CN107629350B - Folding water-proof environmental protection PVC material composition and preparation method thereof, purposes - Google Patents
Folding water-proof environmental protection PVC material composition and preparation method thereof, purposes Download PDFInfo
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- CN107629350B CN107629350B CN201710712101.5A CN201710712101A CN107629350B CN 107629350 B CN107629350 B CN 107629350B CN 201710712101 A CN201710712101 A CN 201710712101A CN 107629350 B CN107629350 B CN 107629350B
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Abstract
The invention discloses a kind of folding water-proof environmental protection PVC material composition and preparation method thereof, purposes, by including prepared by each raw material of parts by weight such as：PVC100 parts, 15 parts of stabilizer, 1 10 parts of epoxidized soybean oil, 1 10 parts of methyl methacrylate butyl acrylate copolymer, 3 20 parts of modification agent, 0.1 1.0 parts of lubricant, 1 20 parts of filler, 0 5.0 parts of colouring matter；The stabilizer is at least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer.The present invention is by selecting at least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer to be used as stabilizer and to the optimization of other raw material components, reduce the toxicity of PVC material composition, and significantly improve the mechanical performance of PVC material composition, water resistance etc..
Description
Technical field
The present invention relates to new material technology field, more particularly to a kind of folding water-proof environmental protection PVC material composition and its
Preparation method, purposes.
Background technology
Playing card playing cards be it is a kind of competed using extensive life, amusement article, it can be life addition enjoyment, existing
Playing card are laminated structure, are generally made using paper material, and it is 1 gram that every board, which weighs about, by the body paper of appropriate grams
Upper pattern is republished after the compound equal procedure technologies processing of casting painting, then cut, be made after waxing processing.
China is paper products playing card big producer, but paper products limited by practical, and there are more deficiencies.Its deficiency
Be in：The playing card of papery are easy to make moist, easily lose, inconvenient the shortcomings that reusing and wasting national woods resource, and
Wearability is poor during the board body use of papery, the phenomenon that being susceptible to crack at edge, and service life is shorter；At used one section
Between after, it is the easy blackening of board body, dirty, influence beauty, can't wash.
Demand of the market to PVC product is especially therein to meet the modern high-end production advocated energetically just in rapid growth
The environment-friendly PVC material of product-kind printing, it is even more very popular.And adding used in the playing card PVC material of current domestic production
Add agent to use such as lead salt, barium cadmium soap, organic tin stabilizer and phthalic ester plasticizer mostly, is more toxic.Its
Middle lead salt is poisonous and harmful heavy metallic compound, has been gradually backed out market；Organic tin stabilizer is in process to environment shadow
It rings greatly, and pollution is larger, while organo-tin compound is harmful to human body.It is generally speaking difficult to reach the requirement of client, also not
The heavy metal analysis of European Union's newest REACH regulations and EN71part3 can be passed through.Above many reasons limit domestic printing playing card
The development of board PVC material.
Invention content
Based on this, it is necessary to be directed to the defects of existing playing card are big, folding waterproof ability is poor with PVC material toxicity, this hair
Bright primary and foremost purpose is to provide a kind of folding water-proof environmental protection PVC material composition being suitable for printing playing card.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of folding water-proof environmental protection PVC material composition, by including prepared by each raw material of parts by weight such as：
The stabilizer is at least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer.
In wherein some embodiments, the folding water-proof environmental protection PVC material composition, by including each such as parts by weight
It is prepared by raw material：
The stabilizer is at least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer.
In wherein some embodiments, the stabilizer is magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare earth-stabilized
The mixture of agent, the wherein amount ratio of three ranging from (0.5-3)：(0.5-2.5)：(0.5-3).Especially Guangdong Sen Deli rings
Protect the magnesium-aluminum-zinc composite stabilizer of new material Science and Technology Ltd..
In wherein some embodiments, the lubricant is calcium stearate, zinc stearate, microcrystalline wax, stearic acid, tristearin
At least one of acid butyl ester, polynary carboxylic ester；The filler is at least one of titanium dioxide, talcum powder, calcium carbonate.
