A foamed wallpaper

Abstract

The present invention discloses a foamed wallpaper, which comprises a base cloth layer and a foamed layer; the foamed layer is composed of the following components in parts by weight: PVC paste resin: 100-200 parts, foaming agent: 1-5 parts, plasticizer: 50-100 parts, stabilizer: 1-10 parts, composite modifier: 30-50 parts; its main body is PVC paste resin as the main material, which is foamed by a foaming agent to obtain wallpaper material, and the key of the present invention lies in the composite modifier. The composite modifier is mainly prepared by first modifying nano-titanium dioxide with silane, then emulsifying it with acrylate, and finally adding modified calcium carbonate to obtain the composite modifier. The composite modifier can improve the mechanical properties of PVC after foaming.

Description

Technical Field

[0001] The present invention relates to the field of polymers, and more specifically to a foamed wallpaper. Background Art

[0002] The foamed wallpaper is a paper made of a base cloth as a substrate, coated with a PVC paste resin mixed with a foaming agent, and then heated and foamed after printing or without printing. "Foaming" is also called screen relief foaming, which means adding a foaming agent to the raw materials and assisting with high temperature during the production process to make the foaming agent complete a process similar to "fermentation".

[0003] In the prior art, since it is a PVC foamed material, the mechanical properties of the PVC material are significantly reduced after foaming. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a high-strength foamed wallpaper.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A foamed wallpaper,

[0007] comprising a base cloth layer and a foamed layer;

[0008] The foamed layer

[0009] comprises the following components in parts by weight:

[0010] PVC paste resin: 100 - 200 parts

[0011] Foaming agent: 1 - 5 parts

[0012] Plasticizer: 50 - 100 parts

[0013] Stabilizer: 1 - 10 parts

[0014] Composite modifier: 30 - 50 parts;

[0015] The modified nano-silica is composed of the following components in parts by weight:

[0016] The composite modifier is:

[0017] Step A: Mix the dried nano-titanium dioxide with a solvent, adjust the pH to 3 - 4 with glacial acetic acid, ultrasonically disperse for 2 h, add a silane coupling agent, raise the temperature to 70 - 80 °C, adjust the pH to 9 - 10 with ammonia water, and mechanically stir for 5 h. After drying and grinding, modified nano-titanium dioxide is obtained;

[0018] Step B: Mix calcium carbonate with deionized water, add sodium stearate, react for 4 h, and obtain modified calcium carbonate after drying and grinding;

[0019] Step C: Take acrylate, emulsifier, modified nano-titanium dioxide, and deionized water, mix them, stir at high speed for 10 min, then perform ultrasonic dispersion for 30 min, add an initiator, raise the temperature to 80 - 90 °C and react for 2 h, cool down to 40 °C, adjust the pH to about 7 - 8 with ammonia water, add modified calcium carbonate, mechanically stir for 1 h, and then perform ultrasonic treatment for 20 - 30 min to obtain a composite modifier.

[0020] As a further improvement of the present invention,

[0021] The blowing agent is an AC blowing agent;

[0022] The plasticizer is a DOP plasticizer;

[0023] The stabilizer is a potassium / zinc stabilizer.

[0024] As a further improvement of the present invention,

[0025] In the said Step A:

[0026] The solvent is a mixture of deionized water and absolute ethanol with a mass ratio of 2:1;

[0027] The mass ratio of the nano-titanium dioxide: solvent: silane coupling agent is 10:30:1;

[0028] The silane coupling agent is a KH-570 silane coupling agent;

[0029] As a further improvement of the present invention,

[0030] In the said Step B:

[0031] The mass ratio of calcium carbonate: deionized water: sodium stearate is 50:100:1 - 3;

[0032] As a further improvement of the present invention,

[0033] In the said Step C:

[0034] Acrylate: emulsifier: modified nano-titanium dioxide: deionized water: modified calcium carbonate: initiator 30:0.2:10:100:100:0.2;

[0036] The emulsifier is sodium dodecyl sulfate.

[0037] The initiator is ammonium persulfate.

[0038] As a further improvement of the present invention,

[0039] In step C, the acrylate is a mixture of methyl methacrylate, 4,4'-biphenyldiol diacrylate, and 2,4,6-trifluorobenzyl methacrylate with a mass ratio of 10:4:1.

