CN106739365A - One kind can laser marking two-way stretching polyamide film and preparation method thereof - Google Patents
One kind can laser marking two-way stretching polyamide film and preparation method thereof Download PDFInfo
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- CN106739365A CN106739365A CN201611113016.9A CN201611113016A CN106739365A CN 106739365 A CN106739365 A CN 106739365A CN 201611113016 A CN201611113016 A CN 201611113016A CN 106739365 A CN106739365 A CN 106739365A
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- laser marking
- layers
- layer
- polyamide
- way stretching
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/80—Medical packaging
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
The present invention disclose one kind can laser marking two-way stretching polyamide film, by A, B, C, tri- layers are constituted, and wherein A layer is outer layer adherent layer, B layer be can laser marking layer, C layers is polyamide internal layer.The composition of raw materials of each layer is made up of the material of following mass percentage content：A layers：Polyamide 99.0~99.5%, antitack agent 0.5~1%；B layers：Polyamide 99.2~99.8%, laser marking auxiliary agent 0.1~0.5%, dispersant 0.1~0.3%；C layers：Polyamide 100%.It is of the present invention can laser marking two-way stretching polyamide film, laser marking excellent performance, it is particularly well-suited to low-power CO 2 laser marking machine, only laser engraving icon can be produced at B layers of film, make icon that there is the antiforge function such as very strong scratch-resistant, corrosion-resistant and anti-tamper, be widely used in the packagings such as packaging for foodstuff, pharmaceuticals packaging and electronic device.The present invention also provide it is a kind of prepare can laser marking two-way stretching polyamide film method.
Description
Technical field
The present invention relates to a kind of polyamide film and preparation method thereof, more particularly to one kind can laser marking biaxial tension gather
Amide film and preparation method thereof.
Technical background
Two-way stretching polyamide film has larger tensile strength, excellent wear-resistant, paracentesis resistance, and has preferably
Barrier.In terms of chemical property, polyamide film is alkaline-resisting, organic solvent-resistant and grease, also resistance to most acid.Because having
These good characteristics, and be widely used in numerous industries such as packaging for foodstuff, electronic packaging, medical packaging and field.It is most of
Packaging be required for printed patterns, it is general on polyamide film that inner print is carried out using intaglio printing, it is thin with other after printing
Bag after film is compound, printed patterns are placed on the center section of whole package construction layer, but date of manufacture, batch number are even
It is some numberings, coding or customization of individual character icon etc., can only is the follow-up appearance in film due to printing cannot be previously set
The direct table print in face.The packaging coder of the most frequently used date of manufacture etc. uses ink at present, and the icon such as date of manufacture is used
Ink is attached to the outer surface of packaging film, so allows for the icon and have being worn, corroding even in process is transported
The risk being tampered.
Laser marking be the laser beam using high-energy-density to interacting goals, target surface is occurred physically or chemically
Change, so as to obtain the mark mode of visible pattern, the laser beam focus of high-energy make material rapid vaporization in material surface,
Form pit.Cut-offfing for laser is controlled simultaneously as laser beam is regularly moved in material surface.Laser beam is also just in material
A pattern specified is processed on surface.Compared with conventional tag technique, laser marking has signature velocity fast, and writing is clear
It is clear, it is not easy to wear, the features such as antiforge function is strong.
Laser markup can have differences to different macromolecule polymer materials, absorption of the most polymers to laser
Poor, particularly polyamide using laser it is difficult to be marked, and is a kind of to improve poly- using laser marking auxiliary agent
Compound can be markup common method.Laser marking auxiliary agent is that the light wave for sending laser machine absorbs and is transformed into heat energy, this
Heat energy can make the polymer carbonization or foaming near it, so as to produce mark.
The content of the invention
The scope of the present invention only receives claims defined, not by this section institute those set forth in any degree
Limitation.
Can laser marking two-way stretching polyamide film present invention aim at one kind is provided so that in low-power titanium dioxide
Also polyamide film can be made obvious laser marking pattern is produced under carbon laser marking machine, and the pattern only occurs in film
Sandwich layer, so that the icon of the packaging has the antiforge function such as very strong scratch-resistant, corrosion-resistant and anti-tamper, it is adaptable to food
The fields such as packaging, electronic packaging, medical packaging.Meanwhile, can laser marking two-way stretching polyamide present invention also offers one kind
The preparation method of film.
To reach above-mentioned purpose, the present invention is achieved by the following technical solutions：
One kind can laser marking two-way stretching polyamide film, it is characterised in that by A, B, C, tri- layers are constituted, and wherein A layers is
Outer layer adherent layer, B layers for can laser marking layer, C layer be polyamide internal layer.The composition of raw materials of each layer is contained by following mass percent
The material composition of amount：A layers：Polyamide 99.0~99.5%, antitack agent 0.5~1%；B layers：Polyamide 99.2~99.8%, swashs
Light mark auxiliary agent 0.1~0.5%, dispersant 0.1~0.3%；C layers：Polyamide 100%.
