CN105440491A - High-resilience stereo polyvinyl chloride sheet and preparation method thereof - Google Patents
High-resilience stereo polyvinyl chloride sheet and preparation method thereof Download PDFInfo
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- CN105440491A CN105440491A CN201510947991.9A CN201510947991A CN105440491A CN 105440491 A CN105440491 A CN 105440491A CN 201510947991 A CN201510947991 A CN 201510947991A CN 105440491 A CN105440491 A CN 105440491A
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/06—Homopolymers or copolymers of vinyl chloride
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- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of sheet, and particularly, relates to a high-resilience stereo polyvinyl chloride (PVC) sheet and a preparation method thereof. The high-resilience stereo PVC sheet includes the following raw materials in parts by weight: 80-100 parts of PVC resin, 5-10 parts of a plasticizer, 1-3 parts of a heat stabilizer, 1-5 parts of an elastic modifier, 2-4 parts of a foaming agent and 6-10 parts of a lubricant. According to the sheet, the raw materials are adopted, the weight ratios of the raw materials are strictly controlled, and the prepared sheet has the advantages of good resilience effect, heat resistance, cold resistance, acid resistance, alkali resistance, great pressure resistance, aging resistance, static electricity resistance, smooth surface, no cracks, no bubbles, uniform color and luster, soft texture, comfortable hand feeling, health and environmental protection.
Description
Technical field
The present invention relates to sheet technology field, be specifically related to three-dimensional polychlorovinyl sheet material of a kind of high resilience and preparation method thereof.
Background technology
Soft PVC sheet material transparent attractive in appearance, quality is soft, has been widely used in everyday articles field, as the tablecloth, mat applying and table mat etc.This based article is generally enclose transparent film at the another side of printed patterns, when cover furniture especially on glass furniture time, both can show the printed patterns on transparent film, and the pattern of furniture can have been observed again through transparent film, play good decorative effect.But existing pattern is generally all plane pattern, and appreciative value is less; And sheet material resilience effect is bad, overall performance is poor.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide the three-dimensional polychlorovinyl sheet material of a kind of high resilience, this sheet material resilience is effective, and heat-resisting, cold-resistant, acidproof, alkaline-resisting, resistant to pressure, anti-aging, antistatic, smooth surface, leakless, bubble-free, uniform color, quality is soft, hand feel and drape, health environment-friendly.
Another object of the present invention is to the preparation method providing the three-dimensional polychlorovinyl sheet material of a kind of high resilience, this preparation method's technique is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: the three-dimensional polychlorovinyl sheet material of a kind of high resilience, and the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 80-100 part
Softening agent 5-10 part
Thermo-stabilizer 1-3 part
Elastomeric modification agent 1-5 part
Whipping agent 2-4 part
Lubricant 6-10 part.
Sheet material of the present invention is by adopting above-mentioned raw materials, and the strict weight proportion controlling each raw material, obtained sheet material resilience is effective, and heat-resisting, cold-resistant, acidproof, alkaline-resisting, resistant to pressure, anti-aging, antistatic, smooth surface, leakless, bubble-free, uniform color, quality is soft, hand feel and drape, health environment-friendly.
Preferably, the mixture that is made up of with weight ratio 1:2-4 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin of described polyvinyl chloride resin.
The present invention adopts calcium carbide process PVC resin and ethylene process polyvinyl chloride resin as the composite use of raw material, and to control its weight ratio be 1:2-4, makes plasticize speed fast, easily processes.
The mixture that described softening agent is made up of with weight ratio 1:0.8-1.2:1.5-2.5 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The present invention adopts epoxy soybean oil, triethyl citrate and synthesis vegetable esters as the composite use of softening agent, three kinds of softening agent are environment-friendly plasticizer, the reactive force between PVC molecular chain can be reduced, the fusing point of the second-order transition temperature of PVC plastic, yield temperature and contained crystallite is all reduced, softening agent can improve the plasticity-of resin, makes goods softness, resistance to low temperature good; And when the use composite with weight ratio 1:0.8-1.2:1.5-2.5 of three kinds of softening agent, flexibility and the resistance to low temperature of goods can be improved.