[0040] As a further improvement of the present invention,

[0041] Its preparation method is as follows:

[0042] Step 1: Mix PVC paste resin, foaming agent, plasticizer, stabilizer, and composite modifier to obtain a slurry.

[0043] Step 2: Coat the slurry on the base fabric and perform pre-plasticization.

[0044] Step 3: After completing pre-plasticization, perform plasticization and foaming to obtain PVC foamed wallpaper.

[0045] As a further improvement of the present invention,

[0046] The pre-plasticization temperature in step 2 is 100 - 150 °C, and the time is 3 - 5 min.

[0047] As a further improvement of the present invention,

[0048] In step 3, the plasticization temperature is 170 - 180 °C, and the time is 3 - 5 min.

[0049] As a further improvement of the present invention,

[0050] The base fabric is release paper or non-woven fabric.

[0051] The beneficial effect of the present invention is that in the present invention, the main body is PVC paste resin as the main material, and it is foamed by a foaming agent to obtain wallpaper material. The key of the present invention lies in the composite modifier. The composite modifier is mainly prepared by first modifying nano-titanium dioxide with silane, then emulsifying it with acrylate, and finally adding modified calcium carbonate to obtain the composite modifier. The composite modifier can improve the mechanical properties of PVC after foaming. Specific Embodiments

[0052] Example 1:

[0053] A foamed wallpaper includes a base fabric layer and a foamed layer;

[0054] The foamed layer

[0055] Comprises the following components in parts by weight:

[0056] PVC paste resin: 150 parts

[0057] AC foaming agent: 3 parts

[0058] DOP plasticizer: 50 parts

[0059] Potassium / zinc stabilizer: 1 part

[0060] Compound modifier: 50 parts;

[0061] The compound modifier is as follows:

[0062] Step A: Mix the dried nano-titanium dioxide with a solvent, adjust the pH to 3 with glacial acetic acid, ultrasonically disperse for 2 h, add a silane coupling agent, heat up to 80 °C, adjust the pH to 9 with ammonia water, mechanically stir for 5 h, and obtain modified nano-titanium dioxide after drying and grinding;

[0063] Step B: Mix calcium carbonate with deionized water, add sodium stearate, react for 4 h, and obtain modified calcium carbonate after drying and grinding;

[0064] Step C: Take methyl methacrylate, an emulsifier, modified nano-titanium dioxide, and deionized water and mix them, stir at high speed for 10 min, then ultrasonically disperse for 30 min, add an initiator, heat up to 85 °C and react for 2 h, cool down to 40 °C, adjust the pH to about 7 with ammonia water, add modified calcium carbonate, mechanically stir for 1 h and then ultrasonically treat for 20 min to obtain the compound modifier.

[0065] In the said Step A:

[0066] The solvent is a mixture of deionized water and absolute ethanol with a mass ratio of 2:1;

[0067] The mass ratio of the nano-titanium dioxide: the solvent: the silane coupling agent is 10:30:1;

[0068] The silane coupling agent is KH-570 silane coupling agent;

[0069] In the said Step B:

[0070] The mass ratio of calcium carbonate: deionized water: sodium stearate is 50:100:1 - 3;

[0071] In the said Step C:

[0072] Methyl methacrylate: emulsifier: modified nano-titanium dioxide: deionized water: modified calcium carbonate: initiator 30:0.2:10:100:100:0.2;

[0074] The emulsifier is sodium dodecyl sulfate.

[0075] The initiator is ammonium persulfate.

[0076] The preparation method of the foamed wallpaper is as follows:

[0077] Step 1: Mix PVC paste resin, foaming agent, plasticizer, stabilizer, and composite modifier to obtain a slurry.

[0078] Step 2: Apply the slurry onto the non-woven fabric using two 35-wire gravure printing rollers by superimposed roll coating, and perform pre-plasticization on the base fabric through pre-drying.

[0079] Step 3: After completing pre-plasticization, perform plasticization and foaming to obtain PVC foamed wallpaper.

[0080] The pre-plasticization temperature in Step 2 is 120 °C, and the time is 3 min.

