CN100338135C - Composition of emulational plastic and preparation method - Google Patents
Composition of emulational plastic and preparation method Download PDFInfo
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- CN100338135C CN100338135C CNB2004101015509A CN200410101550A CN100338135C CN 100338135 C CN100338135 C CN 100338135C CN B2004101015509 A CNB2004101015509 A CN B2004101015509A CN 200410101550 A CN200410101550 A CN 200410101550A CN 100338135 C CN100338135 C CN 100338135C
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Abstract
The present invention provides an emulational plastic composition and a preparation method thereof, which relates to the field of emulational plastics. In this invention, components including polyvinyl chloride paste resin and powdered rubber with diameters in the range of 30-200 nm and gel content higher than 60% are uniformly mixed and molded to obtain the emulational plastic composition, wherein the components can also comprise a light-storing luminescent material which can be one or a plurality of kinds of the light-storing luminescent material series: silicate system, aluminate system and sulfide series. The emulational plastic composition of the present invention has the advantages of high strength, high elasticity, favorable texture and favorable brightness in case of need. The composition comprises 1 to 40 portions of luminescent materials and 2 to 8 portions of powdered rubber when measuring the polyvinyl chloride paste resin as 100 portions by weight. The composition of the present invention is suitable for manufacturing various organism imitators, and has wide application.
Description
Technical field
The present invention relates to a kind of composition of emulational plastic, say further, relate to a kind of translucent, soft and whippy polyvinyl chloride paste resin combination.
Background technology
The preparation method of the emulation goods on mimic biology physique ground has following a few class both at home and abroad at present: the first kind is made with degradation material or water-soluble material.As U.S. Pat 6,174,525, US5,554,659, US5,554,658, Chinese patent 97116425.8,94102951.4 etc., it relates to product and is mixed and made into seasonings and pigment etc. with materials such as gelatin, starch, polyvinyl alcohol, corns; Second class is to make with metal, timber, leather or other material, as U.S. Pat 5,193, and 299, US4,654,995, Chinese patent 91232037.0 or the like; The 3rd class is to make with high molecular synthetic material, comprise polyvinyl chloride (PVC), SBS, SEBS, polyurethane (PU), ethylene-propylene diene copolymer (EPDM), EVA, polyethylene, polypropylene etc., as U.S. Pat 4,625,447, US20040018272, US20040018223, US2003130407, US20020188057 and WO03003825 or the like.
The above the 3rd class material has advantage but still the several like this problems of existence such as certain texture and intensity:
1, insufficient strength height.As US4,214,397, because a large amount of softening agent that add in the prescription, indexs such as the tensile strength of material reduce a lot; But if do not add softening agent in a large number, the meat feeling and the elasticity of material come in nowhere again;
2, hardness is too high or too low, tension set is big, elongation at break is low, thereby the emulation effect is general, particularly aspect meat feeling and elasticity, as WO03003825 etc.;
3, cost height, as US20040018272, US20040018223, US5709047, US2003130407 etc., they are to be the base mateiral preparation with a large amount of oil-filled SEBS or SBS or silicon rubber, material cost is higher;
4, in the dark can not luminous, need the luminous occasion of material inapplicable for some, when for example doing the bait material, many fish have phototaxis, in order better to attract fish, some product design electroluminescent device, as US4,625,447 and Chinese patent 02204353.5 etc.
Summary of the invention
The present invention is directed to above problems of the prior art, be intended to obtain a kind of as required can also self luminous emulational plastic when having high strength and favorable elasticity and texture.
Therefore, the purpose of this invention is to provide a kind of have good luminous property and high strength, snappiness composition of emulational plastic.
Another object of the present invention provides the preparation method of described composition of emulational plastic.
A kind of composition of emulational plastic provided by the present invention includes the following component of blend: a. pvc resin paste grade; The b powdered rubber.It preferably also comprises the c. light-storing and emitting material.
