CN102587218A - Composite wallpaper containing polyvinyl chloride - Google Patents

Abstract

The invention relates to a composite wallpaper containing polyvinyl chloride. The invention discloses a composite PVC wallpaper with a flame-retardant polyvinyl chloride (referred to as flame-retardant PVC) coating or film as the surface layer and a flame-retardant paper as the bottom layer. The weight ratio of flame-retardant PVC surface layer components is: PVC resin 100, plasticizer 0-50, flame retardant 20-80, stabilizer 0.01-1, filler 40-150, foaming agent 0-1, thinner dose 0-10. Flame retardant paper is made by dipping, spraying or brushing flame retardant liquid on non-flame retardant paper first, and then drying it. Compared with the traditional treatment method of using antimony trioxide as the flame retardant of the PVC surface layer and ammonium polyphosphate as the flame retardant of the paper base layer, the flame-retardant PVC wallpaper is more environmentally friendly, has low toxicity, and has low smoke density during combustion. It can reach more than 32%, and the combustion performance can reach GB8624-2006B level.

Description

Composite wallpaper containing polyvinyl chloride

technical field

The invention relates to wallpaper, in particular to a composite wallpaper containing polyvinyl chloride.

Background technique

As a kind of interior decoration material for rooms, wallpaper is not only widely used in public places such as restaurants and hotels, but also has entered thousands of households along with the improvement of people's living standards and housing conditions. Decorative wallpaper, although it can beautify the room, is a potential fire hazard because the commonly used wallpaper is flammable. Once a fire breaks out in the room, the wallpaper may be ignited, or the flame may spread along the wallpaper to expand the fire. From the perspective of fire safety, it is necessary to develop and use non-combustible or flame-retardant wallpapers.

With the enhancement of people's awareness of fire protection and environmental protection and a series of national standards, such as GB50222-95 "Code for Fire Protection Design of Building Interior Decoration", GB20286-2006 "Requirements and Marking of Combustion Performance of Flame-retardant Products and Components in Public Places", GB 8624-2006 The promulgation and implementation of "Classification of Combustion Behavior of Building Materials and Products", GB18585-2001 "Limits of Hazardous Substances in Wallpapers of Interior Decoration Materials", etc., the wallpapers used for interior decoration must be environmentally friendly in addition to maintaining flame retardant and other functions, so there is an urgent need to develop new ones. Environmentally friendly flame-retardant wallpaper and its corresponding technology.

PVC wallpaper usually consists of a paper base layer and a PVC surface layer. PVC molecules contain 56% chlorine, which is a self-extinguishing polymer with a limiting oxygen index of >45%. But in the wallpaper production process, in order to make the wallpaper elastic and soft, it is necessary to add 30%-80% plasticizer to PVC. When the total chlorine content of PVC is reduced to about 30% due to the dilution of plasticizers or other additives, the oxygen index of the product is greatly reduced. The content of plasticizer in the PVC surface paste of wallpaper can be as high as 70 parts (100 parts of PVC), the oxygen index of the base paper is generally 19-20%, and the composite PVC wallpaper has an oxygen index of about 21%. , easy to burn. Therefore, the fire department has clear regulations on plastic wallpapers, especially wallpapers used in high-rise buildings, generally requiring its oxygen index to be ≥ 27%.

The flame retardant technology of base paper has not really passed the customs in my country at present. Because the base paper has to withstand a high temperature of about 200°C in the PVC plasticization process on its surface, when most water-soluble inorganic flame retardants are used to flame-retardant the base paper, the color of the paper tends to turn yellow, the strength decreases severely, and the brittleness increases. Folding resistance is very poor and other problems, more seriously, the flame retardant is easy to crystallize and precipitate, the paper is easy to absorb moisture, and stick to each other, which brings many problems to the storage and use of wallpaper. For example, the Chinese patent (application number: 87105201) discloses polyvinyl chloride flame-retardant wallpaper, wherein the flame retardant used in the base paper layer of the wallpaper is ammonium polyphosphate, and the base paper treated with this flame retardant will have the above-mentioned many problems.

The most commonly used method of flame-retardant treatment of PVC surface is to add antimony trioxide (Sb2O3). The agent is Sb2O3. However, the national standard GB 18585-2001 "Limits of Hazardous Substances in Interior Decoration Materials and Wallpapers" has strict restrictions on the content of heavy metals in wallpapers, such as antimony, and requires that its content in wallpapers should not exceed 20 mg per kg. This regulation restricts the application of Sb2O3 as a flame retardant in wallpaper. Therefore, it is urgent to develop new flame-retardant technology to replace the use of Sb2O3 in PVC flame-retardant wallpaper.