[0081] In Step 3, the plasticization temperature is 170 °C, and the time is 3 min.

[0082] The base fabric is non-woven fabric.

[0083] Example 2:

[0084] A foamed wallpaper, comprising a base fabric layer and a foamed layer;

[0085] The foamed layer

[0086] Comprises the following components by weight:

[0087] PVC paste resin: 150 parts

[0088] AC foaming agent: 3 parts

[0089] DOP plasticizer: 50 parts

[0090] Potassium / zinc stabilizer: 1 part

[0091] Composite modifier: 50 parts;

[0092] The composite modifier is:

[0093] Step A: Mix the dried nano-titanium dioxide with a solvent, adjust the pH to 3 with glacial acetic acid, perform ultrasonic dispersion for 2 h, add a silane coupling agent, raise the temperature to 80 °C, adjust the pH to 9 with ammonia water, and perform mechanical stirring for 5 h. After drying and grinding, obtain modified nano-titanium dioxide.

[0094] Step B: Mix calcium carbonate with deionized water, add sodium stearate, react for 4 h, and obtain modified calcium carbonate after drying and grinding.

[0095] Step C: Take acrylate, emulsifier, modified nano-titanium dioxide, and deionized water for mixing, perform high-speed stirring for 10 min, then perform ultrasonic dispersion for 30 min, add an initiator, raise the temperature to 85 °C and react for 2 h, cool down to 40 °C, adjust the pH to about 7 with ammonia water, add modified calcium carbonate, perform mechanical stirring for 1 h, and then perform ultrasonic treatment for 20 min to obtain the composite modifier.

[0096] In step A:

[0097] The solvent is a mixture of deionized water and absolute ethanol with a mass ratio of 2:1;

[0098] The mass ratio of the nano-titanium dioxide: the solvent: the silane coupling agent is 10:30:1;

[0099] The silane coupling agent is KH-570 silane coupling agent;

[0100] In step B:

[0101] The mass ratio of calcium carbonate: deionized water: sodium stearate is 50:100:1 - 3;

[0102] In step C:

[0103] Acrylate: emulsifier: modified nano-titanium dioxide: deionized water: modified calcium carbonate: initiator 30:0.2:10:100:100:0.2;

[0105] The emulsifier is sodium dodecyl sulfate.

[0106] The initiator is ammonium persulfate.

[0107] In step C, the acrylate is a mixture of methyl methacrylate, 4,4'-biphenyldiol diacrylate, and 2,4,6-trifluorobenzyl methacrylate with a mass ratio of 10:4:1.

[0108] The preparation method of the foamed wallpaper is as follows:

[0109] Step 1: Mix PVC paste resin, foaming agent, plasticizer, stabilizer, and composite modifier to obtain a slurry;

[0110] Step 2: Use two 35-wire gravure printing rollers to apply the slurry onto the non-woven fabric by superimposed roller coating, and pre-dry it on the base fabric for pre-plasticization;

[0111] Step 3: After completing the pre-plasticization, perform plasticization and foaming to obtain the PVC foamed wallpaper.

[0112] The pre-plasticization temperature in step 2 is 120°C, and the time is 3 min.

[0113] In step 3, the plasticization temperature is 170°C, and the time is 3 min.

[0114] The base fabric is non-woven fabric.

[0115] Comparative example 1:

[0116] It includes a base fabric layer and a foaming layer;

[0117] The foaming layer

[0118] comprises the following components by weight:

[0119] PVC paste resin: 150 parts

[0120] AC blowing agent: 3 parts

[0121] DOP plasticizer: 50 parts

[0122] Potassium / zinc stabilizer: 1 part

[0123] The preparation method of the foamed wallpaper is as follows:

[0124] Step 1: Mix PVC paste resin, blowing agent, plasticizer, and stabilizer to obtain a slurry;

[0125] Step 2: Apply the slurry onto the non-woven fabric using two 35-wire gravure printing rollers by superimposed roll coating, and pre-dry it on the base fabric for pre-plasticization;

[0126] Step 3: After completing the pre-plasticization, perform plasticization and foaming to obtain PVC foamed wallpaper.

[0127] The pre-plasticization temperature in Step 2 is 120°C, and the time is 3 min.