In the composition of emulational plastic of the invention described above, described pvc resin paste grade is the disclosed pvc resin paste grade of prior art.
The above composition of emulational plastic of the present invention, wherein components b is median size 30～200nm, is preferably 40～150nm; Gel content is 60% weight or higher, is preferably 80% weight or higher powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.This kind powdered rubber is selected from a kind of or its mixing in powder nbr rubber and the carboxyl butyronitrile powdered rubber.
The powdered rubber of described components b can adopt according to the inventor in the prepared fully vulcanized powder rubber of the Chinese patent ZL00816450.9 of on September 18th, 2000 application (is right of priority with Chinese patent application 99125530.5, priority date on December 3rd, 1999).Be preferably form of finely divided powder, mehtod paracril and/or form of finely divided powder, mehtod carboxy nitrile rubber.This kind fully vulcanized powder rubber gel content reaches 60% weight or higher, need not after the drying to get final product unrestricted flow with separant.Each particulate in this fully vulcanized powder rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.This fully vulcanized powder rubber gets by to the rubber latex cross-linking radiation rubber particles particle diameter being fixed.So the particle diameter of latex particle is consistent substantially in its median size and the rubber latex, the size scope of the latex particle that described rubber latex obtains when synthetic is the particle size range of gained fully vulcanized powder rubber particle, be generally 20～2000nm, preferred 30～1500nm, more preferably 50～500nm.
The powdered rubber of the above components b can also adopt the prepared cross-linked powdered rubber of Chinese patent ZL00130386.4 in application on November 3rd, 2000 according to the applicant.Be preferably cross-linked powdery acrylonitrile butadiene and/or cross-linked powdery carboxy nitrile rubber.This kind cross-linked powdered rubber is a kind ofly (to have some rubber latexs between the rubber molecule certain cross can take place in the synthetic process with cross-linking type synthetic rubber latex, thereby make resulting rubber latex have certain crosslinking degree, be referred to as crosslinking-type rubber latex) be raw material, the powdered rubber that drying obtains.The particle diameter of latex particle is consistent substantially in its median size and the crosslinking-type rubber latex, and the size scope of the latex particle that crosslinking-type rubber latex obtains when synthetic is the particle size range of gained cross-linked powdered rubber particle, is generally 50～300nm.This cross-linked powdered rubber need not add separant and get final product unrestricted flow.Its gel content is consistent with gel content as the cross-linking type synthetic rubber latex of raw material, is 80% weight or higher, is preferably 85% weight or higher.Each particulate in this cross-linked powdered rubber all is a homogeneous, and promptly single particulate all is a homogeneous on forming, and does not find layering in the particulate under the observation of existing microtechnique, divides the phenomenon that equates uneven phase.
Described components b powdered rubber also can be the mixing of the above fully vulcanized powder rubber and cross-linked powdered rubber.
The content of described components b powdered rubber is 100 parts by weight in component a pvc resin paste grade, is 2～8 parts.The preferable range of its content is 3～6 parts.
The above composition of emulational plastic of the present invention, wherein amount of component b be in silicate systems light-storing and emitting material of the prior art, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material one or more (see " light-storing and emitting material and goods thereof " second and third, four chapters, the Xiao Zhiguo chief editor, Chemical Industry Press publishes in October, 2002).Be preferably in different kinds of ions activated silicate, the different kinds of ions activated aluminate one or more.Different kinds of ions activated silicate and aluminate among the present invention, (patentee: different kinds of ions activated silicate and the aluminate Luming technology Group Co., Ltd., Dalian city) is consistent with Chinese patent CN 1120207C.