Contents of the invention

In order to overcome the disadvantages of poor flame-retardant effect and non-environmental protection of the wallpaper in the prior art, the present invention provides an environmentally friendly flame-retardant, low-smoke, low-toxic composite PVC wallpaper.

One aspect of the present invention provides a composite wallpaper with a surface layer of flame-retardant polyvinyl chloride coating or film and a bottom layer of flame-retardant paper. The surface layer is composed of the following components by weight: PVC resin 100 parts, 0-50 parts of plasticizer, 20-80 parts of flame retardant, 0.01-1 part of stabilizer, 40-95 parts of filler, 0-1 part of foaming agent, 3-10 parts of diluent; The flame retardant is zinc borate, aluminum hydroxide, triethyl phosphate, magnesium hydroxide, diphenyl 2-ethylhexyl phosphate, chlorinated paraffin, ammonium polyphosphate, tributyl phosphate, tris(2-chloroethyl phosphate) base) ester; the plasticizer is dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, dioctyl adipate, decane One or more of dioctyl dioic acid; the stabilizer is one of calcium zinc stabilizer or isooctyl dimercaptoacetate di-n-octyl tin stabilizer; the filler is talcum powder, calcium carbonate, titanium dioxide A kind of; The blowing agent is azodicarbonamide or azobisisobutyronitrile; The diluent is toluene or xylene.

The surface layer of the composite wallpaper is preferably composed of the following components by weight: 100 parts of PVC resin, 10 parts of ammonium polyphosphate, 40 parts of tributyl phosphate, 10 parts of chlorinated paraffin, 10 parts of isooctyl dimercaptoacetate 0.3 parts of n-octyl tin stabilizer, 60 parts of titanium dioxide, and 10 parts of xylene.

The surface layer of the composite wallpaper is preferably composed of the following components by weight: 100 parts of PVC resin, 25 parts of dibutyl phthalate, 5 parts of zinc borate, 5 parts of aluminum hydroxide, triethyl phosphate 10 parts, G-618CZ type calcium zinc stabilizer 0.01 parts, talcum powder 40 parts, azodicarbonamide 1 part, toluene 10 parts.

The surface layer of the above-mentioned composite wallpaper is also preferably composed of the following components by weight: 100 parts of PVC resin, 50 parts of diisobutyl phthalate, 20 parts of magnesium hydroxide, diphenyl 2-ethylhexyl phosphate 30 parts of ester, 30 parts of chlorinated paraffin, 1 part of G-618CZ type calcium zinc stabilizer, 150 parts of calcium carbonate, 3 parts of toluene.

The surface layer of the above-mentioned composite wallpaper is also preferably composed of the following components by weight: 100 parts of PVC resin, 25 parts of dioctyl phthalate, 10 parts of magnesium hydroxide, tris(2-chloroethyl) phosphate 40 parts of esters, 0.5 parts of isooctyl dimercaptoacetate di-n-octyl tin stabilizer, 95 parts of titanium dioxide, 0.5 parts of azobisisobutyronitrile, and 5 parts of diluent xylene.

The present invention also provides a method for preparing the bottom flame-retardant paper of the composite wallpaper, which is specifically prepared by the following method: first dipping or spraying or brushing the non-flame-retardant paper in the flame-retardant liquid, and then It is then made by drying; wherein the flame retardant liquid is an aqueous solution or an emulsion, and the flame retardant in the flame retardant liquid is a) one or more nitrogen-containing flame retardants, b) phosphorus-containing flame retardant One or more in the agent or c) one or more in aluminum hydroxide, magnesium hydroxide, boric acid, zinc borate, zinc stannate.

The weight percent concentration of the aqueous solution or emulsion described in the preparation method of the bottom flame-retardant paper of the composite wallpaper is preferably 10-35%.

The flame retardant in the flame retardant liquid described in the preparation method of the bottom flame retardant paper of the above composite wallpaper is preferably composed of the following components in percentage by weight: 5% dicyandiamide, 10% ammonium polyphosphate, Zinc borate 5%.

The flame retardant in the flame retardant liquid described in the preparation method of the bottom flame retardant paper of the composite wallpaper is also preferably composed of the following components in percentage by weight: melamine 3%, ammonium polyphosphate 4%, boric acid 3%.

The flame retardant in the flame retardant liquid described in the preparation method of the bottom flame retardant paper of the composite wallpaper is also preferably composed of the following components in percentage by weight: 5% melamine, 10% ammonium polyphosphate, amino Guanidine sulfonate 20%.

