvinyl chloride resin PVC to dioctyl phthalate DOP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding heavy calcium carbonate CaCO ₃ into the PVC premix, stirring and mixing at a high speed to obtain the PVC paste;

Step 3: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Referring to Example 18

Step 1: Weigh each component according to the formula:

100 parts of polyvinyl chloride resin PVC;

Liquid plasticizer dioctyl phthalate DOP 50 parts;

7.5 parts of ammonium polyphosphate APP;

Step 2: adding polyvinyl chloride resin PVC to dioctyl phthalate DOP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Referring to Example 19

Step 1: Weigh each component according to the formula:

100 parts of polyvinyl chloride resin PVC;

50 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Heavy calcium carbonate CaCO ₃ 55 parts;

Step 2: adding polyvinyl chloride resin PVC to cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding heavy calcium carbonate CaCO ₃ into the PVC premix, stirring and mixing at a high speed to obtain the PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

The preparation method of the non-woven paper-based polyvinyl chloride wallpaper with high flame retardancy of the present invention

Example 1

Step 1: Weigh each component according to the formula:

100 parts of polyvinyl chloride resin PVC;

50 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

7.5 parts of ammonium polyphosphate APP;

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Reference examples 17-19 are respectively using dioctyl phthalate DOP or cresyl diphenyl phosphate CDP as liquid plasticizers, without adding inorganic flame retardants or adding 5% ammonium polyphosphate APP to prepare non-woven paper For polyvinyl chloride wallpaper as the base material, when no inorganic flame retardant is added, filler ground calcium carbonate CaCO ₃ is added to the components to make the polyvinyl chloride wallpaper solidify and form. The polyvinyl chloride wallpaper with non-woven paper as the base material prepared in reference examples 17-19 and example 1 of the present invention was tested for limiting oxygen index values, and the specific test results are shown in FIG. 5 .

It can be seen from Figure 5 that the limiting oxygen index of the polyvinyl chloride wallpaper based on non-woven paper prepared in Example 19 using cresyl diphenyl phosphate CDP as a liquid plasticizer without adding a flame retardant can reach 27.0, Compared with reference example 17, the polyvinyl chloride wallpaper based on non-woven paper prepared with DOP as plasticizer and without adding inorganic flame retardants increased by 25.6%; Example 1 of the present invention further added 5% ammonium polyphosphate After APP, the limit oxygen index of the prepared polyvinyl chloride wallpaper based on non-woven paper can reach 33.8, which is 57.2% higher than that of reference example 16, and meets the limit oxygen index _of B1 grade materials in the national standard GB 8624-2012 Flame retardant requirements with an index ≥ 32. This shows that the present invention can improve the flame retardancy of polyvinyl chloride wallpaper with cresyl diphenyl phosphate CDP as liquid plasticizer, meanwhile, cresyl diphenyl phosphate CDP can cooperate with ammonium polyphosphate APP to further improve the flame retardancy of polyvinyl chloride wallpaper. Flammability. This is because cresyl diphenyl phosphate CDP can generate polymetaphosphoric acid products when it is burned. This product is in a viscous liquid film covering the surface of unburned polyvinyl chloride wallpaper, and can carbonize PVC into a solid film at the same time. All forms of film can prevent PVC from contacting with _O2 , thus playing a flame retardant effect.

The thermogravimetric analysis of two liquid plasticizers, dioctyl phthalate DOP or cresyl diphenyl phosphate CDP, is shown in Figure 6 for specific analysis results. It can be seen from Figure 6 that the initial decomposition temperatures of DOP and CDP are 167 and 240°C, respectively; the thermal weight loss curves of the two liquid accelerators start to separate at 167°C, and in the subsequent heating process, the thermal stability of CDP is better than that of DOP. This is because DOP contains an ester group, and the "C-O bond" in it has poor thermal stability and is easily broken after being heated, resulting in the pyrolysis of DOP. Therefore, the non-woven paper-based polyvinyl chloride wallpaper prepared with CDP as a liquid plasticizer has better flame retardancy than the non-woven paper-based polyvinyl chloride wallpaper prepared with DOP as a plasticizer. .

In the prior art, the polyvinyl chloride wallpaper prepared with non-woven paper as the base material will emit a large amount of black smoke when burning, which will cause great harm to the life safety of the masses in the fire scene and on-site evacuation and rescue. Adding an appropriate amount of inorganic flame retardants to PVC can usually play a dual role in flame retardancy and smoke elimination. The polyvinyl chloride wallpaper based on non-woven paper prepared by referring to Example 17 using DOP as a plasticizer without adding an inorganic flame retardant, and the polyvinyl chloride wallpaper based on non-woven paper prepared in Example 1 of the present invention Vinyl chloride wallpaper for the determination of smoke density. The specific operation is as follows: with reference to the national standard GB/T 8627-2007, use the JCY-1 building material smoke density tester (Jiangning District Analytical Instrument Factory, Nanjing City) to measure the smoke production of the prepared polyvinyl chloride wallpaper static combustion, The smoke density measured every 15s for each group of 3 samples is drawn as a line graph. The change of smoke density during the combustion process of the sample can be reflected from the figure, and the specific results are shown in Figure 7.