The chemical constitution expression that is multiple activated silicate luminescent material is:
αMO·βM’O·γSiO
2·δR:Eu
xLn
y
Wherein M is the combination of one or more elements among Sr, Ca, Ba, the Zn;
M ' is the combination of one or more elements among Mg, Cd, the Be;
R is B
2O
3, P
2O
5In one or both combination of compounds;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Pr, Tb, Ce, Er, Mn, Bi, Sn, the Sb;
α, β, γ, δ, x, y are mole coefficient,
0.6≤α≤6；0≤β≤5；1≤γ≤9；
0≤δ≤0.7、0.00001≤x≤0.2、0≤y≤0.3。
The chemical constitution expression of multiple activated aluminate luminescent material is:
αMO·βAl
2O
3·γB
2O
3:Eu
xLn
y
Wherein M is the combination of one or more elements among Mg, Ca, Sr, Ba, Zn, the Cd;
Ln is the combination of one or more elements among Nd, Dy, Ho, Tm, La, Ce, Er, Pr, the Bi;
α, β, γ, x, y are mole coefficient,
0.5≤α≤6；0.5≤β≤9；0.0001≤γ≤0.3；
0.00001≤x≤0.15、0.00001≤y≤0.2。
The big more briliancy of the above light-storing and emitting material particle is high more, but can improve the frictional force in the course of processing, and too conference is unfavorable for the composition mechanical property; The little frictional force that can reduce in the processing of particle, but briliancy can decrease, and also too little particle also is unfavorable for disperseing.Help luminescent material to disperse, reduce friction, raising luminescent material add-on, improve composition flexible powdered rubber, owing to added among the present invention so the granular size of these light-storing and emitting materials is not remarkable to the influence of composition properties in the present invention in the prior art.But consider the problem of dispersed and cost, its median size can be preferably 10～40 μ m, more preferably 10～20 μ m.
The content of described amount of component b is 100 parts by weight in component a pvc resin paste grade, is 1～40 part.The preferable range of its content is 10～30 parts.
Composition of emulational plastic of the present invention also comprises general stablizer in the existing pvc resin paste grade processing technology, comprises organic tin, barium zinc class stablizer.Its consumption is a conventional amount used.As calcium-zinc stable composition system, its consumption is that 100 parts by weight are counted 2～5 weight parts with pvc resin paste grade, preferred 5 weight parts;
In addition, can also include some auxiliary agents such as pigment, softening agent etc. commonly used in the pvc resin paste grade course of processing in the composition of composition of emulational plastic of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.For softening agent, can comprise conventional softening agent such as sebacic acid ethylhexyl (DOS), dioctyl phthalate (DOP) (DOP), dibutyl phthalate (DBP).Wherein preferred high temperature performance is good, the softening agent DOS of low migration, can obviously improve shortcomings such as goods are hard because of the winter that season, the temperature difference caused, summer is soft, and the shelf-time is disconnected, and plasticizer migration is serious.Its consumption is that 100 parts by weight are counted 250～450 weight parts with pvc resin paste grade, preferred 300～400 weight parts.
The preparation method of composition of emulational plastic of the present invention, comprise the component that will include described pvc resin paste grade, powdered rubber, and the component that preferably also comprises light-storing and emitting material mixes, molded step, and makes composition of emulational plastic.Described molded be to utilize the concrete step of the moulding technology of pvc resin paste grade in the prior art, can comprise the material behind the uniform mixing is poured in the mould, make it plasticizing forming 155～170 ℃ of heating, be quickly cooled to the demoulding after the room temperature.Wherein the particular case of, thin and thick big less according to goods heat-up time and mould thermal conductivity is regulated.Its heat-up time when molded can be for general goods at 4～8 minutes.
In the preparation method of the composition of emulational plastic of the invention described above, described pvc resin paste grade comprises the disclosed pvc resin paste grade of prior art.