In wherein some embodiments, the lubricant is polynary carboxylic ester；The filler is titanium dioxide, in talcum powder extremely
Few one kind.
In wherein some embodiments, the PVC uses SG-7, SG-5, S-65, HG-800, DG-800, TL-800, TL-
1000, at least one of S-1007, S-1008；The modification agent is at least one of MBS, ACR, ABS.
It is a further object of the present invention to provide a kind of preparation methods of folding water-proof environmental protection PVC material composition, including such as
Lower step：
To the PVC of the mass fraction, stabilizer, epoxidized soybean oil, methyl methacrylate-butyl acrylate copolymerization
Object, modification agent, lubricant, filler, colorant are mixed, and mixture material is obtained；
The mixture material squeezes out after screw extruder shears preplasticizing, then through calender compression molding, stretching-machine
Winding is to get the folding water-proof environmental protection PVC material composition after extraction, cooling and shaping, corona.
In wherein some embodiments, the equipment that uses of mixing for thermal agitation machine or mixing machine, the mixing
Time is 5-10min；The screw extruder is star row screw extruder, and the temperature of the screw extruder is 130-180 DEG C,
The rotating speed of the screw extruder is 35-60rpm.
Another object of the present invention is to provide a kind of folding water-proof environmental protection PVC material composition conduct printing playing card
Purposes in board material.
It is yet another object of the invention to provide a kind of playing card, contain above-mentioned folding water-proof environmental protection PVC material composition.
Compared with prior art, the invention has the advantages that：
The present invention is by selecting at least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer to be used as
Stabilizer and optimization to other raw material components, reduce the toxicity of PVC material composition, and significantly improve PVC material
Mechanical performance (such as tearing strength, falling sphere loudness, impact strength), the water resistance of composition.The present invention passes through to stabilization
Agent type it is preferred, realize under conditions of it is not necessary that ultraviolet absorber is added realize mechanical strength promotion.
Further, stabilizer is limited to magnesium-aluminum-zinc composite stabilizer, calcium zinc is stablized by the application also by formulation optimization
Agent, rare-earth stabilizer compound and limit mixed proportion so that the mechanical performance of PVC material composition, water resistance are into one
Step is promoted, and the favorable dispersibility of stabilizer.
In addition, the present invention is by lubricant by being limited to polynary carboxylic ester, by filler be preferably in titanium dioxide, talcum powder extremely
Few one kind, it is furthermore achieved that production efficiency is high, production cost is low, has good economic benefits.
Specific implementation mode
Below in conjunction with specific embodiment to folding water-proof environmental protection PVC material composition of the present invention and preparation method thereof, use
Way is described in further detail.
First, the embodiment of the present invention is related to a kind of folding water-proof environmental protection PVC material composition, by including such as parts by weight
Each raw material prepare：PVC100 parts, 1-5 parts of stabilizer, 1-10 parts of epoxidized soybean oil, methyl methacrylate-butyl acrylate
- 10 parts of copolymer 1,3-20 parts of modification agent, 0.1-1 parts of lubricant, 1-20 parts of filler, 0-5 parts of colouring matter；The stabilizer is
At least one of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer.It is described in wherein some embodiments
Stabilizer is only magnesium-aluminum-zinc composite stabilizer.In wherein some embodiments, the PVC uses SG-5, S-65, HG-800, DG-
800, at least one of TL-800, TL-1000, S-1007, S-1008.In wherein some embodiments, the modification agent is
At least one of MBS, ACR, ABS.In wherein some embodiments, the lubricant is calcium stearate, zinc stearate, crystallite
At least one of paraffin, stearic acid, butyl stearate, polynary carboxylic ester.In wherein some embodiments, the filler is titanium
At least one of white powder, talcum powder, calcium carbonate.