It can be seen from Fig. 7 that the polyvinyl chloride wallpaper with non-woven paper as the base material prepared by adding 5% ammonium polyphosphate APP to CDP as the liquid plasticizer in Example 1 of the present invention has a maximum smoke density of 9.8%, which is higher than Referring to Example 17, the traditional material with DOP as the plasticizer and no inorganic flame retardant was reduced by 35.1%. After the flame-retardant modification, the smoke density of the prepared non-woven paper-based PVC wallpaper was lower than that before the modification throughout the combustion process. This shows that the non-woven paper-based polyvinyl chloride wallpaper prepared by the present invention has reduced smoke generation after flame-retardant modification and has better smoke-eliminating properties.

Adding inorganic flame retardants to polyvinyl chloride wallpaper based on non-woven paper must be based on the premise of not reducing its mechanical properties. The polyvinyl chloride wallpaper based on non-woven paper prepared by referring to Example 17 using DOP as a plasticizer without adding an inorganic flame retardant, and the polyvinyl chloride wallpaper based on non-woven paper prepared in Example 1 of the present invention Vinyl chloride wallpaper was tested for wet tensile strength. The specific measurement method is: refer to the light industry standard QB/T 4034-2010 to cut the tensile sample of the PVC wallpaper produced, soak the sample in ultrapure water for 5 minutes, take out the sample and dry the water with filter paper. Using DCP-KZ(W)300 computer-controlled horizontal tensile testing machine (Sichuan Changjiang Paper Instrument Co., Ltd.) to measure the wet tensile strength of the specimen in the transverse and longitudinal directions. Each sample was tested 10 times in parallel, and the average value was taken as the transverse and longitudinal wet tensile strength values of the sample. The test results are shown in Table 1.

As can be seen from Table 1, Example 1 of the present invention uses CDP as a plasticizer and adds 5% ammonium polyphosphate APP to prepare polyvinyl chloride wallpaper with non-woven paper as the base material. The reference example 17 has increased by 7.1% and 7.8%. Under the action of tensile stress, PVC will have stress concentration in some weak places, resulting in local plastic deformation, so that fine grooves or cracks are produced on the surface or inside of the PVC wallpaper perpendicular to the stress direction, which is called "Silver streak" phenomenon. Adding an appropriate amount of inorganic powder to PVC can improve this undesirable phenomenon, thereby improving the mechanical properties of PVC wallpaper based on non-woven paper. It can also be seen from Table 1 that the longitudinal wet tensile strength of the polyvinyl chloride wallpaper based on non-woven paper prepared in reference to Example 17 and Example 1 of the present invention is greater than the transverse wet tensile strength. This is because the substrate of the polyvinyl chloride wallpaper prepared in the present invention is non-woven paper, and its wet tensile strength in the longitudinal direction is greater than that in the transverse direction. Therefore, the difference in the transverse/longitudinal mechanical properties of non-woven paper determines the difference in the transverse/longitudinal mechanical properties of the material. Therefore, the present invention uses non-woven paper as the base material, uses CDP as the plasticizer, and uses ammonium polyphosphate APP as the inorganic flame retardant to prepare polyvinyl chloride wallpaper with non-woven paper as the base material, which will not reduce the polyvinyl chloride Mechanical properties of wallpaper.

Table 1 compares the wet tensile strength of the polyvinyl chloride wallpaper based on non-woven paper prepared with reference to Example 17 and Example 1

Example 2

Step 1: Weigh each component according to the formula:

100 parts of polyvinyl chloride resin PVC;

50 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 15 parts.

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 90-mesh rotary screen printing. Substrate PVC wallpaper.

Example 3

Step 1: Weigh each component according to the formula:

80 parts of polyvinyl chloride resin PVC;

55 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 10 parts.

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste on the surface of the non ^- woven paper substrate by 100-mesh rotary screen printing. Substrate PVC wallpaper.

Example 4

Step 1: Weigh each component according to the formula:

120 parts of polyvinyl chloride resin PVC;

45 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 12 parts.

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 60-mesh rotary screen printing. PVC wallpaper.

Example 5

Step 1: Weigh each component according to the formula:

90 parts of polyvinyl chloride resin PVC;

40 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 4.5 parts.