At the powdered rubber described in the aforesaid method is median size 30～200nm, is preferably the powdered rubber of 40～150nm.Its gel content is 60% weight or higher, is preferably 80% weight or higher.This kind powdered rubber comprises a kind of or its mixing in powder nbr rubber and the carboxyl butyronitrile powdered rubber.This kind powdered rubber is preferably the rubber particles of equal phase structure.(with Chinese patent application 99125530.5 is right of priority to powdered rubber described in the inventive method Chinese patent ZL00816450.9 preferred above-mentioned, that the inventor applied on September 18th, 2000, priority date on December 3rd, 1999) cross-linked powdered rubber that the fully vulcanized powder rubber that is provided, and/or the inventor is provided in the Chinese patent ZL00130386.4 of application on November 3rd, 2000.
At the light-storing and emitting material described in the preparation method of the invention described above is in silicate systems light-storing and emitting material of the prior art, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material one or more.Be preferably in different kinds of ions activated silicate, the different kinds of ions activated aluminate one or more.Its median size is preferably 10～40 μ m, more preferably 10～20 μ m.
Is 100 parts by weight at the consumption of luminescent material described in the aforesaid method in pvc resin paste grade, is 1～40 part, is preferably 10～30 parts.The powdered rubber consumption is 100 parts by weight in described pvc resin paste grade, is 2～8 parts, is preferably 3～6 parts.
In the preparation process of composition of emulational plastic of the present invention, the molded temperature of material is plasticization temperature in the common pvc resin paste grade course of processing, is generally 155～170 ℃.In addition, according to the processing needs, can add some auxiliary agents such as stablizer commonly used in the pvc resin paste grade course of processing in right amount in material, comprise organic tin, barium zinc class stablizer etc., its consumption is a conventional amount used.As calcium-zinc stable composition system, its consumption is that 100 parts by weight are counted 2～5 weight parts with pvc resin paste grade, preferred 5 weight parts;
Can also include some auxiliary agents such as pigment, softening agent etc. commonly used in the pvc resin paste grade course of processing in the composition of composition of emulational plastic of the present invention, its consumption is conventional amount used, or adjusts according to practical requirements.As conventional softening agent sebacic acid ethylhexyl (DOS), consumption is that 100 parts by weight are counted 250～450 weight parts with pvc resin paste grade, preferred 300～400 weight parts.
The equipment of mixing of materials can adopt various mixing equipments used in the prior art in the preparation method of the invention described above, as stirrer, kneading machine etc.
Composition of emulational plastic of the present invention has effectively solved above-mentioned problems of the prior art:
1. in order to improve the flexibility of goods, all add the very high softening agent of content in the existing emulation goods, add elastomeric modification agent superfine fully vulcanized powder rubber in the present invention in right amount, can obviously improve the tensile strength and the elasticity of material, under the synergy of softening agent, make the meat feeling of material and fidelity obtain bigger raising;
2. add the accumulating type self-luminescent material, long fluorescent lifetime and higher brightness can in the dark be arranged;
3. the present invention adopts polyvinyl chloride to stick with paste resin to be base resin, to cooperate the formula system with the elastomeric modification agent, and the existing patent formulation of contrast is as having the cost competitive edge with oil-filled SEBS and SBS etc., and emulation is good.
The favorable elasticity that composition of emulational plastic of the present invention had, higher-strength, luminescent properties is good, texture good, transparency good nontoxic to human body, environment is not had advantages such as any pollution, be specially adapted to make organism emulation goods.Preparation method's technology of the present composition is simple, easy handling, is suitable for industrial applications.
Embodiment
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1～6:
Softening agent sebacic acid ethylhexyl (DOS, U.S. Exxon company produces), calcium-zinc stabilizer (Shenzhen's will sea company produces non-toxic, environmental friendly) and pigment are mixed by prescription; With pvc resin paste grade (chemical plant, Shenyang, PSH-31), vulcanize powder nbr rubber (VP-401 entirely, the Beijing Chemical Research Institute produces, particle diameter 80～110nm, gel content 83%wt), (Luming technology Group Co., Ltd., Dalian city produces the light-accumulating alkaline earth aluminate, trade mark PLO-6D, particle size range is 12～18 μ) carry out uniform mixing with above-mentioned mixed solution.Leave standstill and poured in the mould after (the also bubble of vacuum-pumping) in 48 hours, made it plasticizing forming in 4 minutes, be quickly cooled to the demoulding after the room temperature 160 ± 5 ℃ of heating to go out in the mixed solution.Carry out the test of every performance with cutting out good batten.Concrete prescription sees Table 1, and wherein various component concentrations are 100 parts by weight in the pvc resin paste grade gross weight.Results of property is as shown in table 1.