The flame retardant in the flame retardant liquid described in the preparation method of the bottom flame retardant paper of the composite wallpaper is also preferably composed of the following components in percentage by weight: 5% dicyandiamide, 5% phosphoric acid, amino Guanidine sulfonate 12%.

Compared with the prior art, the composite PVC wallpaper of the present invention has the following advantages:

1) The wallpaper surface layer does not contain heavy metal toxic flame retardants, such as Sb ₂ O ₃ , which meets environmental protection requirements;

2) The bottom layer of the wallpaper adopts a compound flame retardant. After the flame retardant treatment, the bottom layer of the wallpaper will not turn yellow or become brittle in the subsequent high-temperature process. The flame retardant is not easy to crystallize during storage, and the paper does not absorb moisture and stick together;

3) The PVC wallpaper produced by the present invention is tested by the national standard GB8624-2006, and can reach Class B, with low toxicity, low smoke density, and an oxygen index of more than 32%, which improves its fireproof performance.

the

Detailed ways

The present invention will be further described below in conjunction with specific examples, but this description does not limit the protection scope of the present invention.

The environment-friendly flame-retardant low-smoke and low-toxic composite PVC wallpaper of the invention uses flame-retardant PVC coating or film as the surface layer and flame-retardant paper as the bottom layer.

Example 1

According to the patent (application number: 87105201), a composite PVC wallpaper with flame-retardant PVC film as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of the flame-retardant PVC surface layer components is: 100 parts of PVC resin, phthalic acid Dioctyl ester (DOP) 52 parts, liquid Ba-Cd-Zn 2 parts, tri-salt lead stearate 1 part, lead stearate 1 part, stearic acid 0.2 part, CaCO ₃ 80 parts, antimony trioxide 5 parts parts; flame-retardant paper is made by impregnating non-flame-retardant paper with an aqueous solution containing 30% ammonium polyphosphate (weight white content), and then drying. According to the test of GB5454-1997, the flame-retardant PVC wallpaper made by this method has an oxygen index of 27%; according to the test of GB5455-1997, the damage length is >200mm, the smoldering time is >5s, and the burning time is >5s. In addition, the bottom layer of the wallpaper after flame-retardant treatment will turn yellow and become brittle in the subsequent high-temperature process. During the storage process, the flame retardant is easy to crystallize and precipitate, and the paper absorbs moisture and sticks.

Example 2

Composite PVC wallpaper with flame-retardant PVC coating as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of flame-retardant PVC surface layer components is: 100 parts of PVC resin, 25 parts of dibutyl phthalate (DBP) , 5 parts of zinc borate, 5 parts of aluminum hydroxide, 10 parts of triethyl phosphate, 0.01 part of G-618CZ type calcium zinc stabilizer (Xiamen Tongan Lianxiang Chemical Co., Ltd.), 40 parts of talcum powder, azodimethazine 1 part of amide, 10 parts of toluene; the flame-retardant paper is made of non-flame-retardant paper firstly impregnated with 5% (weight percentage) of dicyandiamide, 10% (weight percentage) of ammonium polyphosphate, and 5% (weight percentage) of zinc borate. The flame retardant liquid is then made by drying. The flame-retardant composite PVC wallpaper, according to the test of GB5454-1997, has an oxygen index of 32%; according to the test of GB5455-1997, the damage length is 120mm, the smoldering time is 1s, and the continuous burning time is 1s; according to the GB8624-2006 test, the combustion performance reaches B -s2, d0, t1 levels. The bottom layer of the wallpaper after flame retardant treatment has no yellowing and brittleness in the subsequent high-temperature process, no crystallization of the flame retardant during storage, and no moisture absorption and adhesion of the paper.

Example 3

Composite PVC wallpaper with flame-retardant PVC film as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of the flame-retardant PVC surface layer components is: 100 parts of PVC resin, 50 parts of diisobutyl phthalate, hydrogen 20 parts of magnesium, 30 parts of diphenyl 2-ethylhexyl phosphate, 30 parts of chlorinated paraffin, 1 part of G-618CZ type calcium zinc stabilizer, 150 parts of calcium carbonate, 3 parts of toluene; The paper is firstly made by impregnating a flame retardant solution containing 3% (weight percent) of melamine, 4% (weight percent) of ammonium polyphosphate and 3% (weight percent) of boric acid, and then dried. The flame-retardant composite PVC wallpaper, according to the test of GB5454-1997, has an oxygen index of 33%; according to the test of GB5455-1997, the damage length is 100mm, the smoldering time is 0, and the continuous burning time is 1s; according to the test of GB8624-2006, the combustion performance reaches B -s2, d0, t1 levels. The bottom layer of the wallpaper after flame retardant treatment has no yellowing and brittleness in the subsequent high-temperature process, no crystallization of the flame retardant during storage, and no moisture absorption and adhesion of the paper.