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 70-mesh rotary screen printing. Substrate PVC wallpaper.

Example 6

Step 1: Weigh each component according to the formula:

110 parts of polyvinyl chloride resin PVC;

60 parts of liquid plasticizer cresyl diphenyl phosphate CDP;

Ammonium polyphosphate APP 18 parts.

Step 2: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix;

Step 3: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain PVC paste;

Step 4: Apply the PVC paste ^on the surface of the non-woven paper substrate by 80-mesh rotary screen printing. Substrate PVC wallpaper.

Example 7

Step 1: Weigh each component according to the formula:

The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion.

Step 2: Add polyvinyl chloride resin PVC, auxiliary plasticizer epoxy soybean oil ESO, potassium zinc composite heat stabilizer, viscosity reducer D40 solvent oil into liquid plasticizer cresyl diphenyl phosphate CDP respectively, with 400r Stir at a speed of 1/min to obtain a PVC premix evenly;

Step 3: Add ammonium polyphosphate APP, titanium dioxide TiO ₂ , foaming agent azodicarbonamide ADC, and foaming aid zinc oxide ZnO to the PVC premix respectively, and carry out the process at a speed of 1000r/min. Stir until it is evenly stirred to obtain a PVC paste;

Step 4: Coat the PVC paste on the surface of the non-woven paper substrate by 60-mesh rotary screen printing, the coating dosage is 140g/m ² , dry at 200°C for 1 min and form into foam to obtain non-woven paper as Substrate PVC wallpaper.

Example 8

Step 1: Weigh each component according to the formula:

The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion.

Step 2: Add polyvinyl chloride resin PVC, auxiliary plasticizer epoxy soybean oil ESO, potassium zinc composite heat stabilizer, viscosity reducer D40 solvent oil into liquid plasticizer cresyl diphenyl phosphate CDP respectively, with 400r Stir at a speed of 1/min to obtain a PVC premix evenly;

Step 3: Add ammonium polyphosphate APP, titanium dioxide TiO ₂ , foaming agent azodicarbonamide ADC, and foaming aid zinc oxide ZnO to the PVC premix respectively, and carry out the process at a speed of 1000r/min. Stir until it is evenly stirred to obtain a PVC paste;

Step 4: Coat the PVC paste on the surface of the non-woven paper substrate by 60-mesh rotary screen printing, the coating dosage is 140g/m ² , dry at 200°C for 1 min and form into foam to obtain non-woven paper as Substrate PVC wallpaper.

The polyvinyl chloride wallpaper based on non-woven paper prepared in Examples 2-8 was tested for limiting oxygen index values, and the specific test results are shown in FIG. 8 . It can be seen from Fig. 8 that, by adopting the preparation method of the present invention, the limiting oxygen index values of the polyvinyl chloride wallpaper obtained with non-woven paper as the base material are all greater than 32, which meets the limiting oxygen index of B1 grade materials in the national standard GB 8624-2012 ≥32 flame retardant requirements.

From the above analysis of the present invention, it can be seen that inorganic flame retardants Mg(OH) ₂ , Al(OH) ₃ and ammonium polyphosphate APP can improve the flame retardant effect of polyvinyl chloride wallpaper with non-woven paper as the base material to varying degrees, wherein Ammonium polyphosphate APP has the best flame retardant effect; ammonium polyphosphate APP accelerates pyrolysis at 250°C, releasing a large amount of CO ₂ , NH ₃ gas, and producing decomposition products P ₂ O ₅ and P ₂ O ₃ , Covering the surface of polyvinyl chloride, inhibiting the generation of flammable gases, thereby slowing down the burning speed of polyvinyl chloride wallpaper materials, and improving the dimensional stability, thermal stability and flame retardancy of polyvinyl chloride wallpaper materials.

At the same time, the inorganic flame retardant ammonium polyphosphate APP added in the present invention can also be used as a filler, and can replace heavy calcium carbonate in the prior art, which can not only reduce production costs, but also improve the quality of the prepared polyvinyl chloride wallpaper. Flame retardant properties.

The traditional production process uses the flammable material dioctyl phthalate as a plasticizer, which will affect the flame retardancy of non-woven paper-based PVC wallpaper. The invention adopts cresyl diphenyl phosphate CDP not only to have the effect of plasticizer, but also to have certain flame retardant effect. In the absence of inorganic flame retardants, compared with dioctyl phthalate, the present invention uses cresyl diphenyl phosphate CDP as the plasticizer, and the polyvinyl chloride wallpaper with non-woven paper as the base material limit oxygen The index improved by 25.6%.

