CN109294225A - A kind of two-way stretching polyamide film functional master batch and preparation method thereof - Google Patents
A kind of two-way stretching polyamide film functional master batch and preparation method thereof Download PDFInfo
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- CN109294225A CN109294225A CN201811291568.8A CN201811291568A CN109294225A CN 109294225 A CN109294225 A CN 109294225A CN 201811291568 A CN201811291568 A CN 201811291568A CN 109294225 A CN109294225 A CN 109294225A
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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Abstract
The invention proposes a kind of two-way stretching polyamide film functional master batch and preparation method thereof, wherein, a kind of two-way stretching polyamide film functional master batch includes that following component is made in parts by weight: 80~100 parts of polyamides, 4~15 parts of opening agents, the smooth auxiliary agent of 0.5~5 part of opening, 0.5~7 part of processing aid, 0~3 part of antioxidant.The no added migration slipping agent of polyamide film functional master batch provided by the invention adds corona surface and non-corona surface in film when suitable for producing two-way stretching polyamide film；Die head material deposition in polyamide film production process can be reduced by adding the functional master batch, extends and shuts down " clear lip " time interval；The coefficient of friction of polyamide film obtained is low, no small molecule transfer, and corona free is decayed under particular surroundings.
Description
Technical field
The present invention relates to functional agglomerate, in particular to a kind of two-way stretching polyamide film functional master batch and its preparation side
Method.
Background technique
Polyamide film has the characteristics that excellent high barrier, puncture-resistant, low temperature resistant, oil resistivity and flexibility, wide
The general fields such as daily necessities, electronic product, food and drug that are applied to are as packaging material.
Two-way stretching polyamide film finds that mouth mold just has continuous production 6-12 hours or so in the actual production process
A large amount of material deposition just will appear the increase of rupture of membranes frequency and film surface be deposited what object scratched if not shutting down " clear lip "
Phenomenon.In order to guarantee that polyamide film is not bonded to together, additive opening agent and slipping agent concentration in polyamide film are needed
Anti-adhesion master batch, to guarantee normal production, storage and transportation and the following process application of plastic film.
The polyamide anti-adhesion master batch of the prior art can all add the migration slipping agent such as amide wax class to reduce polyamide
The coefficient of friction of film improves the smooth effect of film.For example, the Chinese patent of Ems-Inventa AG of Switzerland application
97122705.5 use N, and N '-ethylidene-bis--fatty acid amide is as slipping agent；Sinopec Group Shen
Chinese patent CN1775858 please uses stearmide, erucyl amide, ethylene bis stearamide, stearic acid stearmide, tristearin
Sour erucyl amide and stearyl alcohol, stearate cover denier acid esters as slipping agent.The migration slipping agent of amide wax class is felt well
Sliding mechanism is: slipping agent molecular migration to film surface forms one layer of crystalline wax, reduces the coefficient of friction of film surface.But
If slipping agent molecular migration is excessive, the corona value that will cause film surface is reduced, to influence the printing effect of polyamide film
Fruit will also result in the relatively low problem of the combined strength bination of polyamide film.
Migration slipping agent adverse effect caused by polyamide film in existing anti-adhesion master batch how is thus solved, together
When, it obtains a kind of anti-adhesion master batch and is able to extend in polyamide film production and shut down " clear lip " time interval, guarantee polyamide film
Processing continuity, to extend the demand that the polyamide film continuous production time is current major polyamide film manufacturer.
Summary of the invention
Aiming at the problem that being mentioned in background technique, the present invention is intended to provide it is a kind of without adding migration slipping agent, it can
Extend in polyamide film production and shut down " clear lip " time interval, extends the functional master batch of polyamide film continuous production time.
A kind of two-way stretching polyamide film functional master batch provided by the invention, in parts by weight, including following component system
It is standby to obtain:
Further, in parts by weight, including following component is prepared:
Further, the polyamide carrier is at least one of polyamide and polyamide resin blends object；
Wherein, the polyamide is nylon 6, in nylon 7, nylon 11, nylon 12, nylon66 fiber, nylon 6T, nylon 46
At least one；
The polyamide resin blends object is at least one of polyamide resin resin copolymer and polyamide alloy；
The preferred nylon 6 of polyamide carrier.
Further, the opening agent is non-migratory slipping agent；The opening agent be calcium carbonate, diatomite, talcum powder,
At least one of silica, glass microballoon, silicate；The preferred hollow silicon dioxide of opening agent；The opening agent is flat
Equal partial size is 2~6um；Preferable particle size is the opening agent of 2.5~4.0um.