Secondly, the embodiment of the present invention is related to a kind of preparation method of folding water-proof environmental protection PVC material composition, to described
The PVC of mass fraction, stabilizer, epoxidized soybean oil, methyl methacrylate-butyl acrylate copolymer, modification agent, lubrication
Agent, filler, colorant are mixed, and mixture material is obtained；The mixture material squeezes out after screw extruder shears preplasticizing,
Again through calender compression molding, winding is to get the folding water-proof environmental protection PVC material after stretching-machine extraction, cooling and shaping, corona
Composition.In wherein some embodiments, the equipment that uses of mixing for thermal agitation machine or mixing machine, the mixing when
Between be 5-10min.In wherein some embodiments, the screw extruder is star row screw extruder, the screw extruder
Temperature be 130-190 DEG C, rotating speed 35-60rpm.For the preparation method of the present invention, step and its parameter are hairs
What a person of good sense accordingly screened on the basis of preferred to folding water-proof environmental protection PVC material composite formula.
In addition, the invention further relates to a kind of folding water-proof environmental protection PVC material compositions as printing playing card material
In purposes.Playing card, which prepare material thickness, between 0.20-0.40mm to be had environmental protection, folding, waterproof the characteristics such as moisture-sensitive not to be simultaneously
And it uses stabilizer processing to be dispersed in materials microstructure, meets the not stanniferous requirement of environmental protection.
In order to enable technical scheme of the present invention is more specific, clear, it is exemplified below：
Embodiment 1-3
Embodiment 1 provides a kind of folding water-proof environmental protection PVC material composition and preparation method thereof, purposes, and concrete scheme is such as
Under：
The formula of three embodiment folding water-proof environmental protection PVC material compositions is referring to table 1；
The step of preparing folding water-proof environmental protection PVC material composition and obtaining 0.325mm printing playing card materials is as follows：
Each raw material shown in table 1 is sequentially first put into mixing machine to be uniformly mixed, obtains mixed material；
Mixed material is again through star multi-screw extruder (temperature is 130-190 DEG C, rotating speed 35-60rpm) shearing plasticizing
After squeeze out, feeding to four-wheel shears tabletting against L type calender (domestic system, specification ∮ 550mm × L 1850mm), and thickness control exists
The hot melt adhesive plaster of 0.33mm；Then stretching-machine draws, adhesive plaster is introduced to cooling wheel group cooling and shaping, and rolling machine winding is cooling hard
Change sizing to get folding water-proof environmental protection PVC material composition, the folding water-proof environmental protection print of thickness 0.325mm is obtained through batching
Brush playing card material.
Embodiment 2, embodiment 3 are the change case of embodiment 1, and variation place is only that folding water-proof environmental protection PVC material group
The formula for closing object, specifically refers to table 1.
Table 1
Embodiment 4-8
Embodiment 4-8 is a kind of folding water-proof environmental protection PVC material composition of offer and its preparation side of embodiment 1 respectively
Method, purposes, variation place, which is only that, has been respectively adopted formula as shown in table 2 below.
Table 2
Comparative example 1-3
Comparative example 1-3 is the comparative example of embodiment 4, and comparison place is only that formula is different, specifically refers to table 3：
Table 3
According to upper table 3 it is found that being only that in place of comparative example 1,2 and the comparison of embodiment 4：Calcium zinc stabilizer is not used, and
Using organic tin stabilizer.Comparative example 3 is differed only in the application's：Contain acrylic resin, ultraviolet absorber.
Performance test
The performance parameter of above each example is tested, the method for performance test includes：
(1) tin and organo-tin compound content measuring：The test of adhesive plaster content tin (Sr) and organo-tin compound, commission
Third party's SGS detections embodiment meets the newest REACH regulations of European Union and the heavy metal and organo-tin compound limit value of EN71part3
It is required that specification.It can be seen that stanniferous and organo-tin compound is lower represents the more environmentally friendly of polyvinylchloride material.
(2) steam penetrating capacity is tested：Steam penetrating capacity is tested, the Key works Drug packing product inspection of commission third party Guangdong Province
It tests station detection embodiment and meets YBB00212005 requirement specifications.Steam penetrating capacity is smaller to represent the anti-of polyvinylchloride material
It is aqueous better.
(3) tearing strength test：Using U.S.'s TMI boards, model 83-11-01, the folding waterproof ring of testing example
Printing playing card PVC material is protected, method meets 1922 specifications of ASTM-D.Tearing strength is bigger to represent polyvinylchloride material
The folding resistance of material is better.