Therefore, the present invention uses non-woven paper as a base material, uses lower-priced ammonium polyphosphate APP as an inorganic flame retardant, and uses cresyl diphenyl phosphate CDP as a liquid plasticizer to prepare a low-cost, high-flame-retardant Non-woven paper-based PVC wallpaper with high smoke suppression and high mechanical properties. The limit oxygen index of the polyvinyl chloride wallpaper based on non-woven paper prepared by the invention can reach 33.8 after flame-retardant modification, which is 57.2% higher than that of the prior art; the maximum smoke density is 9.8%, which is 9.8% higher than that of the prior art. The reduction is 35.1%; the transverse and longitudinal wet tensile strengths reach 1.21 and 1.24kN·m ^-1 respectively, which are 7.1% and 7.8% higher than the prior art. The polyvinyl chloride wallpaper prepared with the non-woven paper as the base material meets the flame-retardant requirement of B1-grade material limit oxygen index ≥ 32 in the national standard GB 8624-2012.

The above is only an embodiment of the present invention, and does not limit the scope of patent protection of the present invention. Any equivalent structure or equivalent process conversion made by using the content of the description of the present invention, or directly or indirectly used in other related technical fields, All are included in the scope of patent protection of the present invention in the same way.

Claims (8)

1. Polyvinyl chloride wallpaper based on non-woven paper with high flame resistance, which includes a base material and a coating slurry, the base material is a non-woven paper, and the coating slurry is a PVC paste, The coating dosage is 100-140g/m ² ; it is characterized in that: the PVC paste includes the following components in parts by weight: Polyvinyl chloride resin PVC 80-120 parts; 40-60 parts of liquid plasticizer cresyl diphenyl phosphate CDP; Ammonium polyphosphate APP 4.5-18 parts. 2. The highly flame-retardant polyvinyl chloride wallpaper based on non-woven paper according to claim 1, wherein the PVC paste comprises the following components in parts by weight: Polyvinyl chloride resin PVC 90-110 parts; 45-55 parts of liquid plasticizer toluene diphenyl phosphate CDP; Ammonium polyphosphate APP 6-10 parts. 3. The highly flame-retardant polyvinyl chloride wallpaper based on non-woven paper according to claim 2, characterized in that: the PVC paste comprises the following components in parts by weight: 100 parts of polyvinyl chloride resin PVC; 50 parts of liquid plasticizer cresyl diphenyl phosphate CDP; Ammonium polyphosphate APP 7.5 parts. 4. The highly flame-retardant polyvinyl chloride wallpaper based on non-woven paper according to any one of claims 1-3, characterized in that: the PVC paste also includes the following components in parts by weight: The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion. 5. The method for preparing polyvinyl chloride wallpaper based on non-woven paper according to one of claims 1-3, characterized in that it comprises the following steps: Step 1: adding polyvinyl chloride resin PVC to liquid plasticizer cresyl diphenyl phosphate CDP, stirring and mixing at a high speed to obtain a PVC premix; Step 2: adding ammonium polyphosphate APP into the PVC premix, stirring and mixing at a high speed to obtain a PVC paste; Step 3: apply the PVC paste on the surface of the non-woven paper base material by rotary screen printing, solidify and shape after drying, and obtain the non-woven paper-based polyvinyl chloride wallpaper with high flame retardancy. 6. The preparation method of the polyvinyl chloride wallpaper based on non-woven paper according to claim 5, characterized in that: it specifically comprises the following steps: Step 1: Add polyvinyl chloride resin PVC, auxiliary plasticizer epoxy soybean oil ESO, potassium-zinc composite heat stabilizer, viscosity reducer D40 solvent oil to the liquid plasticizer cresyl diphenyl phosphate CDP, and stir at high speed Get the PVC premix after mixing; Step 2: Add ammonium polyphosphate APP, titanium dioxide TiO ₂ , foaming agent azodicarbonamide ADC, and foaming aid zinc oxide ZnO to the PVC premix, and stir and mix at high speed to obtain PVC paste; Step 3: apply the PVC paste on the surface of the non-woven paper base material by rotary screen printing, foam molding after drying, and obtain the non-woven paper-based polyvinyl chloride wallpaper with high flame retardancy; Wherein, the parts by weight of each auxiliary material component are: The potassium-zinc composite heat stabilizer is a mixture of potassium stearate and zinc stearate in any proportion. 7. The preparation method of the polyvinyl chloride wallpaper based on non-woven paper with high flame retardancy according to claim 5, characterized in that: in the step 3, the mesh number of the cylinder is 50- 100 mesh. 8. The method for preparing polyvinyl chloride wallpaper based on non-woven paper with high flame retardancy according to claim 5, characterized in that: in the step 3, the PVC paste is coated on the After the surface of the non-woven paper substrate is dried, it is dried at 180-250°C for 0.5-1.5 minutes to solidify and form.