CN102587218B - Composite wallpaper containing polyvinyl chloride - Google Patents
Composite wallpaper containing polyvinyl chloride Download PDFInfo
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- CN102587218B CN102587218B CN201110411352.2A CN201110411352A CN102587218B CN 102587218 B CN102587218 B CN 102587218B CN 201110411352 A CN201110411352 A CN 201110411352A CN 102587218 B CN102587218 B CN 102587218B
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Abstract
The invention relates to composite wallpaper containing polyvinyl chloride and discloses composite polyvinyl chloride (PVC) wallpaper with a flame retarding polyvinyl chloride (for short flame retarding PVC) coating or film as a surface layer and flame retarding paper as a bottom layer. Components of the flame retarding PVC surface layer, by weight ratio, comprise PVC resin 100, a plasticizer 0-50, a flame retardant 20-80, a stabilizing agent 0.01-1, filler 40-150, a foaming agent 0-1 and a thinning agent 0-10. Paper which is not flame retarding is soaked, flame retarding liquid is sprayed or brush-coated on the paper which is not flame retarding, and then drying is conducted to obtain the flame retarding paper. Compared with a traditional processing method of adopting antimonous oxide as a PVC surface layer flame retardant and adopting ammonium polyphosphate as a paper base layer flame retardant, the flame retarding PVC wallpaper is environment-friendly, low in toxicity and small in smoke density during burning, oxygen index can reach above 32%, and burning performance can reach a GB8624-2006B level.
Description
Technical field
The present invention relates to wallpaper, be specifically related to a kind of composite wallpaper containing polyvinyl chloride.
Background technology
Wallpaper, as a kind of inner decoration material in room, is not only widely used in the public places such as hotels, and along with the improvement of living standards of the people and house condition, steps into huge numbers of families.Decorative wall paper, although can beautify room, because the wallpaper generally used is all inflammable, this is potential fire hazard just.Once room breaking out of fire, just may ignite wallpaper, or flame spreads along wallpaper, and the intensity of a fire is expanded.From the angle of fire safety, that development and application does not fire or fire-retardant wallpaper is necessary.
Along with enhancing and a series of national standard of people's fire-fighting and environmental consciousness, as promulgation and the enforcement of GB50222-95 " code for fire prevention design of interior decoration of buildings ", GB20286-2006 " public place fire-retardant product and assembly combustibility require and mark ", GB 8624-2006 " construction material and product burns grading performance ", GB18585-2001 " in indoor decorating and refurnishing materials wallpaper limits of harmful substances " etc., interior decoration wallpaper used the maintenance function such as fire-retardant is outer also must environmental protection, be therefore badly in need of the new environmental-protection flame-retardant wallpaper of research and development and relevant art thereof.
PVC wallpaper is made up of paper substrate and PVC surface layer usually.Chloridely in PVC molecule reaching 56%, is a kind of self-extinguishing polymer, its limited oxygen index >45%.But in wallpaper production process, in order to make wallpaper high resilience and flexibility, need the plasticizer adding 30%-80% in PVC.When PVC is due to the diluting effect of plasticizer or other additive and when making its total chlorinty drop to about 30%, the oxygen index (OI) of goods declines greatly.In the PVC surface layer thickener of wallpaper, the content of plasticizer can reach 70 parts (100 parts of PVC), and the oxygen index (OI) of base paper is generally 19 ~ 20%, the PVC wallpaper be composited, and its oxygen index (OI), about 21%, easily burns.Therefore, the wallpaper of fire department to plastic wall paper especially skyscraper has clear stipulaties, its oxygen index (OI) >=27% of General Requirements.
Base paper flame-retarded technology not yet really reaches a standard at present completely in China.Because base paper will bear the high temperature of about 200 DEG C in its surperficial PVC plastic chemical industry sequence, most water-soluble inorganic flame retardant often occurs that paper color turns to be yellow when being used to flame treatment base paper, intensity degradation, fragility increases, the problems such as folding resistance is very poor, more seriously, the easy crystallization of fire retardant, the easy moisture absorption of paper, inter-adhesive, a lot of problem is brought to the storage of wallpaper and use.As Chinese patent, (application number: 87105201) disclose fire-resisting wallpaper of polyvinyl chloride, the fire retardant that wherein wallpaper base paper layer is used is APP, adopts the base paper of this fire retardant process namely to there will be above-mentioned problems.