[0128] In Step 3, the plasticization temperature is 170°C, and the time is 3 min.

[0129] Comparative Example 2:

[0130] It includes a base fabric layer and a foaming layer;

[0131] The foaming layer

[0132] comprises the following components by weight:

[0133] PVC paste resin: 150 parts

[0134] AC blowing agent: 3 parts

[0135] DOP plasticizer: 50 parts

[0136] Potassium / zinc stabilizer: 1 part

[0137] Nano-titanium dioxide: 3.5 parts

[0138] Calcium carbonate: 35 parts Methyl methacrylate: 10 parts.

[0139] Step 1: Mix PVC paste resin, blowing agent, plasticizer, stabilizer, nano-titanium dioxide, calcium carbonate, and methyl methacrylate to obtain a slurry;

[0140] Step 2: The slurry is applied to the non-woven fabric by superimposed roller coating using two 35-wire gravure printing rollers, and pre-dried on the base fabric for pre-plasticization;

[0141] Step 3: After the pre-plasticization is completed, plasticization and foaming are carried out to obtain a PVC foamed wallpaper.

[0142] The pre-plasticization temperature in Step 2 is 120 °C and the time is 3 min.

[0143] In Step 3, the plasticization temperature is 170 °C and the time is 3 min.

[0144] Raw materials Manufacturer PVC paste resin CPM-31 Jinan Xiangfeng Weiye Chemical Co., Ltd. AC blowing agent Hebei Jinhaili Chemical Technology Co., Ltd. DOP plasticizer Shandong Anhe Chemical Co., Ltd. Potassium / zinc stabilizer Qingdao Tuozhi Technology Co., Ltd. Nano titanium dioxide Hubei Huifu Nano Materials Co., Ltd. Glacial acetic acid Jinan Linsheng Chemical Co., Ltd. Calcium carbonate Xuancheng Huaxin Chemical Co., Ltd. Sodium stearate Jinan Xichuan Chemical Technology Co., Ltd. Methyl methacrylate Shandong Jin'en New Materials Co., Ltd. Absolute ethanol Jinan Bozhi Chemical Co., Ltd. KH-570 silane coupling agent Shandong Yuanjin New Materials Co., Ltd. Sodium dodecyl sulfate Changzhou Baiyundu Chemical Co., Ltd. Ammonium persulfate Shandong Xinhe New Materials Co., Ltd. 4,4′-Biphenyldiol diacrylate Zhengzhou Alpha Chemical Co., Ltd. 2,4,6-Trifluorobenzyl methacrylate Shanghai Enfluorine Technology Co., Ltd. Ammonia water Shandong Xinjiucheng Chemical Technology Co., Ltd.

[0145] The thickness is tested according to GB / T6672-2001 "Plastics films and sheets - Determination of thickness - Mechanical measurement method"; the wet tensile load test is carried out according to QB / T4034-2010 "Wallpaper";

[0146] The pencil scratch hardness and the positive and negative folding performance are tested according to Q / TXZJH003-2013 "PVC foamed wallpaper".

[0147]

[0148] The difference between Example 1 and Example 2 is that in Example 1, when preparing the composite modifier, the acrylate used is methyl methacrylate, while in Example 2, a mixture of methyl methacrylate, 4,4'-biphenyldiol diacrylate, and 2,4,6-trifluorobenzyl methacrylate with a mass ratio of 10:4:1 is used. Comparing Example 1 and Example 2, it can be clearly found that the tensile load of Example 2 has been significantly improved, which shows that compared with single methyl methacrylate, the mixture of methyl methacrylate, 4,4'-biphenyldiol diacrylate, and 2,4,6-trifluorobenzyl methacrylate with a mass ratio of 10:4:1 used in combination has a better strengthening effect.

[0149] In Comparative Example 1, no modifier was added. In Comparative Example 2, methyl methacrylate, nano-titanium dioxide, and calcium carbonate were added separately without reacting them first to form a modifier. From the test results, compared with Comparative Example 1, the hardness and tensile load of Comparative Example 2 have both increased, and no breakage was found in the positive and negative folding, which shows that methyl methacrylate, nano-titanium dioxide, and calcium carbonate have an improvement on the material. In Example 1, methyl methacrylate, nano-titanium dioxide, and calcium carbonate were first subjected to a chemical reaction to obtain a modifier and then used, and its strength has been more significantly improved compared with Comparative Example 2, while Example 2 has a greater improvement.