Preferably, the mixture that is made up of with weight ratio 1:0.8-1.2 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer of described thermo-stabilizer.
Ca-Zn composite heat stabilizer not only can replace the poisonous stablizers such as plumbous cadmium salt class and organic tin, and has goodish thermostability, light stability and the transparency and tinting strength.Facts have proved, in polyvinyl chloride resin goods, good processability, heat stabilization is equivalent to lead salt stabilizer, is a kind of good non-toxic stabilizer.
Hydrotalcite stablizer has high thermal stability: distinctive sour absorption mechanism, result in its thermostability of thermostability higher than lead base; High transparent: have identical specific refractory power with PVC; High-insulativity: by anion exchange reaction, absorbed muriate can not discharge, and insulativity is splendid; High security: hydrotalcite can be applicable in the food pack of polymer materials; Good weathering resistance (environmental compatibility is strong), can not produce sulfide staining: can with various thermo-stabilizer with the use of.
The present invention is by adopting Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer as the composite use of thermo-stabilizer, and to control its weight ratio be 1:0.8-1.2, can make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5-1.5:1:0.5-1.5:0.8-1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The present invention is by adopting calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate as Ca-Zn composite heat stabilizer, and to control its weight ratio be 0.5-1.5:1:0.5-1.5:0.8-1.2, there is goodish thermostability, light stability and the transparency and tinting strength, and good processability.
Preferably, described elastomeric modification agent be second-order transition temperature 80-90 DEG C, density is at 1.04-1.06g/cm
3polystyrene foamed.
Polystyrene foamed (EPS), also known as Expandable Polystyrene (EPS), is be polymerized by styrene suspension, then adds whipping agent and obtain.EPS is the hard honeycomb shape foam thing of polystyrene (PS), and have good thermal insulation and shock absorption effect, high compression-strength, very light weight, polystyrene foamed joins in PVC, can improve the elasticity of material.
The present invention by the second-order transition temperature of polystyrene foamed is controlled 80-90 DEG C, density domination is at 1.04-1.06g/cm
3, obtained elastic properties of materials is good, tensile strength and elongation large, the elasticity of material be improved significantly.
Preferably, the mixture that is made up of with weight ratio 2-4:1 Cellmic C 121 and diisopropyl azodiformate of described whipping agent.
The present invention is by adopting Cellmic C 121 and diisopropyl azodiformate as the composite use of whipping agent, and to control its weight ratio be 2-4:1, and foaming effect is good, and gas forming amount is maximum, superior performance.
Preferably, the mixture that is made up of with weight ratio 1.5-2.5:1:0.8-1.2 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide of described lubricant.
The present invention adopts oxidized polyethlene wax as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt pentaerythritol stearate and ethylene bis stearic acid amide as internal lubricant, the intermolecular friction of PVC melt can be reduced; Three kinds of lubricants can make material in the course of processing, improve the mobility of material and the release property of goods with the composite use of weight ratio 1.5-2.5:1:0.8-1.2.
Preferably, the three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 10-20 part and impact modifier 1-5 part, and described weighting agent is that particle diameter is at 1-10nm and through the nano-calcium carbonate of silane coupling agent process.
The particle diameter of weighting agent is less, to the tensile strength of packing material and shock strength more useful, the present invention, by adopting nano-calcium carbonate as weighting agent and controlling its particle diameter at 1-10nm, can improve the intensity of material; Weighting agent and the good consistency of resin play its key acting on and control addition, and the present invention adopts the nano-calcium carbonate through silane coupling agent process, can improve the consistency of nano-calcium carbonate and polyvinyl chloride resin, thus the intensity of raising material.
Described impact modifier is the mixture that the chlorinatedpolyethylene of 25%-45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 5%-25% form with weight ratio 1.5-2.5:1 by chlorinity.