Carrying out the most frequently used method of flame treatment to PVC surface layer is add antimonous oxide (Sb2O3), as Chinese patent (application number: 87105201) disclose fire-resisting wallpaper of polyvinyl chloride, the fire retardant that wherein polyvinyl chloride film is used is Sb2O3, but standard GB/T 18585-2001 " in indoor decorating and refurnishing materials wallpaper limits of harmful substances " is to content of beary metal in wallpaper, content as antimony has strict restriction, require that its content in wallpaper is no more than 20 milligrams per kilogram, this regulation limits Sb2O3 as the application of fire retardant in wallpaper.Therefore be badly in need of the new flame-retarded technology of exploitation, replace the use of Sb2O3 in PVC flame wallpaper.
Summary of the invention
Poor in order to overcome wallpaper flame retardant effect in prior art, the shortcoming such as not environmentally, the invention provides the compound PVC wallpaper of a kind of environmental protection flame retardant low-smoke low-toxicity.
It is flame-proof polyvinyl chloride coating or film that one aspect of the present invention provides a kind of surface layer, bottom is the composite wallpaper of fire retardant papers, and surface layer described in it is made up of the component of following weight proportioning: polyvinyl chloride resin 100 parts, 0 ~ 50 part, plasticizer, fire retardant 20 ~ 80 parts, stabilizing agent 0.01 ~ 1 part, filler 40 ~ 95 parts, blowing agent 0 ~ 1 part, diluent 3 ~ 10 parts; Wherein said fire retardant is one or more in Firebrake ZB, aluminium hydroxide, triethyl phosphate, magnesium hydroxide, phosphoric acid hexichol 2-Octyl Nitrite, chlorinated paraffin wax, APP, tributyl phosphate, tricresyl phosphate (2-chloroethyl) ester; Described plasticizer be dibutyl phthalate, o-phthalic acid dibutyl ester, diisobutyl phthalate, dioctyl adipate, di-n-octyl sebacate one or more; Described stabilizing agent is the one of calcium zinc stabilizer or dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent; Described filler is the one of talcum powder, calcium carbonate, titanium dioxide; Described blowing agent is Celogen Az or azodiisobutyronitrile; Described diluent is toluene or dimethylbenzene.
The surface layer of above-mentioned composite wallpaper is preferably made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, APP 10 parts, tributyl phosphate 40 parts, chlorinated paraffin wax 10 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.3 part, titanium dioxide 60 parts, dimethylbenzene 10 parts.
The surface layer of above-mentioned composite wallpaper is preferably made up of the component of following weight proportion again: polyvinyl chloride resin 100 parts, dibutyl phthalate 25 parts, Firebrake ZB 5 parts, 5 parts, aluminium hydroxide, triethyl phosphate 10 parts, G-618CZ type calcium zinc stabilizer 0.01 part, talcum powder 40 parts, Celogen Az 1 part, toluene 10 parts.
The surface layer of above-mentioned composite wallpaper is also preferably made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, diisobutyl phthalate 50 parts, magnesium hydroxide 20 parts, phosphoric acid hexichol 2-Octyl Nitrite 30 parts, chlorinated paraffin wax 30 parts, G-618CZ type calcium zinc stabilizer 1 part, 150 parts, calcium carbonate, toluene 3 parts.
The surface layer of above-mentioned composite wallpaper is also preferably made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, o-phthalic acid dibutyl ester 25 parts, magnesium hydroxide 10 parts, tricresyl phosphate (2-chloroethyl) ester 40 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.5 part, titanium dioxide 95 parts, azodiisobutyronitrile 0.5 part, diluent dimethylbenzene 5 parts.
Present invention also offers a kind of preparation method of bottom fire retardant papers of composite wallpaper, be specifically prepared from by following method: will not fire retardant papers first in fire resistant fluid dipping or spraying, brush fire resistant fluid, and then through super-dry method and make; Wherein said fire resistant fluid is the aqueous solution or emulsion, the fire retardant in fire resistant fluid be a) nitrogenous flame ratardant one or more, one or more or one or more c) in aluminium hydroxide, magnesium hydroxide, boric acid, Firebrake ZB, zinc stannate b) in phosphonium flame retardant.