Further, the smooth auxiliary agent of opening is the polymethyl methacrylate of crosslinking, ptfe micropowder, crosslinking
Silicon powder, crosslinked polystyrene particle, at least one of solid preparing spherical SiO 2；The slipping agent that is open be it is solid spherical or
Person's spheroid shape particle；The smooth auxiliary agent preferably polytetrafluoroethylene micro mist of opening；The average grain diameter of the smooth auxiliary agent of opening is 2
~6um；It is preferred that draw partial size is the smooth auxiliary agent of opening of 2.5~4.0um；More preferably, the average grain of the smooth auxiliary agent of opening
Diameter is greater than above-mentioned opening agent partial size.
Further, the processing aid is at least one of fluorine-containing polymer processing aid and silane processing aid；
It is preferred that the fluorine-containing polymer processing aid of vinylidene fluoride-hexafluoropropylene copolymer.
Further, the antioxidant is antioxidant 1010, antioxidant 1098, antioxidant 1076, antioxidant 264, antioxygen
At least one of agent 168；It is preferred that antioxidant 1010.
The present invention also provides a kind of preparation methods of above-mentioned two-way stretching polyamide film functional master batch, including walk as follows
It is rapid:
Step 1: weighing nylon resin carrier, opening agent, the smooth auxiliary agent of opening, processing aid, antioxidant according to the ratio, add
Enter to double screw extruder and carries out melt blending extrusion；
Step 2: the material after melt blending extrusion, crosses water cooling, pelletizing, drying, packaging to get poly- to biaxial tension
Amide functional master batch.
Further, the screw diameter of double screw extruder is 40~100mm in step 1, and draw ratio is 30~60, is squeezed
Out-of-machine temperature is 180~300 DEG C, and the die head temperature of extruder is 230~270 DEG C, and rate of feeding is 10~60r/min, screw rod
Revolving speed is 250~600r/min.
Further, the cooling water length in step 2 is 3~5m, and pelleter revolving speed is 200~400r/min, using aluminium
Foil bag packaging.
Compared with existing polyamide film anti-adhesion master batch, have has amide film functional master batch provided by the invention as follows
Beneficial effect:
1, polyamide functional master batch of the invention does not add migration slipping agent, and coefficient of friction is lower than 0.30, has excellent
The smooth effect of opening, the migration of no slipping agent causes the corona value of polyamide film surface decay, printing effect difference and it is compound by force
Spend the problems such as relatively low；
2, polyamide functional master batch of the invention also has die head material deposition in reduction film production process, extends and shuts down
" clear lip " time interval；
3, the two-way stretching polyamide functional master batch obtained by above-mentioned preparation method is in two-way stretching polyamide film
Using so that polyamide film have the effect of it is good anti-sticking smooth.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
Every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
It should be noted that the examples of the embodiments are intended to be used to explain the present invention, and should not be understood as to the present invention
Limitation, in the examples where no specific technique or condition is specified, according to the literature in the art described technology or conditions or
Person carries out according to product description, reagents or instruments used without specified manufacturer, and being can be by the normal of commercially available acquisition
Advise product.
It is 40~100m that the present invention, which selects screw diameter, and draw ratio is the double screw extruder of 30~60m；Extruder temperature
Control is at 180~300 DEG C, and at 230~270 DEG C, rate of feeding is controlled in 10~60r/min for the die head temperature control of extruder,
Screw speed is controlled in 250~600r/min；Cooling water length is controlled in 3~5m；Pelleter revolving speed is 200~400r/min；
Using packaging of aluminium foil bag functional master batch.
