CN112745557B - Yellowing-resistant permanent antistatic breathable film and preparation method and application thereof - Google Patents
Yellowing-resistant permanent antistatic breathable film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a yellowing-resistant permanent antistatic breathable film and a preparation method and application thereof, wherein the breathable film comprises the following components in parts by weight: 35-55 parts of polyolefin resin; 40-60 parts of heavy calcium carbonate; 10-30 parts of a permanent antistatic agent; 0.5-2 parts of a yellowing inhibitor; 0.5-2 parts of an antioxidant; 0.5-2 parts of a processing aid. The surface resistivity of the gas permeable film is 1 x 10 9 Within omega.M, yellowing degree Delta b is less than or equal to 0.4, and moisture permeability is more than or equal to 2159g/M 2 24 h; hydrostatic pressure of 819mmH or more 2 And (O). The breathable film can be applied to protective clothing, paper diapers and sanitary towels.
Description
Technical Field
The invention relates to the technical field of modified plastics, in particular to a yellowing-resistant permanent antistatic breathable film and a preparation method and application thereof.
Background
The static electricity of fabrics and clothes is mainly generated by the friction and the induction of fabrics, and the static electricity can adsorb dust, particles and pathogenic bacteria with opposite charges to the surface of clothes, so that the phenomenon of discharging can cause safety accidents under extreme conditions. The following protective clothing application scenarios have stringent antistatic requirements: (1) hospitals, operating rooms, and the like, have a high risk of infection; (2) the micro-electronic component is processed and operated, so that breakdown caused by discharge is prevented; (3) mine, volatile solvent, dust processing and other occasions with explosion risks.
The conventional antistatic treatment techniques are generally as follows: firstly, antistatic liquid spraying or dipping treatment is carried out on the fabric, and the micromolecule antistatic agent is adsorbed on the surface of the non-woven fabric to directly act or is transferred to the surface of the fabric to act. In typical medical/industrial protective clothing application, non-woven fabrics subjected to antistatic treatment are compounded with polyolefin breathable films, and small-molecule antistatic agents migrate to the breathable film layers to play a role, so that the method is most widely applied at present, but the durability of the antistatic effect is poor, and the antistatic performance is easy to attenuate in the use process (friction or washing); secondly, the antistatic agent is blended and extruded, the small molecular antistatic agent migrates to the surface of the fabric to play a role, and the antistatic agent is easy to influence spinning and film making processes (yarn breakage, mouth mold precipitation and the like), so that the method is limited in application; thirdly, the antistatic effect is good when the conductive filler (conductive carbon black, graphite, carbon nano tube and the like) is added, but the filler is difficult to disperse, the appearance and the physical properties of the film are easily influenced, and the method is limited in application. The antistatic technology still has a problem that the antistatic technology is easy to yellow during storage and use and becomes an industrial technical problem;
although the Chinese patent (101250302A) discloses an antistatic polyolefin breathable film composition and a method for preparing the breathable film, the antistatic resin is prepared by synthesis and added into a polyolefin breathable film substrate to achieve the antistatic effect, the method still has the problems of yellowing and poor antistatic effect in the storage and use processes.
Disclosure of Invention
The invention provides a yellowing-resistant permanent antistatic breathable film for overcoming the defects of poor antistatic effect and easy yellowing in the prior art.
The invention also aims to provide a preparation method of the yellowing-resistant permanent antistatic breathable film.
The invention also aims to provide application of the yellowing-resistant permanent antistatic breathable film.
In order to achieve the purpose, the invention adopts the technical scheme that:
a yellowing-resistant permanent antistatic breathable film comprises the following components in parts by weight:
generally, both small-molecule antistatic agents and permanent antistatic agents are added into polyolefin resin, although the antistatic effect is improved, the yellowing problem also occurs, especially after polyolefin is made into a film, the yellowing effect is more obvious, and especially for small-molecule antistatic agents, the antistatic effect is greatly reduced after yellowing.
According to the invention, the yellowing inhibitor and the permanent antistatic agent are adopted to improve the performance of the breathable film, and on one hand, the permanent antistatic agent is added into the polyolefin resin to improve the antistatic effect of the polyolefin resin; on the other hand, the yellowing inhibitor is adopted to inhibit the oxidation of metal ions in the permanent antistatic agent, so that the permanent antistatic agent is prevented from discoloring, and the problem of discoloration of the polyolefin breathable film in the use process is greatly reduced.