The aqueous solution described in preparation method of the bottom fire retardant papers of above-mentioned a kind of composite wallpaper or the concentration expressed in percentage by weight of emulsion are preferably 10 ~ 35%.
Fire retardant in fire resistant fluid described in the preparation method of the bottom fire retardant papers of above-mentioned a kind of composite wallpaper is preferably made up of the component of following weight percentage: dicyandiamide 5%, APP 10%, Firebrake ZB 5%.
Fire retardant in fire resistant fluid described in the preparation method of the bottom fire retardant papers of above-mentioned a kind of composite wallpaper is also preferably made up of the component of following weight percentage: melamine 3%, APP 4%, boric acid 3%.
Fire retardant in fire resistant fluid described in the preparation method of the bottom fire retardant papers of above-mentioned a kind of composite wallpaper is also preferably made up of the component of following weight percentage: melamine 5%, APP 10%, Guanidine Sulfamate 99 20%.
Fire retardant in fire resistant fluid described in the preparation method of the bottom fire retardant papers of above-mentioned a kind of composite wallpaper is also preferably made up of the component of following weight percentage: dicyandiamide 5%, phosphoric acid 5%, Guanidine Sulfamate 99 12%.
Compound PVC wallpaper of the present invention compared with prior art, has the following advantages:
1) the poisonous fire retardant of heavy metal is not contained in wallpaper surface layer, as Sb
2o
3, meet environmental requirement;
2) wallpaper bottom adopts compound flame retardant, and the wallpaper bottom after flame treatment is nothing jaundice, embrittlement phenomenon in subsequent high temperature operation, fire retardant not easily crystallization in storing process, and the moisture absorption and adhesion do not occur paper;
3) PVC wallpaper adopting the present invention to produce adopts standard GB/T 8624-2006 to detect, and can reach B level, toxicity is low, smoke density is little, and oxygen index (OI) can reach more than 32%, improves its fire protecting performance.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but this explanation does not limit the scope of the invention.
The compound PVC wallpaper of environmental-protection flame-retardant low-smoke low-toxicity of the present invention, with flame-proof PVC coating or film for surface layer, fire retardant papers is bottom.
Embodiment 1
According to patent (application number: 87105201), with flame-proof PVC film for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, dioctyl phthalate (DOP) 52 parts, liquid Ba-Cd-Zn 2 parts, three salt lead stearate 1 part, lead stearate 1 part, stearic acid 0.2 part, CaCO
380 parts, antimonous oxide 5 parts; Fire retardant papers is containing the white component of APP 30%(weight by not fire retardant papers dipping) the aqueous solution, then dry and form.Adopt the flame-proof PVC wallpaper that the method is made, by GB5454-1997 test, oxygen index (OI) is 27%; According to GB5455-1997 test, char length >200mm, glow time >5s, after flame time >5s.In addition, the wallpaper bottom after flame treatment has jaundice, embrittlement phenomenon in subsequent high temperature operation, the easy crystallization of fire retardant in storing process, the paper generation moisture absorption and adhesion.
Embodiment 2
With flame-proof PVC coating for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, dibutyl phthalate (DBP) 25 parts, Firebrake ZB 5 parts, 5 parts, aluminium hydroxide, triethyl phosphate 10 parts, G-618CZ type calcium zinc stabilizer (Xiamen City is with auspicious Chemical Co., Ltd. of Allianz) 0.01 part, talcum powder 40 parts, Celogen Az 1 part, toluene 10 parts; Fire retardant papers be by not fire retardant papers first through dipping containing dicyandiamide 5%(percentage by weight), APP 10%(percentage by weight), Firebrake ZB 5%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 32%; According to GB5455-1997 test, char length 120mm, glow time 1s, after flame time 1s; By GB8624-2006 test, combustibility reaches B-s2, d0, t1 level.Wallpaper bottom after flame treatment is without jaundice, embrittlement phenomenon in subsequent high temperature operation, and in storing process, fire retardant nodeless mesh is separated out, and paper is without the moisture absorption and adhesion phenomenon.