Embodiment 1
(1) 90 parts of nylon, 6,6 parts of fumed silicas, 2 parts of ptfe micropowders, 3 parts of inclined fluorine second proportion weighing: are weighed
Alkene-hexafluoropropylene copolymer, 1 part of antioxidant 1010；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Ptfe micropowder, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 add from the side of double screw extruder position material mouth
Add, carries out melt blending；Before side position material mouth is located at the mixing section of double screw extruder；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Embodiment 2
(1) 90 parts of nylon, 6,6 parts of silica, 3 parts of ptfe micropowders, 5 parts of vinylidenes-proportion weighing: are weighed
Hexafluoropropylene copolymer, 0.5 part of antioxidant 1010；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, calcium carbonate, polytetrafluoro
Ethylene micro mist, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 are carried out from the material mouth addition of the side of double screw extruder position
Melt blending；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Embodiment 3
(1) 85 parts of nylon, 6,8 parts of fumed silicas, 1 part of ptfe micropowder, 2 parts of inclined fluorine second proportion weighing: are weighed
Alkene-hexafluoropropylene copolymer, 2 parts of antioxidant 1010s；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Ptfe micropowder, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 add from the side of double screw extruder position material mouth
Add, carries out melt blending；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Embodiment 4
(1) 95 parts of nylon, 6,5 parts of fumed silicas, 3 parts of ptfe micropowders, 2 parts of inclined fluorine second proportion weighing: are weighed
Alkene-hexafluoropropylene copolymer, 0.5 part of antioxidant 1010；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Ptfe micropowder, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 add from the side of double screw extruder position material mouth
Add, carries out melt blending；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Embodiment 5
(1) 90 parts of nylon, 6,6 parts of calcium carbonate, 2 parts of ptfe micropowders, 3 parts of vinylidenes-six proportion weighing: are weighed
Fluoropropene copolymer, 1 part of antioxidant 1010；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, calcium carbonate, polytetrafluoro
Ethylene micro mist, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 are carried out from the material mouth addition of the side of double screw extruder position
Melt blending；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Embodiment 6
(1) 95 parts of nylon, 6,8 parts of fumed silicas, 3 parts of medicine ball silicon, 2 parts of vinylidenes-six proportion weighing: are weighed
Fluoropropene copolymer, 2 parts of antioxidant 1010s；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Medicine ball silicon, vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 are carried out from the material mouth addition of the side of double screw extruder position
Melt blending；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get to originally
The invention functional master batch.
Reference examples 1
(1) 90 parts of nylon, 6,6 parts of calcium carbonate, 4 parts of erucyl amides proportion weighing: are weighed；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, calcium carbonate, erucic acid acyl
Amine carries out melt blending from the material mouth addition of the side of double screw extruder position；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get one kind
Functional master batch.
Reference examples 2
(1) proportion weighing: weigh 90 parts of nylon, 6,6 parts of fumed silicas, 2 parts of vinylidene fluoride-hexafluoropropylene copolymers,
0.5 part of antioxidant 1010；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Vinylidene fluoride-hexafluoropropylene copolymer, antioxidant 1010 carry out melt blending from the material mouth addition of the side of double screw extruder position；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get one kind
Functional master batch.
Reference examples 3
(1) 90 parts of nylon, 6,6 parts of fumed silicas, 2 parts of ptfe micropowders, 1.5 parts of poly- second proportion weighing: are weighed
Alkene wax；
(2) melt blending: above-mentioned weighed nylon 6 is added from the main spout of double screw extruder, fumed silica,
Ptfe micropowder, polyethylene wax carry out melt blending from the material mouth addition of the side of double screw extruder position；
(3) extruded stock post-processes: the material squeezed out through melt blending, crosses water cooling, pelletizing, drying, packaging to get one kind
Functional master batch.
Reference examples 4
Commercially available 6 anti-adhesion master batch of nylon.
By the functional master batch of Examples 1 to 6 and reference examples 1~4 according to the dosage and surface layer relative viscosity of mass fraction 4%
3.2 polyamide mixing, produces two-way stretching polyamide film, and production equipment is that three layers of German Bruckner company squeeze
Machine and step drawing unit, main production are as follows out:
Processing temperature: 220~250 DEG C
Screw speed: 45~90rpm
Longitudinal stretching ratio: 2.85
Cross directional stretch ratio: 3.3
Heat setting temperature: 195 DEG C.
Corresponding test is done to the polyamide film of addition different formulations functional master batch preparation, such as table 1:
Coefficient of friction is tested according to GB/T10006-1988 plastic film and thin slice measuring friction coefficient method；
Tensile strength is tested according to GB/T13022-1991 stretched plastic film method for testing performance；
Mist degree is tested according to the measuring method of GB/T2410-2008 transparent plastic light transmittance and mist degree；
Corona decaying: corona is tested according to the method for measuring of GB/T14126-2008 plastic foil and piece moistened surface tension
Then film is continuously dried 7 days in 60 DEG C of baking ovens, tests the final corona value of corona surface, initially by the corona value in initial corona face
The final corona value=corona pad value of corona value-.
" clear lip " time interval is film continuous production since mouth mold material deposition leads to rupture of membranes and scratches film surface not
Obtain the time interval for not shutting down cleaning mouth mold.