Chlorinatedpolyethylene (CPE) is a kind of properties-correcting agent of thermoplastics, has good over-all properties.Appropriate CPE is added, the processing characteristics that can reduce the melt viscosity of resin, improve mobility, improve plastics in polyvinyl chloride (PVC) resin; The work-ing life of the shock strength of PVC, resistance to low temperature, weathering performance, prolongation goods can also be improved.CPE is added in calcic-plastic composite material, not only can replace Plasticizer DBP, also contributes to the dispersed of calcium carbonate and polyvinyl chloride resin; And when the chlorinity (weight content) of chlorinatedpolyethylene is for 25%-45%, make the resistance to impact shock of material best.
Ethylene-vinyl acetate copolymer (EVA) can be used as the impact modifying agent of PVC, has good flexibility, obdurability, lower temperature resistance (-58 DEG C still have pliability), weathering resistance, stress cracking resistance, heat sealer, agglutinating value(of coal), the transparency and glossiness; Also there is the elasticity as rubber simultaneously, excellent chemical stability, thermostability (heat decomposition temperature 229 ~ 230 DEG C), ozone resistance, nontoxicity, good processibility and dyeability; Fine with the miscibility of filler, even if fill more filler, also unlikelyly have a strong impact on its physical and mechanical property.
EVA is as the impact modifying agent of PVC, its effect is different with the content of vinyl acetate between to for plastic in multipolymer, when the content of vinyl acetate between to for plastic is low, with the poor compatibility of PVC, reinforced effects is poor, and goods are opaque, along with the increase of vinyl acetate between to for plastic unit content, the consistency of multipolymer and PVC improves, and reinforced effects improves, and the goods transparency is also better; But the content of vinyl acetate between to for plastic also can not be too high, during vinyl acetate between to for plastic unit content 5%-25%, obviously can improve the shock strength of PVC, compared with the impact modifying agent containing carbon-carbon double bond, also there is the good advantage of ageing resistance.
The present invention is by adopting chlorinatedpolyethylene and ethylene-vinyl acetate copolymer as the composite use of impact modifier, and to control its weight ratio be 1.5-2.5:1, the high temperature resistant of material and resistance to low temperature can be improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the work-ing life of the shock strength of material, weathering performance, prolongation goods.
Preferably, the three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 1-5 part, slipping agent 0.05-0.15 part and pigment powder 0.01-0.05 part; The mixture that described fire retardant is made up of with weight ratio 0.5-1.5:1 antimonous oxide and zinc borate.
Antimony peroxide and lime borate are inorganic environment-friendly fire retardant, the present invention is by adopting antimonous oxide and zinc borate as the composite use of fire retardant, and to control its weight ratio be 0.5-1.5:1, good flame retardant effect can be reached, Drawing abillity and mechanical property can also be improved.
Described slipping agent is the mixture be made up of with weight ratio 1.5-2.5:0.8-1.2:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide.
The present invention is by adopting erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide is as slipping agent and to control its weight ratio be 1.5-2.5:0.8-1.2:1, mechanical resistant stirring capacity and fingerprinting stress can be strengthened, finished product good forming effect, any surface finish, the extensibility of finished product can also be strengthened, easy-to-draw not easily broken.
Described pigment powder is particle diameter at the titanium dioxide of 1-5 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.5-2.5 Rutile type Titanium Dioxide and anatase thpe white powder.
The present invention adopts particle diameter at the titanium dioxide of 1-5 μm as pigment powder, further employing Rutile type Titanium Dioxide and the composite use of anatase thpe white powder, and to control its weight ratio be 1:1.5-2.5, there is superior whiteness, tinting strength, opacifying power, weathering resistance, thermotolerance and chemical stability, particularly there is no toxicity.
Another object of the present invention is achieved through the following technical solutions: the preparation method of the three-dimensional polychlorovinyl sheet material of a kind of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 12-18min at 35-40 DEG C of temperature, and the rotating speed of stirring is 1000-1160RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 15-25s at 170-190 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Preferably, in described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 140-150 DEG C, 135-145 DEG C, 135-145 DEG C, 130-140 DEG C, 130-140 DEG C and 125-135 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: a district temperature 175-185 DEG C, two district temperature 190-200 DEG C, three district temperature 190-200 DEG CHe tetra-district temperature 175-185 DEG C.