Embodiment 3
With flame-proof PVC film for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, diisobutyl phthalate 50 parts, magnesium hydroxide 20 parts, phosphoric acid hexichol 2-Octyl Nitrite 30 parts, chlorinated paraffin wax 30 parts, G-618CZ type calcium zinc stabilizer 1 part, 150 parts, calcium carbonate, toluene 3 parts; Fire retardant papers be by not fire retardant papers first through dipping containing melamine 3%(percentage by weight), APP 4%(percentage by weight), boric acid 3%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 33%; According to GB5455-1997 test, char length 100mm, glows the time 0, after flame time 1s; By GB8624-2006 test, combustibility reaches B-s2, d0, t1 level.Wallpaper bottom after flame treatment is without jaundice, embrittlement phenomenon in subsequent high temperature operation, and in storing process, fire retardant nodeless mesh is separated out, and paper is without the moisture absorption and adhesion phenomenon.
Embodiment 4
With flame-proof PVC film for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, APP 10 parts, tributyl phosphate 40 parts, chlorinated paraffin wax 10 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.3 part, titanium dioxide 60 parts, dimethylbenzene 10 parts; Fire retardant papers be by not fire retardant papers first through dipping containing melamine 5%(percentage by weight), APP 10%(percentage by weight), Guanidine Sulfamate 99 20%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 33.4%; According to GB5455-1997 test, char length 80mm, glows the time 0, after flame time 0; By GB8624-2006 test, combustibility reaches B-s2, d0, t1 level.Wallpaper bottom after flame treatment is without jaundice, embrittlement phenomenon in subsequent high temperature operation, and in storing process, fire retardant nodeless mesh is separated out, and paper is without the moisture absorption and adhesion phenomenon.
Embodiment 5
With flame-proof PVC film for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, o-phthalic acid dibutyl ester (DOP) 25 parts, magnesium hydroxide 10 parts, tricresyl phosphate (2-chloroethyl) ester 40 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.5 part, titanium dioxide 95 parts, azodiisobutyronitrile 0.5 part, dimethylbenzene 5 parts; Fire retardant papers be by not fire retardant papers first through dipping containing dicyandiamide 5%(percentage by weight), phosphoric acid 5%(percentage by weight), Guanidine Sulfamate 99 12%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 32.6%; According to GB5455-1997 test, char length 95mm, glow time 1s, after flame time 0; By GB8624-2006 test, combustibility reaches B-s2, d0, t1 level.Wallpaper bottom after flame treatment is without jaundice, embrittlement phenomenon in subsequent high temperature operation, and in storing process, fire retardant nodeless mesh is separated out, and paper is without the moisture absorption and adhesion phenomenon.
Embodiment 6
With flame-proof PVC film for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, dioctyl adipate (DOA) 60 parts, APP 10 parts, tributyl phosphate 40 parts, chlorinated paraffin wax 10 parts, G-618CZ type calcium zinc stabilizer 0.3 part, 60 parts, barium sulfate, triethanolamine 5 parts; Fire retardant papers be by not fire retardant papers first through dipping containing melamine 5%(percentage by weight), APP 8%(percentage by weight), Guanidine Sulfamate 99 15%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 25%; According to GB5455-1997 test, char length >150mm; By GB8624-2006 test, combustibility fails to reach B level.
Embodiment 7
With flame-proof PVC coating for surface layer, fire retardant papers is the compound PVC wallpaper of bottom, and the weight ratio of flame-proof PVC surface layer component is: polyvinyl chloride resin 100 parts, di-n-octyl sebacate DOS 50 parts, APP 10 parts, chlorinated paraffin wax 8 parts, G-618CZ type calcium zinc stabilizer 0.3 part, 60 parts, potter's clay, dimethylbenzene 5 parts; Fire retardant papers be by not fire retardant papers first through dipping containing melamine 5%(percentage by weight), APP 8%(percentage by weight), Guanidine Sulfamate 99 15%(percentage by weight) fire resistant fluid, and then through super-dry method and make.This fire-retardant compound PVC wallpaper, by GB5454-1997 test, oxygen index (OI) is 22%; According to GB5455-1997 test, char length >150mm; By GB8624-2006 test, combustibility fails to reach B level.