Table 1
By the experimental data of Examples 1 to 6 in upper table 1 it is found that two-way drawing provided by the invention compared with reference examples 1~4
It stretches polyamide film functional master batch and extends shutdown " clear lip " time interval in the production process of polyamide film with outstanding
Excellent effect shuts down " clear lip " time interval and reaches 30h or more, and wherein shutdown " clear lip " time interval of embodiment 1 is up to
41h；By adding the experimental data of Examples 1 to 6 in upper table 1 it is found that compared with reference examples 1, corona free decaying risk, friction system
Number is extremely low less than 0.3；The data of table 1 are also found that polyamide film prepared by embodiment 1 and embodiment 4 in comprehensive analysis
Risk that mist degree is low, coefficient of friction is small, tensile strength is high and corona free is decayed, extension shutdown " clear lip " time interval is long, comprehensive
It can be excellent.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of two-way stretching polyamide film functional master batch, which is characterized in that in parts by weight, including following component is prepared into
It arrives:
2. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that with parts by weight
Meter, including following component are prepared:
3. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that the polyamide
Carrier is at least one of polyamide and polyamide resin blends object；
Wherein, the polyamide be nylon 6, nylon 7, nylon 11, nylon 12, nylon66 fiber, nylon 6T, in nylon 46 extremely
Few one kind；
The polyamide resin blends object is at least one of polyamide resin resin copolymer and polyamide alloy.
4. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that the opening agent
For at least one of calcium carbonate, diatomite, talcum powder, silica, glass microballoon, silicate；The opening agent is averaged grain
Diameter is 2~6um.
5. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that the opening is refreshing
Sliding auxiliary agent be the polymethyl methacrylate being crosslinked, ptfe micropowder, the silicon powder of crosslinking, crosslinked polystyrene particle,
At least one of solid preparing spherical SiO 2；The average grain diameter of the smooth auxiliary agent of opening is 2~6um.
6. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that the processing helps
Agent is at least one of fluorine-containing polymer processing aid and silane processing aid.
7. a kind of two-way stretching polyamide film functional master batch according to claim 1, which is characterized in that the antioxidant
For at least one of antioxidant 1010, antioxidant 1098, antioxidant 1076, antioxidant 264, irgasfos 168.
8. a kind of preparation method of such as described in any item two-way stretching polyamide film functional master batch of the claims 1~7,
It is characterized by comprising the following steps:
Step 1: weighing nylon resin carrier, opening agent, the smooth auxiliary agent of opening, processing aid, antioxidant according to the ratio, it is added extremely
Double screw extruder carries out melt blending extrusion；
Step 2: melt blending squeeze out after material, cross water cooling, pelletizing, drying, packaging to get to two-way stretching polyamide
Functional master batch.
9. a kind of preparation method of two-way stretching polyamide film functional master batch according to claim 8, it is characterised in that:
The screw diameter of double screw extruder is 40~100mm in step 1, and draw ratio is 30~60, and extruder temperature is 180~300
DEG C, the die head temperature of extruder is 230~270 DEG C, and rate of feeding is 10~60r/min, and screw speed is 250~600r/
min。
10. a kind of preparation method of two-way stretching polyamide film functional master batch, feature according to requiring 8 exist
In the cooling water length in step 2 is 3~5m, and pelleter revolving speed is 200~400r/min, using packaging of aluminium foil bag.
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Cited By (7)
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| CN110540747A (en) * | 2019-10-12 | 2019-12-06 | 厦门长塑实业有限公司 | Ultrahigh-friction master batch and preparation method thereof, ultrahigh-friction polyamide film and preparation method thereof |
| CN111574826A (en) * | 2020-04-27 | 2020-08-25 | 浙江巨化新材料研究院有限公司 | Polytetrafluoroethylene master batch for nylon modification and preparation method thereof |
| CN112405935A (en) * | 2020-11-19 | 2021-02-26 | 厦门长塑实业有限公司 | Matte black polyamide film for lithium ion battery, black master batch of matte black polyamide film and preparation method of black master batch |
| CN112745666A (en) * | 2020-12-24 | 2021-05-04 | 沧州东鸿包装材料有限公司 | Method for manufacturing special opening master batch for BOPA (biaxially-oriented polyamide) film |
| CN113248909A (en) * | 2021-05-06 | 2021-08-13 | 昆山运城塑业有限公司 | High-puncture-force biaxially oriented polyamide film and preparation method thereof |
| CN113265073A (en) * | 2021-06-02 | 2021-08-17 | 昆山运融新材料科技有限公司 | Biaxially oriented polyamide film smooth brightening functional master batch and preparation method thereof |
| CN114702746A (en) * | 2022-05-16 | 2022-07-05 | 成都思立可科技有限公司 | Polyolefin film opening smooth master batch and preparation method thereof |
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