Beneficial effect of the present invention is: sheet material resilience of the present invention is effective, and heat-resisting, cold-resistant, acidproof, alkaline-resisting, resistant to pressure, anti-aging, antistatic, smooth surface, leakless, bubble-free, uniform color, quality is soft, hand feel and drape, health environment-friendly.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
The three-dimensional polychlorovinyl sheet material of a kind of high resilience, the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 80 parts
5 parts, softening agent
Thermo-stabilizer 1 part
Elastomeric modification agent 1 part
Whipping agent 2 parts
Lubricant 6 parts.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 1:2 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:0.8:1.5 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:0.8 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5:1:0.5:0.8 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
Described elastomeric modification agent be second-order transition temperature 80 DEG C, density is at 1.04g/cm
3polystyrene foamed.
The mixture that described whipping agent is made up of with weight ratio 2:1 Cellmic C 121 and diisopropyl azodiformate.
The mixture that described lubricant is made up of with weight ratio 1.5:1:0.8 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 10 parts and impact modifier 1 part, and described weighting agent is that particle diameter is at 1nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 25% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 5% form with weight ratio 1.5:1 by chlorinity.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 1 part, slipping agent 0.05 part and 0.01 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.1:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 1.5:0.8:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 1 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.5 Rutile type Titanium Dioxide and anatase thpe white powder.
A preparation method for the three-dimensional polychlorovinyl sheet material of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 12min at 35 DEG C of temperature, and the rotating speed of stirring is 1000RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 15s at 170 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
In described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 140 DEG C, 135 DEG C, 135 DEG C, 130 DEG C, 130 DEG C and 125 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: district's temperature 175 DEG C, two district's temperature 190 DEG C, three district's temperature 190 DEG CHe tetra-district temperature 175 DEG C.
Embodiment 2
The three-dimensional polychlorovinyl sheet material of a kind of high resilience, the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 85 parts
6 parts, softening agent
Thermo-stabilizer 1.5 parts
Elastomeric modification agent 2 parts
Whipping agent 2.5 parts
Lubricant 7 parts.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 1:2.5 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:0.9:1.8 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:0.9 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.8:1:0.8:0.9 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
Described elastomeric modification agent be second-order transition temperature 82 DEG C, density is at 1.04g/cm
3polystyrene foamed.
The mixture that described whipping agent is made up of with weight ratio 2.5:1 Cellmic C 121 and diisopropyl azodiformate.
The mixture that described lubricant is made up of with weight ratio 1.8:1:0.9 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 12 parts and impact modifier 2 parts, and described weighting agent is that particle diameter is at 3nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 30% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 10% form with weight ratio 1.8:1 by chlorinity.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 2 parts, slipping agent 0.08 part and 0.02 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.2:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 1.8:0.9:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 2 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.8 Rutile type Titanium Dioxide and anatase thpe white powder.
A preparation method for the three-dimensional polychlorovinyl sheet material of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 13min at 36 DEG C of temperature, and the rotating speed of stirring is 1040RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 17s at 175 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
In described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 142 DEG C, 137 DEG C, 137 DEG C, 132 DEG C, 132 DEG C and 127 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: district's temperature 177 DEG C, two district's temperature 192 DEG C, three district's temperature 192 DEG CHe tetra-district temperature 177 DEG C.
Embodiment 3
The three-dimensional polychlorovinyl sheet material of a kind of high resilience, the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 90 parts
7 parts, softening agent
Thermo-stabilizer 2 parts
Elastomeric modification agent 3 parts
Whipping agent 3 parts
Lubricant 8 parts.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 1:2 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:1:2 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1:1:1:1 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
Described elastomeric modification agent be second-order transition temperature 85 DEG C, density is at 1.05g/cm
3polystyrene foamed.
The mixture that described whipping agent is made up of with weight ratio 3:1 Cellmic C 121 and diisopropyl azodiformate.