Claims (10)
1. a surface layer is flame-proof polyvinyl chloride coating or film, bottom is the composite wallpaper of fire retardant papers, it is characterized in that described surface layer is made up of the component of following weight proportioning: polyvinyl chloride resin 100 parts, 0 ~ 50 part, plasticizer, fire retardant 20 ~ 80 parts, stabilizing agent 0.01 ~ 1 part, filler 40 ~ 95 parts, blowing agent 0 ~ 1 part, diluent 3 ~ 10 parts; Wherein said fire retardant is one or more in Firebrake ZB, aluminium hydroxide, triethyl phosphate, magnesium hydroxide, phosphoric acid hexichol 2-Octyl Nitrite, chlorinated paraffin wax, APP, tributyl phosphate, tricresyl phosphate (2-chloroethyl) ester; Described plasticizer be dibutyl phthalate, o-phthalic acid dibutyl ester, diisobutyl phthalate one or more; Described stabilizing agent is the one of calcium zinc stabilizer or dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent; Described filler is the one of talcum powder, calcium carbonate, titanium dioxide; Described blowing agent is Celogen Az or azodiisobutyronitrile; Described diluent is toluene or dimethylbenzene;
The bottom fire retardant papers of described wallpaper is prepared from by following method: will not fire retardant papers first in fire resistant fluid dipping or spraying, brush fire resistant fluid, and then through super-dry method and make; Wherein said fire resistant fluid is the aqueous solution or emulsion, the fire retardant in fire resistant fluid be a) nitrogenous flame ratardant one or more, one or more or one or more c) in aluminium hydroxide, magnesium hydroxide, boric acid, Firebrake ZB, zinc stannate b) in phosphonium flame retardant.
2. composite wallpaper according to claim 1, is characterized in that the surface layer of described wallpaper is made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, APP 10 parts, tributyl phosphate 40 parts, chlorinated paraffin wax 10 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.3 part, titanium dioxide 60 parts, dimethylbenzene 10 parts.
3. composite wallpaper according to claim 1, is characterized in that the surface layer of described wallpaper is made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, dibutyl phthalate 25 parts, Firebrake ZB 5 parts, 5 parts, aluminium hydroxide, triethyl phosphate 10 parts, G-618CZ type calcium zinc stabilizer 0.01 part, talcum powder 40 parts, Celogen Az 1 part, toluene 10 parts.
4. composite wallpaper according to claim 1, is characterized in that the surface layer of described wallpaper is made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, diisobutyl phthalate 50 parts, magnesium hydroxide 20 parts, phosphoric acid hexichol 2-Octyl Nitrite 30 parts, chlorinated paraffin wax 30 parts, G-618CZ type calcium zinc stabilizer 1 part, 150 parts, calcium carbonate, toluene 3 parts.
5. composite wallpaper according to claim 1, is characterized in that the surface layer of described wallpaper is made up of the component of following weight proportion: polyvinyl chloride resin 100 parts, o-phthalic acid dibutyl ester 25 parts, magnesium hydroxide 10 parts, tricresyl phosphate (2-chloroethyl) ester 40 parts, dimercapto 2-ethyl hexyl ethanoate dioctyltin stabilizing agent 0.5 part, titanium dioxide 95 parts, azodiisobutyronitrile 0.5 part, diluent dimethylbenzene 5 parts.
6. composite wallpaper according to claim 1, is characterized in that the concentration expressed in percentage by weight of the described aqueous solution or emulsion is preferably 10 ~ 35%.
7. composite wallpaper according to claim 1, is characterized in that the fire retardant in described fire resistant fluid is made up of the component of following weight percentage: dicyandiamide 5%, APP 10%, Firebrake ZB 5%.
8. composite wallpaper according to claim 1, is characterized in that the fire retardant in described fire resistant fluid is made up of the component of following weight percentage: melamine 3%, APP 4%, boric acid 3%.
9. composite wallpaper according to claim 1, is characterized in that the fire retardant in described fire resistant fluid is made up of the component of following weight percentage: melamine 5%, APP 10%, Guanidine Sulfamate 99 20%.
10. composite wallpaper according to claim 1, is characterized in that the fire retardant in described fire resistant fluid is made up of the component of following weight percentage: dicyandiamide 5%, phosphoric acid 5%, Guanidine Sulfamate 99 12%.
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| CN201110411352.2A CN102587218B (en) | 2011-12-12 | 2011-12-12 | Composite wallpaper containing polyvinyl chloride |
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| CN101397377A (en) * | 2007-09-25 | 2009-04-01 | Sk能源株式会社 | Auxiliary plasticizers of PVC and PVC sol composition and products containing the same |
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| CN102587218A (en) | 2012-07-18 |
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