Preferably, the polyolefin resin is one of polyethylene or polypropylene.
The low-density polyethylene has a melt index of 5-10 g/10min and MWD (measurement while molecular weight) more than 5, the metallocene polyethylene has a melt index of 1.0-5 g/10min, a comonomer is hexene or octene, and the concentration of the comonomer is 4-10%.
The polypropylene is one or a composition of random copolymerization, block copolymerization and homopolymerized polypropylene, and the melt index is 2-5 g/10 min.
Preferably, the polyethylene is a mixture of low density polyethylene and metallocene polyethylene; wherein the weight of the low-density polyethylene is 5-10 parts; 30-45 parts of metallocene polyethylene.
Preferably, the yellowing inhibitor is 0.5-1 part.
Preferably, the yellowing inhibitor is one of hydrazide type yellowing inhibitors, salicylic acid type yellowing inhibitors or oxalic acid type yellowing inhibitors.
The hydrazide yellowing inhibitor is an N, N' -disubstituted hydrazine compound which is an acyl chloride derivative of aromatic hydrazide and hindered phenol disubstituted fatty acid, and a hydrazide compound generated by reacting hydrazide of aliphatic dicarboxylic acid with fatty acyl chloride.
The salicylic acid yellowing inhibitor is an N, N-disalicylidene-1, 2-propylene diamine compound.
The oxalic yellowing inhibitor is an oxalyl diphenylamine compound.
Preferably, the average particle size of the heavy calcium carbonate is 1-3 μm, and the heavy calcium carbonate is coated by a surface treatment agent.
The surface treating agent is one of stearic acid, titanate or aluminate.
Preferably, the permanent antistatic agent is one of polyether type permanent antistatic resin or quaternary ammonium salt type permanent antistatic resin.
More preferably, the melt index of the polyether type permanent antistatic resin or the quaternary ammonium salt type permanent antistatic resin is between 2 and 15g/10 min.
The polyether permanent antistatic agent is polyolefin polyether block copolymer, polyether ester amide or polyether amide imine.
The quaternary ammonium salt type permanent antistatic resin is a copolymer of polyolefin polycondensate containing quaternary ammonium salt and methacrylate ester and a copolymer of polycondensate containing quaternary ammonium salt and maleimide.
The antioxidant is hindered phenol and/or phosphite ester.
The hindered phenol antioxidant is one or more of antioxidant 1010, antioxidant 1076 and antioxidant 1790.
The phosphite ester antioxidant comprises the following components: one or more of antioxidant 168 and TNPP.
The invention also provides a preparation method of the yellowing-resistant permanent antistatic breathable film, which comprises the following steps:
s1, respectively drying a permanent antistatic agent and polyolefin resin;
the drying temperature is 75-95 ℃, and the drying time is not less than 3 hours;
s2, conveying the materials dried in the step S1 to an extruder respectively, and adjusting the conveying proportion according to the thickness of the surface layer;
s3, melting and plasticizing the rest materials by an extruder screw, then feeding the melted and plasticized materials into a multi-layer structure die head, and extruding the melt through an oral die;
the multi-layer structure die head is a clothes hanger type die or a circular ring die;
s4, cooling the melt, and then carrying out preheating, stretching, shaping and cooling processes;
the stretching process is single-stage stretching or multi-stage stretching, and the stretching ratio is 2.0-5.0;
and S5, rolling and packaging the film.
Preferably, sealed packaging is performed.
The yellowing-resistant permanent antistatic breathable film is applied to preparation of protective clothing, paper diapers and sanitary towels.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts the antistatic agent and the yellowing inhibitorThe breathable film prepared by adding the antistatic agent into polyolefin resin not only has permanent antistatic property, but also solves the problem of yellowing caused by the permanent antistatic agent, and the surface resistivity of the breathable film is 1 x 10 9 Within omega.M, yellowing degree Delta b is less than or equal to 0.4, and moisture permeability is more than or equal to 2159g/M 2 24 h; hydrostatic pressure of 819mmH or more 2 And O. The breathable film can be applied to protective clothing, paper diapers and sanitary towels.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment used in the invention are conventional in the technical field unless otherwise specified.