Comparative example 1～4:
All the other components and condition are all with embodiment 1 except that not adding full sulfuration butylbenzene powdered rubber.Concrete prescription sees Table 1, and each component concentration is 100 weight parts in pvc resin paste grade all.Results of property is as shown in table 1.
Comparative example 5:
All the other components and condition are all with embodiment 1 except that not adding full sulfuration butylbenzene powdered rubber and energy-saving luminous material.Concrete prescription sees Table 1, and each component concentration is 100 weight parts in pvc resin paste grade all.Results of property is as shown in table 1.
The standard of the material for preparing in above embodiment and the Comparative Examples being carried out performance test is as follows:
Tensile strength, elongation at break: GB/T1040-92;
Shore A hardness: GB/T2411-80;
Permanent set: GB/T7795-96;
Luminescent properties (briliancy) test: adopt brightness to come the luminescent properties of exosyndrome material in the embodiment of the invention and the Comparative Examples.Concrete testing method is as follows: two 40W fluorescent tubes are positioned over print apart from light source 13cm place during test as light source, behind the irradiation 20min, test its luminous intensity with the MINOLTACS-100 chromascope in the darkroom.
Fidelity: comprehensive elongation at break, permanent set and hardness number are evaluated, general elongation at break is big more, permanent set is low more, shore hardness 3～22 when (more preferably 4～15) goods have texture preferably, simulated effect is good.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Pvc resin paste grade | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| DOS | 350 | 400 | 400 | 300 | 250 | 450 | 250 | 300 | 350 | 400 | 300 |
| Powdered acrylonitrile-butadiene rubber | 4 | 6 | 3 | 3 | 3 | 6 | - | - | - | - | - |
| The steady persistence alkaline earth aluminate | 10 | 10 | 10 | 10 | 30 | 30 | 10 | 10 | 10 | 10 | - |
| The Ca-Zn stablizer | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Pigment | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Tensile strength (KPa) | 893 | 1313 | 655 | 936 | 995 | 1270 | 509 | 472 | 417 | 326 | 520 |
| Elongation at break (%) | 250 | 265 | 230 | 242 | 245 | 242 | 210 | 192 | 180 | 170 | 220 |
| Shao Shi A | 10 | 9 | 8 | 10 | 12 | 9 | 4 | 3 | 3 | 1 | 2 |
| Permanent set (%) | 4 | 3 | 6 | 6 | 7 | 4 | 12 | 13 | 13 | 15 | 13 |
| Briliancy 5min (cd/m 2) | 0.56 | 0.47 | 0.49 | 0.48 | 0.92 | 0.81 | 0.51 | 0.53 | 0.57 | 0.59 | 0 |
| Briliancy 10min (cd/m 2) | 0.15 | 0.16 | 0.15 | 0.14 | 0.32 | 0.30 | 0.14 | 0.14 | 0.15 | 0.16 | 0 |
| The emulation degree * | √ | √ | ● | ● | ● | √ | ▲ | ▲ | ▲ | × | × |
*Annotate: √---excellent; ●---good; ▲---poor; *---very poor.
The embodiment that from table 1, lists and the result of comparative example as can be seen, emulational plastic tensile strength height of the present invention, elongation at break is big, permanent set is low, shore hardness is moderate, and good texture and simulated effect are arranged.