Example 4

Composite PVC wallpaper with flame-retardant PVC film as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of flame-retardant PVC surface layer components is: 100 parts of PVC resin, 10 parts of ammonium polyphosphate, 40 parts of tributyl phosphate, 10 parts of chlorinated paraffin, 0.3 parts of isooctyl dimercaptoacetate di-n-octyl tin stabilizer, 60 parts of titanium dioxide, 10 parts of xylene; the flame-retardant paper is that the non-flame-retardant paper is impregnated with melamine 5% (percentage by weight) , ammonium polyphosphate 10% (weight percentage), guanidine sulfamate 20% (weight percentage) flame retardant liquid, and then dried. According to the test of GB5454-1997, the flame-retardant composite PVC wallpaper has an oxygen index of 33.4%; according to the test of GB5455-1997, the damage length is 80mm, the smoldering time is 0, and the continuous burning time is 0; according to the GB8624-2006 test, the combustion performance reaches B -s2, d0, t1 levels. The bottom layer of the wallpaper after flame retardant treatment has no yellowing and brittleness in the subsequent high-temperature process, no crystallization of the flame retardant during storage, and no moisture absorption and adhesion of the paper.

Example 5

Composite PVC wallpaper with flame-retardant PVC film as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of the flame-retardant PVC surface layer components is: 100 parts of PVC resin, 25 parts of dioctyl phthalate (DOP), 10 parts of magnesium hydroxide, 40 parts of tris (2-chloroethyl) phosphate, 0.5 parts of isooctyl dimercaptoacetate di-n-octyl tin stabilizer, 95 parts of titanium dioxide, 0.5 parts of azobisisobutyronitrile, 5 parts of xylene parts; flame retardant paper is first impregnated with non-flame retardant paper containing 5% dicyandiamide (weight percentage), phosphoric acid 5% (weight percentage), guanidine sulfamate 12% (weight percentage) flame retardant liquid, and then Made by drying method. According to the test of GB5454-1997, the flame-retardant composite PVC wallpaper has an oxygen index of 32.6%; according to the test of GB5455-1997, the damage length is 95mm, the smoldering time is 1s, and the continuous burning time is 0; according to the test of GB8624-2006, the combustion performance reaches B -s2, d0, t1 levels. The bottom layer of the wallpaper after flame retardant treatment has no yellowing and brittleness in the subsequent high-temperature process, no crystallization of the flame retardant during storage, and no moisture absorption and adhesion of the paper.

Example 6

Composite PVC wallpaper with flame-retardant PVC film as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of the flame-retardant PVC surface layer components is: 100 parts of PVC resin, 60 parts of dioctyl adipate (DOA), 60 parts of polyester 10 parts of ammonium phosphate, 40 parts of tributyl phosphate, 10 parts of chlorinated paraffin, 0.3 parts of G-618CZ type calcium zinc stabilizer, 60 parts of barium sulfate, and 5 parts of triethanolamine; It is made by impregnating flame retardant liquid containing 5% (weight percentage) of melamine, 8% (weight percentage) of ammonium polyphosphate and 15% (weight percentage) of guanidine sulfamate, and then drying. According to the test of GB5454-1997, the flame-retardant composite PVC wallpaper has an oxygen index of 25%; according to the test of GB5455-1997, the damage length is >150mm; according to the test of GB8624-2006, the combustion performance fails to reach Class B.

Example 7

Composite PVC wallpaper with flame-retardant PVC coating as the surface layer and flame-retardant paper as the bottom layer. The weight ratio of the flame-retardant PVC surface layer components is: 100 parts of PVC resin, 50 parts of dioctyl sebacate DOS, polyphosphoric acid 10 parts of ammonium, 8 parts of chlorinated paraffin, 0.3 parts of G-618CZ type calcium-zinc stabilizer, 60 parts of clay, 5 parts of xylene; the flame-retardant paper is that the non-flame-retardant paper is impregnated with melamine 5% (percentage by weight) , ammonium polyphosphate 8% (weight percentage), guanidine sulfamate 15% (weight percentage) flame retardant liquid, and then dried. According to the test of GB5454-1997, the flame-retardant composite PVC wallpaper has an oxygen index of 22%; according to the test of GB5455-1997, the damage length is >150mm; according to the test of GB8624-2006, the combustion performance fails to reach Class B.