(4) test of falling sphere intensity：Using Germany instrument power believe instrument, model 304-ASTM, testing example it is resistance to
It rolls over water-proof environmental protection and prints playing card PVC material, method meets ASTM-D2794 specifications.Higher represent of falling sphere intensity fraction is gathered
The falling sphere intensity of vinyl chloride PVC material is better.
(5) test of impact strength：Board, model VF-40DCA- are tested using the homemade impact resistance of Hong Xin companies
10, the polyvinylchloride material of testing example, method meets the inspection criterion of macro letter impact strength.Impact strength score
It is better that intensity is patted in the higher impact resistance for representing polyvinylchloride material.
(6) test of gloss value：Using the instrument of the Ke Shijia photoelectric instruments research institute of Quanzhou City of China, model
The folding water-proof environmental protection of WGG60-E4, testing example print playing card PVC material, and method meets ASTM-D523-89 rule
Model.The lower printing effect for representing polyvinylchloride material of gloss value and three-dimensional sense are better.
Test result is shown in Table 4.
Table 4
According to the result of table 4：
According to embodiment 4,5 properties of product test result of embodiment it is found that the present invention is at PVC100 parts, 1-5 parts of stabilizer,
1-10 parts of epoxidized soybean oil, -10 parts of methyl methacrylate-butyl acrylate copolymer 1,3-20 parts of modification agent, lubricant
0.1-1 parts, 1-20 parts of filler, 0-5 parts of colouring matter and the stabilizer be magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, dilute
The toxicity of PVC material composition can be reduced by holding in the range of at least one of soil stabilizer, and significantly improve PVC materials
Mechanical performance (such as tearing strength, falling sphere loudness, impact strength), the water resistance of feed composition.
According to embodiment 1-3, embodiment 8, embodiment 6-7 properties of product test result it is found that the present invention there is also preferred
Scheme, the application are limited to magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare earth-stabilized also by formulation optimization, by stabilizer
The compound of agent simultaneously limits mixed proportion so that and mechanical performance, the water resistance of PVC material composition are further promoted, and
The favorable dispersibility of stabilizer.
According to the comparison of embodiment 4 and comparative example 1-3 it is found that the advantageous effect of the present invention is by selecting magnalium zinc compound
The base of the optimization of at least one of stabilizer, calcium zinc stabilizer, rare-earth stabilizer as stabilizer and to other raw material components
It is realized on plinth, if the type to stabilizer is replaced, even if increasing dosage, it is also not possible to which realization is equal to the present invention
Effect, the application realizes compared with the existing technology realizes carrying for mechanical strength under conditions of it is not necessary that ultraviolet absorber is added
It rises.
The performance of the product of the present invention is presented on the whole：Moisture-sensitive, vapor is not saturating for resistant to chemical etching, acid and alkali-resistance, waterproof
Excessive ＜ 2.5g/ (m2.24h)；Glossiness (60 °) ＜ 100GU of products obtained therefrom, using high tenacity modification agent, material is not easy to tear
It splits, folding, impact strength is good (＞ 85%), and falling sphere intensity is good (＞ 200g.m), tearing strength (longitudinal direction) ＞ 3000g/mm, tearing
Intensity (transverse direction) ＞ 5000g/mm；Flame retardant property is good, printing is good, and it is interesting to can print various numbers, Logo, word, letter etc.
Pattern.Happy atmosphere is brought to life, is brought aesthetic feeling and happy to people, is a kind of product joy being brought the world.
Generally speaking, the present invention passes through the screening of stabilizer and the optimization of material compositions integral formula so that gained produces
Product reach environmental protection, mechanical strength, water resistance are taken into account, meet European Union newest REACH regulations and EN71part3 heavy metal and
The requirement of organo-tin compound limit value.The preparation method very simple of the present invention, production efficiency is high, and production cost is low, has fine
Economic benefits.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of folding water-proof environmental protection PVC material composition, which is characterized in that by including prepared by each raw material of parts by weight such as：
The stabilizer is the mixture of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer, the wherein weight of three
It is (0.5-3) to measure portion rate：(0.5-2.5)：(0.5-3).