The mixture that described lubricant is made up of with weight ratio 2:1:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 15 parts and impact modifier 3 parts, and described weighting agent is that particle diameter is at 5nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 35% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 15% form with weight ratio 2:1 by chlorinity.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 3 parts, slipping agent 0.1 part and 0.03 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.3:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2:1:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 3 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2 Rutile type Titanium Dioxide and anatase thpe white powder.
A preparation method for the three-dimensional polychlorovinyl sheet material of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 15min at 37 DEG C of temperature, and the rotating speed of stirring is 1080RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 20s at 180 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
In described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 145 DEG C, 140 DEG C, 140 DEG C, 135 DEG C, 135 DEG C and 130 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: district's temperature 180 DEG C, two district's temperature 195 DEG C, three district's temperature 195 DEG CHe tetra-district temperature 180 DEG C.
Embodiment 4
The three-dimensional polychlorovinyl sheet material of a kind of high resilience, the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 95 parts
8.5 parts, softening agent
Thermo-stabilizer 2.5 parts
Elastomeric modification agent 4 parts
Whipping agent 3.5 parts
Lubricant 9 parts.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 1:3.5 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:1.1:2.2 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:1.1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1.2:1:1.2:1.1 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
Described elastomeric modification agent be second-order transition temperature 88 DEG C, density is at 1.05g/cm
3polystyrene foamed.
The mixture that described whipping agent is made up of with weight ratio 3.5:1 Cellmic C 121 and diisopropyl azodiformate.
The mixture that described lubricant is made up of with weight ratio 2.2:1:1.1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 18 parts and impact modifier 4 parts, and described weighting agent is that particle diameter is at 8nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 40% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 20% form with weight ratio 2.2:1 by chlorinity.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 4 parts, slipping agent 0.12 part and 0.04 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.4:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2.2:1.1:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 4 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2.2 Rutile type Titanium Dioxide and anatase thpe white powder.
A preparation method for the three-dimensional polychlorovinyl sheet material of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 17min at 38 DEG C of temperature, and the rotating speed of stirring is 1120RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 23s at 185 DEG C of temperature;
EE, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
In described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 148 DEG C, 143 DEG C, 143 DEG C, 138 DEG C, 138 DEG C and 133 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: district's temperature 183 DEG C, two district's temperature 198 DEG C, three district's temperature 198 DEG CHe tetra-district temperature 183 DEG C.
Embodiment 5
The three-dimensional polychlorovinyl sheet material of a kind of high resilience, the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 100 parts
10 parts, softening agent
Thermo-stabilizer 3 parts
Elastomeric modification agent 5 parts
Whipping agent 4 parts
Lubricant 10 parts.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 1:4 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:1.2:2.5 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:1.2 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1.5:1:1.5:1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
Described elastomeric modification agent be second-order transition temperature 90 DEG C, density is at 1.06g/cm
3polystyrene foamed.
The mixture that described whipping agent is made up of with weight ratio 4:1 Cellmic C 121 and diisopropyl azodiformate.
The mixture that described lubricant is made up of with weight ratio 2.5:1:1.2 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 20 parts and impact modifier 5 parts, and described weighting agent is that particle diameter is at 10nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 25% form with weight ratio 2.5:1 by chlorinity.
The three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 5 parts, slipping agent 0.15 part and 0.05 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.5:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2.5:1.2:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 5 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2.5 Rutile type Titanium Dioxide and anatase thpe white powder.
A preparation method for the three-dimensional polychlorovinyl sheet material of high resilience, comprises the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 18min at 40 DEG C of temperature, and the rotating speed of stirring is 1160RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 25s at 190 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
In described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 150 DEG C, 145 DEG C, 145 DEG C, 140 DEG C, 140 DEG C and 135 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: district's temperature 185 DEG C, two district's temperature 200 DEG C, three district's temperature 200 DEG CHe tetra-district temperature 185 DEG C.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. the three-dimensional polychlorovinyl sheet material of high resilience, is characterized in that: the three-dimensional polychlorovinyl sheet material of described high resilience comprises the raw material of following weight part:
Polyvinyl chloride resin 80-100 part
Softening agent 5-10 part
Thermo-stabilizer 1-3 part
Elastomeric modification agent 1-5 part
Whipping agent 2-4 part
Lubricant 6-10 part.
2. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: the mixture that described polyvinyl chloride resin is made up of with weight ratio 1:2-4 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin; The mixture that described softening agent is made up of with weight ratio 1:0.8-1.2:1.5-2.5 epoxy soybean oil, triethyl citrate and synthesis vegetable esters.
3. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: the mixture that described thermo-stabilizer is made up of with weight ratio 1:0.8-1.2 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5-1.5:1:0.5-1.5:0.8-1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
4. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: described elastomeric modification agent be second-order transition temperature 80-90 DEG C, density is at 1.04-1.06g/cm
3polystyrene foamed.
5. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: the mixture that described whipping agent is made up of with weight ratio 2-4:1 Cellmic C 121 and diisopropyl azodiformate.
6. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: the mixture that described lubricant is made up of with weight ratio 1.5-2.5:1:0.8-1.2 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
7. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, it is characterized in that: the three-dimensional polychlorovinyl sheet material of described high resilience also comprises weighting agent 10-20 part and impact modifier 1-5 part, described weighting agent is that particle diameter is at 1-10nm and through the nano-calcium carbonate of silane coupling agent process; Described impact modifier is the mixture that the chlorinatedpolyethylene of 25%-45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 5%-25% form with weight ratio 1.5-2.5:1 by chlorinity.
8. the three-dimensional polychlorovinyl sheet material of the high resilience of one according to claim 1, is characterized in that: the three-dimensional polychlorovinyl sheet material of described high resilience also comprises fire retardant 1-5 part, slipping agent 0.05-0.15 part and pigment powder 0.01-0.05 part; The mixture that described fire retardant is made up of with weight ratio 0.5-1.5:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 1.5-2.5:0.8-1.2:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 1-5 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.5-2.5 Rutile type Titanium Dioxide and anatase thpe white powder.
9. the preparation method of the three-dimensional polychlorovinyl sheet material of a kind of high resilience as described in any one of claim 1-8, is characterized in that: comprise the steps:
A, raw material prepare: take each raw material by above-mentioned raw materials composition, mixing;
B, high-speed stirring: mixed raw material is put into high speed blender, stir 12-18min at 35-40 DEG C of temperature, and the rotating speed of stirring is 1000-1160RPM, obtains slurry;
C, slurry are coated with: be applied in separate-type paper by the slurry after stirring;
D, slurry are dried: the slurry after coating is dried 15-25s at 170-190 DEG C of temperature;
E, cylinder printing: imported by the slurry of deployed color in cylinder graphic arts die, extruded by high pressure and scrape printing flower pattern local on the shaping rear same stamp PVC of slurry or the stereosopic printing of edge contraposition cylinder;
F, slurry foam: the slurry after printing is put into foaming body of heater and foam;
G, foaming layer laminating: transparent PVC high temperature is fitted in printing foaming layer surface;
H, cooling and shaping: the slurry after foaming is carried out cooling and shaping through drawing cooling wheel;
I, peel off rolling: the foaming layer after shaping and separate-type paper are peeled off, then carry out rolling through winder, obtain high resilience solid polychlorovinyl sheet material.
10. the preparation method of the three-dimensional polychlorovinyl sheet material of a kind of high resilience according to claim 9, it is characterized in that: in described step F, cylinder is six look cylinders, and the bake out temperature of six look cylinders is followed successively by: 140-150 DEG C, 135-145 DEG C, 135-145 DEG C, 130-140 DEG C, 130-140 DEG C and 125-135 DEG C; In described step G, foaming body of heater is divided into 4th district, and four district's temperature are respectively: a district temperature 175-185 DEG C, two district temperature 190-200 DEG C, three district temperature 190-200 DEG CHe tetra-district temperature 175-185 DEG C.
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Application publication date: 20160330 |
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