Claims (10)
1. composition of emulational plastic includes the following component of blend:
A. pvc resin paste grade 100 parts by weight
B. powdered rubber 2～8 parts by weight
Wherein said components b is median size 30～200nm, and gel content is 60% weight or higher powdered rubber, and powdered rubber is the rubber particles of equal phase structure, is in fully vulcanized powder rubber and the cross-linked powdered rubber one or more; The rubber kind of described powdered rubber comprises paracril and/or carboxy nitrile rubber.
2. composition of emulational plastic according to claim 1 includes the following component of blend:
A. pvc resin paste grade 100 parts by weight
B. powdered rubber 3～6 parts by weight.
3. composition of emulational plastic according to claim 1, include amount of component b: light-storing and emitting material, it comprises in silicate systems light-storing and emitting material, aluminates system light-storing and emitting material, the sulfide series light-storing and emitting material one or more; In pvc resin paste grade is 100 parts by weight, and amount of component b is 1～40 parts by weight.
4. composition of emulational plastic according to claim 3, described amount of component b are that 100 parts by weight are counted 10～30 parts by weight with pvc resin paste grade.
5. composition of emulational plastic according to claim 3, the median size of wherein said amount of component b luminescent material are 10～40 μ m.
6. composition of emulational plastic according to claim 5, the median size of wherein said amount of component b luminescent material are 10～20 μ m.
7. composition of emulational plastic according to claim 3, the luminescent material of wherein said amount of component b are one or more in different kinds of ions activated silicate, the different kinds of ions activated aluminate.
8. composition of emulational plastic according to claim 1, the median size of the powdered rubber of wherein said components b are 40～150nm.
9. composition of emulational plastic according to claim 1, the powdered rubber gel content of wherein said components b is 80% weight or higher.
10. according to the preparation method of the described composition of emulational plastic of one of claim 1～9, comprise that the component that will include described pvc resin paste grade, powdered rubber mixes by described component concentration, make described composition of emulational plastic by molded.
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| CN102477190B (en) * | 2010-11-22 | 2013-12-18 | 苏州市医学教学模型制造有限公司 | Method for preparing simulated human body rectum model |
| CN102870750B (en) * | 2012-10-10 | 2016-05-25 | 安徽宏飞钓具有限公司 | A kind of fishing tackle bait that does not contain phthalic acid ester |
| CN104250409B (en) * | 2013-06-28 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of light-accumulating and luminescent type polrvinyl chloride dips in molding composition |
| CN103665665A (en) * | 2013-12-04 | 2014-03-26 | 于义新 | Plastic traffic pier doped with fluorescent powder |
| CN104855349A (en) * | 2015-04-24 | 2015-08-26 | 界首市超强渔具有限公司 | Easily degradable environment-friendly soft color bionic fish bait |
| CN104855350A (en) * | 2015-04-24 | 2015-08-26 | 界首市超强渔具有限公司 | Preparation method for environment-friendly soft colorful biomimetic bait |
| CN115403882B (en) * | 2022-09-27 | 2023-09-12 | 中新巨成医学科技有限公司 | Biological simulation material formed by foaming process and preparation method and application thereof |
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| US20040018272A1 (en) * | 2002-07-20 | 2004-01-29 | Chen John Y. | Gelatinous food elastomer compositions and articles for use as fishing bait |
| AU2003101029A4 (en) * | 2003-01-08 | 2004-02-05 | Chris Palatsides | Soft bodied squid jig |
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| WO2003003825A1 (en) * | 2001-07-03 | 2003-01-16 | Commissariat A L'energie Atomique | Flexible fishing lures |
| JP2003134971A (en) * | 2001-10-31 | 2003-05-13 | Hayashibara Biochem Lab Inc | Artificial bait |
| US20040018272A1 (en) * | 2002-07-20 | 2004-01-29 | Chen John Y. | Gelatinous food elastomer compositions and articles for use as fishing bait |
| AU2003101029A4 (en) * | 2003-01-08 | 2004-02-05 | Chris Palatsides | Soft bodied squid jig |
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