Claims (10)

1. A compound type wallpaper containing polyvinyl chloride, its surface layer is a polyvinyl chloride coating or film, and the bottom layer is a flame-retardant paper, which is characterized in that the surface layer is composed of the following components by weight: PVC 100 parts of resin, 0-50 parts of plasticizer, 20-80 parts of flame retardant, 0.01-1 part of stabilizer, 40-95 parts of filler, 0-1 part of foaming agent, 3-10 parts of thinner; The flame retardant is zinc borate, aluminum hydroxide, triethyl phosphate, magnesium hydroxide, diphenyl 2-ethylhexyl phosphate, chlorinated paraffin, ammonium polyphosphate, tributyl phosphate, tri(2- One or more in chloroethyl) ester; Described plasticizer is dibutyl phthalate, dioctyl phthalate, diisobutyl phthalate, dioctyl adipate , one or more of dioctyl sebacate; the stabilizer is one of calcium zinc stabilizer or isooctyl dimercaptoacetate di-n-octyl tin stabilizer; the filler is talcum powder, calcium carbonate, A kind of titanium dioxide; the foaming agent is azodicarbonamide or azobisisobutyronitrile; the diluent is toluene or xylene. 2. The composite wallpaper according to claim 1, characterized in that the surface layer of the wallpaper is composed of the following components by weight ratio: 100 parts of PVC resin, 10 parts of ammonium polyphosphate, 40 parts of tributyl phosphate, 10 parts of chlorinated paraffin, 0.3 parts of isooctyl dimercaptoacetate di-n-octyl tin stabilizer, 60 parts of titanium dioxide, and 10 parts of xylene. 3. The composite wallpaper according to claim 1, wherein the surface layer of the wallpaper is composed of the following components by weight: 100 parts of PVC resin, 25 parts of dibutyl phthalate, 5 parts of zinc borate 5 parts, aluminum hydroxide 5 parts, triethyl phosphate 10 parts, G-618CZ type calcium zinc stabilizer 0.01 parts, talcum powder 40 parts, azodicarbonamide 1 part, toluene 10 parts. 4. The composite wallpaper according to claim 1, characterized in that the surface layer of the wallpaper is composed of the following components by weight: 100 parts of PVC resin, 50 parts of diisobutyl phthalate, hydrogen 20 parts of magnesium, 30 parts of diphenyl 2-ethylhexyl phosphate, 30 parts of chlorinated paraffin, 1 part of G-618CZ type calcium zinc stabilizer, 150 parts of calcium carbonate, 3 parts of toluene. 5. The composite wallpaper according to claim 1, wherein the surface layer of the wallpaper is composed of the following components by weight: 100 parts of PVC resin, 25 parts of dioctyl phthalate, magnesium hydroxide 10 parts, 40 parts of tris (2-chloroethyl) phosphate, 0.5 parts of isooctyl dimercaptoacetate di-n-octyl tin stabilizer, 95 parts of titanium dioxide, 0.5 parts of azobisisobutyronitrile, 5 parts of diluent xylene . 6. The composite wallpaper according to any one of claims 1-5, characterized in that the bottom flame retardant paper of the wallpaper is prepared by the following method: the non-flame retardant paper is first dipped in the flame retardant liquid or It is made by spraying or brushing flame retardant liquid, and then drying; wherein the flame retardant liquid is an aqueous solution or emulsion, and the flame retardant in the flame retardant liquid is a) one of nitrogen-containing flame retardants or Multiple, b) one or more of phosphorus-containing flame retardants or c) one or more of aluminum hydroxide, magnesium hydroxide, boric acid, zinc borate, zinc stannate; wherein said aqueous solution or The weight percent concentration of the emulsion is preferably 10-35%. 7. The composite wallpaper according to claim 6, characterized in that the flame retardant in the flame retardant liquid consists of the following components in percentage by weight: 5% dicyandiamide, 10% ammonium polyphosphate, boric acid Zinc 5%. 8. The composite wallpaper according to claim 6, characterized in that the flame retardant in the flame retardant liquid consists of the following components in percentage by weight: melamine 3%, ammonium polyphosphate 4%, boric acid 3% . 9. The composite wallpaper according to claim 6, characterized in that the flame retardant in the flame retardant liquid consists of the following components in percentage by weight: 5% melamine, 10% ammonium polyphosphate, sulfamic acid Guanidine 20%. 10. The composite wallpaper according to claim 6, characterized in that the flame retardant in the flame retardant liquid consists of the following components in percentage by weight: 5% dicyandiamide, 5% phosphoric acid, sulfamic acid Guanidine 12%.