2. folding water-proof environmental protection PVC material composition according to claim 1, which is characterized in that by including such as parts by weight
It is prepared by several each raw materials：
The stabilizer is the mixture of magnesium-aluminum-zinc composite stabilizer, calcium zinc stabilizer, rare-earth stabilizer, the wherein weight of three
It is (0.5-3) to measure portion rate：(0.5-2.5)：(0.5-3).
3. folding water-proof environmental protection PVC material composition according to claim 1 or 2, which is characterized in that the lubricant is
At least one of calcium stearate, zinc stearate, microcrystalline wax, stearic acid, butyl stearate, polynary carboxylic ester；The filler
For at least one of titanium dioxide, talcum powder, calcium carbonate.
4. folding water-proof environmental protection PVC material composition according to claim 3, which is characterized in that the lubricant is more
First carboxylic ester；The filler is at least one of titanium dioxide, talcum powder.
5. folding water-proof environmental protection PVC material composition according to claim 1 or 2, which is characterized in that the PVC is used
At least one of SG-7, S-65, HG-800, DG-800, TL-800, TL-1000, S-1007, S-1008；The modification agent is
At least one of MBS, ACR, ABS.
6. a kind of preparation method of folding water-proof environmental protection PVC material composition according to any one of claims 1 to 5,
It is characterized in that, includes the following steps：
To the PVC of the mass fraction, stabilizer, epoxidized soybean oil, methyl methacrylate-butyl acrylate copolymer, change
Matter agent, lubricant, filler, colouring matter are mixed, and mixture material is obtained；
The mixture material squeezes out after screw extruder shears preplasticizing, then through calender compression molding, stretching-machine draws,
Winding is to get the folding water-proof environmental protection PVC material composition after cooling and shaping, corona.
7. the preparation method of folding water-proof environmental protection PVC material composition according to claim 6, which is characterized in that described
The equipment used is mixed as thermal agitation machine or mixing machine；The time of the mixing is 5-10min；The screw extruder is star
The temperature of shape screw extruder, the screw extruder is 130-190 DEG C, and the rotating speed of the screw extruder is 35-60rpm.
8. folding water-proof environmental protection PVC material composition according to any one of claims 1 to 5 is as printing playing card material
In purposes.
9. a kind of playing card, which is characterized in that contain claim 1-5 any one of them folding water-proof environmental protection PVC material groups
Close object.
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| CN111690214A (en) * | 2020-06-15 | 2020-09-22 | 无锡宏义高分子材料科技有限公司 | High-temperature-resistant and folding-resistant PVC membership card base material and preparation method thereof |
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| CN101289552B (en) * | 2008-06-13 | 2011-12-28 | 肇庆市森德利化工实业有限公司 | Magnesium- aluminum-zinc composition for preparing magnesium- aluminum-zinc composite stabilizer and method of making the same |
| CN101565512A (en) * | 2008-08-29 | 2009-10-28 | 内蒙古皓海化工有限责任公司 | Nanometer rare-earth calcium-zinc-magnesium-aluminum PVC composite stabilizer |
| CN101508796A (en) * | 2009-03-25 | 2009-08-19 | 江西宏远化工有限公司 | Ternary hydrotalcite-rare earth-calcium/zinc nontoxic composite heat stabilizer and preparation thereof |
| CN105367940A (en) * | 2015-11-03 | 2016-03-02 | 南京协和助剂有限公司 | Environmental protection stabilizer for PVC |
| CN105647064B (en) * | 2016-03-09 | 2018-02-13 | 广州宏信塑胶工业有限公司 | A kind of weather-proof PVC plastic wallpaper and preparation method thereof |
| CN106565993A (en) * | 2016-11-10 | 2017-04-19 | 周荣 | Preparation method of environment-friendly composite heat stabilizer |
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Effective date of registration: 20191202 Address after: 214000 No.28, Xinzhou Road, national high tech Industrial Development Zone, Wuxi City, Jiangsu Province Patentee after: Wuxi Hongyi polymer material technology Co., Ltd Address before: 510530, No. 1, Po pan Road, Guangzhou, Guangdong, Luogang District Patentee before: GUANGZHOU HAN RIGID INDUSTRIAL CO., LTD. |
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