[0150] In the present invention, the main body is PVC paste resin as the main material, which is foamed by a foaming agent to obtain a wallpaper material. The key of the present invention lies in the composite modifier. The composite modifier mainly modifies nano-titanium dioxide with silane first, then emulsifies it with acrylate, and finally adds modified calcium carbonate to obtain the composite modifier. The composite modifier can improve the mechanical properties of PVC after foaming.

[0151] The above are only the preferred embodiments of the present invention. The protection scope of the present invention is not limited to the above embodiments. All technical solutions falling within the idea of the present invention belong to the protection scope of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A foamed wallpaper, characterized in that: It includes a base cloth layer and a foamed layer; The foamed layer Comprises the following components by weight: PVC paste resin: 100 - 200 parts Foaming agent: 1 - 5 parts Plasticizer: 50 - 100 parts Stabilizer: 1 - 10 parts Composite modifier: 30 - 50 parts; The composite modifier is: Step A: Mix the dried nano-titanium dioxide with a solvent, adjust the pH to 3 - 4 with glacial acetic acid, ultrasonically disperse for 2 h, add a silane coupling agent, raise the temperature to 70 - 80 °C, adjust the pH to 9 - 10 with ammonia water, mechanically stir for 5 h, and obtain modified nano-titanium dioxide after drying and grinding; Step B: Mix calcium carbonate with deionized water, add sodium stearate, react for 4 h, and obtain modified calcium carbonate after drying and grinding; Step C: Take acrylate, emulsifier, modified nano-titanium dioxide, deionized water and mix them, stir at high speed for 10 min, then ultrasonically disperse for 30 min, add an initiator, raise the temperature to 80 - 90 °C and react for 2 h, cool down to 40 °C and adjust the pH to 7 - 8 with ammonia water, add modified calcium carbonate, mechanically stir for 1 h and then ultrasonically treat for 20 - 30 min to obtain the composite modifier.

2. A foamed wallpaper according to claim 1, characterized in that: The foaming agent is an AC foaming agent; The plasticizer is a DOP plasticizer; The stabilizer is a potassium / zinc stabilizer.

3. A foamed wallpaper according to claim 1, characterized in that: In step A: The solvent is a mixture of deionized water and absolute ethanol with a mass ratio of 2:1; The mass ratio of the nano-titanium dioxide: solvent: silane coupling agent is 10:30:1; The silane coupling agent is a KH-570 silane coupling agent.

4. A foamed wallpaper according to claim 1, characterized in that: In step B: The mass ratio of calcium carbonate: deionized water: sodium stearate is 50:100:1 - 3.

5. A foamed wallpaper according to claim 1, characterized in that: In step C: Acrylate: emulsifier: modified nano-titanium dioxide: deionized water: modified calcium carbonate: initiator 30:0.2:10:100:100:0.2; The emulsifier is sodium dodecyl sulfate; The initiator is ammonium persulfate.

6. A foamed wallpaper according to claim 1, characterized in that: In step C, the acrylate is a mixture of methyl methacrylate, 4,4'-biphenyldiol diacrylate, and 2,4,6-trifluorobenzyl methacrylate with a mass ratio of 10:4:

1.

7. A foamed wallpaper according to claim 1, characterized in that: Its preparation method is: Step one: Mix PVC paste resin, foaming agent, plasticizer, stabilizer, and composite modifier to obtain a slurry; Step two: Coat the slurry on the base cloth and perform pre-plasticization; Step three: After completing pre-plasticization, perform plasticization and foaming to obtain a PVC foamed wallpaper.

8. A foamed wallpaper according to claim 7, characterized in that: The pre-plasticization temperature in step two is 100 - 150 °C and the time is 3 - 5 min.

9. A foamed wallpaper according to claim 7, characterized in that: In the third step, the plasticizing temperature is 170-180°C and the time is 3-5 minutes.

10. A foamed wallpaper according to claim 1, characterized in that: The base fabric is release paper or non-woven fabric.

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