The following examples and comparative examples employ the following starting materials:
polyolefin resin a 1: polyethylene, LLDPE EXCEED3518PA, exxonmobil;
polyolefin resin a 2: low density polyethylene and metallocene polyethylene 1:4, low density polyethylene LDPE 1C7A, Yanshan petrochemical, metallocene polyethylene LLDPE EXCEED3518PA, Exxon Mobil;
polyolefin resin B: polypropylene, PP L5D98, medium petroleum Guangxi petrochemical;
heavy calcium carbonate A: the average grain diameter is 1 μm, and the product is treated by stearic acid and sold in the market;
heavy calcium carbonate B: the average grain diameter is 2 μm, and the product is treated by stearic acid and sold in the market;
heavy calcium carbonate C: the average grain diameter is 3 μm, and the product is treated by stearic acid and sold in the market;
heavy calcium carbonate D: the average grain diameter is 5 μm, and the product is treated by stearic acid and sold in the market;
ground calcium carbonate E: the average grain diameter is 0.5 μm, and the product is treated by stearic acid and sold in the market;
permanent antistatic agent A: polyether permanent antistatic agent, 8g/10min, Irgastat P22, BASF;
permanent antistatic agent B: quaternary ammonium salt type permanent antistatic agent, 10g/10min, commercially available;
yellowing inhibitor A: and (3) hydrazide IRGANOX MD-1024.
A yellowing inhibitor B: salicylic acid MARK CAD-1.
A yellowing inhibitor C: oxalic acids, Inhibitor OABH, Eastman kodak.
Yellowing inhibitor D: benzophenone, UV-531, cyanogen specialty chemicals.
Yellowing inhibitor E: benzotriazoles, UV-234, linaloon.
Antioxidant: antioxidant 1010, antioxidant 168 and ethametron.
Processing aid: zinc stearate BS-2818, BELIKE CHEMICAL.
The present invention will be described in detail with reference to examples and comparative examples.
The following examples and comparative examples were all prepared by the following method to prepare a yellowing-resistant permanent antistatic breathable film, and the components were weighed according to the weight ratios in tables 1 to 3; the method comprises the following specific steps:
s1, respectively drying the permanent antistatic agent and the polyolefin resin at 85 ℃ for 4 hours;
s2, conveying the materials dried in the step S1 to an extruder respectively, and adjusting the conveying proportion according to the thickness of the surface layer;
and S3, melting and plasticizing the residual materials by an extruder screw, then feeding the melted and plasticized residual materials into a multi-layer structure die head, and extruding the melt through an oral die, wherein the surface layer is a breathable film component containing the permanent antistatic agent.
And S4, cooling the melt, and then carrying out preheating, stretching, shaping and cooling processes, wherein the stretching process can be single-stage stretching or multi-stage stretching, the stretching ratio is between 2.0 and 5.0, and the permanent antistatic layer and the rest layers form a through microporous network.
And S5, rolling the film and sealing and packaging.
Examples 1 to 7
TABLE 1 formulations (parts) of examples 1 to 7
Examples 8 to 13
TABLE 2 formulations (parts) of examples 8 to 13
Examples 14 to 20 and comparative examples 1 to 3
TABLE 3 formulations (parts) of examples 14 to 20 and comparative examples 1 to 3
The yellowing-resistant permanent antistatic breathable films prepared in the above examples 1 to 18 and comparative examples 1 to 3 were subjected to the following performance tests, and the antistatic durability and color change of the films were tested by accelerated oven aging at an oven temperature of 60 ℃ for a test period of 60 days. The standard and method referenced for the test are as follows:
measurement of surface resistivity: according to the method provided by GB/T12703.4-2010.
Measurement of yellowing: the yellowing degree is characterized by the change of the b value (chromatometer test) of the film before and after aging, and the delta b value corresponds to the yellowing degree and the risk of yellowing.
Measurement of moisture permeability: according to the method provided by GB/T1270.2-2009, the temperature condition is 32 ℃, and the humidity condition is 50% RH.
Measurement of hydrostatic pressure: according to the method provided by GB/T4744-2013, the pressure increasing rate is 60 KPa/min.
TABLE 4 data for examples and comparative examples
From examples 1 to 3, as the content of the polyolefin resin increases, the dispersion density of the permanent antistatic agent decreases (the permanent antistatic agent is dispersed in the polyolefin resin only and cannot enter the calcium carbonate region), the corresponding conductive path decreases, the surface resistivity increases, the antistatic property decreases, and the yellowing degree before and after aging does not show obvious change.
From examples 2 and 4 to 5, with the increase of the content of the heavy calcium carbonate, the dispersion density of the permanent antistatic agent is increased, the surface resistivity is reduced, the antistatic performance is improved, and the yellowing degree before and after aging does not show obvious change.
From examples 2 and 6 to 7, as the content of the permanent antistatic agent increases, the dispersion density of the permanent antistatic agent increases, more conductive paths are formed, the surface resistivity is obviously reduced, and the antistatic performance is improved.
From examples 2 and 8 to 9, it can be seen that different kinds of polyolefin resins are selected, the antistatic property and the yellowing degree do not show obvious change, and the polypropylene resin system shows lower moisture permeability and higher hydrostatic pressure.
From examples 2 and 10 to 12, it can be seen that the properties did not show significant changes with the change in the average particle size of the ground calcium carbonate.
From examples 2 and 13, the choice of the type of permanent antistatic does not affect the change in properties.
From examples 2 and 14 to 16, the effect of inhibiting discoloration is enhanced with the increase of the content of the yellowing inhibitor, and within the range of 0.5 to 2 parts, the color difference change is controlled within 0.4, and a good yellowing inhibition effect is shown.
From examples 2 and 17 to 20, the yellowing inhibitor is hydrazide, salicylic acid or oxalic acid, and has a better yellowing inhibition effect.
From comparative examples 1 to 3, under the condition that no yellowing inhibitor is added, the color change is obvious before and after aging, the delta b value reaches 3.4, the yellowing inhibitor with 0.1 part is added to show the existing effect, but the yellowing resistant effect is not obvious, the delta b value is reduced to 2.1, and when the yellowing inhibitor is increased to 5 parts, the color change inhibiting effect is not further improved, but the hydrostatic pressure performance is deteriorated due to the fact that the content of the small molecular auxiliary agent is too high.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. The yellowing-resistant permanent antistatic breathable film is characterized by comprising the following components in parts by weight:
the yellowing inhibitor is one of hydrazide type yellowing inhibitors, salicylic acid type yellowing inhibitors or oxalic acid type yellowing inhibitors;
the hydrazide yellowing inhibitor is an N, N' -disubstituted hydrazine compound which is an acyl chloride derivative of aromatic hydrazide and hindered phenol disubstituted fatty acid, and a hydrazide compound generated by the reaction of hydrazide of aliphatic dicarboxylic acid and fatty acyl chloride;
the salicylic acid yellowing inhibitor is an N, N-disalicylidene-1, 2-propylene diamine compound;
the oxalic acid type yellowing inhibitor is an oxalyl diphenylamine compound.
2. The permanent anti-yellowing breathable film according to claim 1, wherein the polyolefin resin is one of polyethylene or polypropylene.
3. The yellowing-resistant, permanent, antistatic breathable film of claim 2, wherein the polyethylene is a mixture of low density polyethylene and metallocene polyethylene; wherein the low density polyethylene accounts for 5-10 parts; 30-45 parts of metallocene polyethylene.
4. The permanent anti-yellowing antistatic breathable film according to claim 1, wherein the yellowing inhibitor is 0.5-1 part.
5. The yellowing-resistant permanent antistatic breathable film according to claim 1, wherein the heavy calcium carbonate has an average particle size of 1-3 μm, and is coated with a surface treatment agent.
6. The yellowing-resistant permanent antistatic breathable film according to claim 1, wherein the permanent antistatic agent is one of polyether type permanent antistatic resin or quaternary ammonium salt type permanent antistatic resin.
7. The yellowing-resistant permanent antistatic breathable film according to claim 6, wherein the melt index of the polyether type permanent antistatic resin or quaternary ammonium salt type permanent antistatic resin at 190 ℃ and 2.16Kg is 2-15 g/10 min.
8. The preparation method of the yellowing-resistant permanent antistatic breathable film according to any one of claims 1 to 7, comprising the following steps:
s1, respectively drying a permanent antistatic agent and polyolefin resin;
s2, respectively conveying the materials dried in the step S1 to an extruder, and adjusting the conveying proportion according to the thickness of the surface layer;
s3, melting and plasticizing the residual materials by an extruder screw, and then, allowing the molten materials to enter a multi-layer structure die head, and extruding the melt through a mouth die;
s4, cooling the melt, and then carrying out preheating, stretching, shaping and cooling processes;
and S5, rolling and packaging the film.
9. The application of the yellowing-resistant permanent antistatic breathable film of any one of claims 1-7 in preparation of protective clothing, paper diapers and sanitary towels.
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