Wherein, it is described can laser marking two-way stretching polyamide film, it is characterised in that the polyamide is nylon 6
(PA6), polyhexamethylene adipamide (PA66), nylon 1010 (PA1010), poly- 11 lactams (PA11), in poly- 12
Acid amides (PA12), nylon 46 (PA46), polyhexamethylene sebacamide (PA610), nylon 612
(PA612), acyl dodecane lauryl amine (PA1212) of poly- dodecane two, poly-m-phenylene adipamide (MXD6), poly- paraphenylene terephthalamide
At least one in nonamethylene diamine (PA9T), poly- hexamethylene terephthalamide (PA6T).
Further, above-mentioned polyamide is preferably nylon 6 (PA6).
Wherein, it is described can laser marking two-way stretching polyamide film, it is characterised in that the laser marking auxiliary agent is
TiO2 coated micas, TiO2/SiO2 mixed oxides, antimony oxide, antimony oxide/metal oxide cladding silicate are mixed
At least one in compound, copolymer of methyl methacrylatestyrene/barium sulfate mixture.
Further, above-mentioned laser marking auxiliary agent is preferably antimony oxide/metal oxide cladding silicate mixture.
Further, the particle diameter of above-mentioned laser marking auxiliary agent is 0.1~2 μm.
Wherein, it is described can laser marking two-way stretching polyamide film, it is characterised in that described dispersant is ethene
Base bis-stearamides, glyceryl monostearate, glyceryl tristearate, barium stearate, zinc stearate, calcium stearate, stearic acid
At least one in magnesium, Tissuemat E.
Wherein, it is described can laser marking two-way stretching polyamide film, it is characterised in that described antitack agent is talcum
At least one in powder, silica, calcium carbonate, glass microballoon, clay, diatomite, aluminum oxide, magnesia, Almasilate.
The present invention also provide it is a kind of can laser marking two-way stretching polyamide film preparation method, enter according to the following steps
OK：
The first step, each component in A, B, C layer is mixed respectively in proportion, and be uniformly dispersed by homogenizer；
Second step, by the raw material of tri- layers of A, B, C respectively by respective extruder melting extrusion, flows out by T-shaped mould head,
And non-stretched sheet material is cooled on sharp cooling roll, the wherein temperature of sharp cooling roll is 15~40 DEG C, and the thickness of non-stretched sheet material is
90~500 μm；
3rd step, by non-stretched sheet material after tank carries out damping, heating carries out transverse and longitudinal synchro-draw, wherein stretching
Temperature is 170~200 DEG C, and stretching ratio is 2.5*2.5~3.2*3.2；
4th step, by thermal finalization obtain it is described can laser marking two-way stretching polyamide film, wherein film thickness
Be 12~60 μm, can laser marking layer thickness be 10~30 μm.
The beneficial effects of the invention are as follows：
The invention provides one kind can laser marking two-way stretching polyamide film, its laser marking excellent performance, especially
Suitable for low-power CO 2 laser marking machine, laser engraving icon only can be produced at sandwich layer B layers of film, there is icon
The antiforge function such as very strong scratch-resistant, corrosion-resistant and anti-tamper, is widely portable to packaging for foodstuff, pharmaceuticals packaging and electronics device
Part etc. is packed.Meanwhile, it is that polyamide internal layer (C layers) need not add antitack agent, can also make that the present invention also has a beneficial effect
Film integrally possesses excellent opening performance, advantageously reduces the production cost of product.
Brief description of the drawings
Fig. 1 be the present invention can laser marking two-way stretching polyamide film structural representation.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
One kind can laser marking two-way stretching polyamide film, it is characterised in that by A, B, C, tri- layers are constituted, and wherein A layers is
Outer layer adherent layer, B layers for can laser marking layer, C layer be polyamide internal layer.The composition of raw materials of each layer is contained by following mass percent
The material composition of amount：A layers：Polyamide 99.0~99.5%, antitack agent 0.5~1%；B layers：Polyamide 99.2~99.8%, swashs
Light mark auxiliary agent 0.1~0.5%, dispersant 0.1~0.3%；C layers：Polyamide 100%.
Wherein, the polyamide is nylon 6 (PA6), polyhexamethylene adipamide (PA66), nylon 1010
(PA1010), poly- 11 lactams (PA11), nylon 12 (PA12), nylon 46 (PA46), poly- decanedioyl
Hexamethylene diamine (PA610), nylon 612 (PA612), acyl dodecane lauryl amine (PA1212) of poly- dodecane two, gather oneself
In two acyl m-phenylene diamine (MPD)s (MXD6), poly-paraphenylene terephthalamide's nonamethylene diamine (PA9T), poly- hexamethylene terephthalamide (PA6T) at least
It is a kind of.More preferably nylon 6 (PA6).
Described laser marking auxiliary agent is TiO2 coated micas, TiO2/SiO2 mixed oxides, antimony oxide, three oxygen
In changing two antimony/metal oxide cladding silicate mixture, copolymer of methyl methacrylatestyrene/barium sulfate mixture
At least one.Described laser marking auxiliary agent is preferably antimony oxide/metal oxide cladding silicate mixture, its grain
Footpath is 0.1~2 μm.
Described dispersant is vinyl bis-stearamides, glyceryl monostearate, glyceryl tristearate, stearic acid
At least one in barium, zinc stearate, calcium stearate, magnesium stearate, Tissuemat E.
Described antitack agent is talcum powder, silica, calcium carbonate, glass microballoon, clay, diatomite, aluminum oxide, oxidation
At least one in magnesium, Almasilate.
It is described can laser marking two-way stretching polyamide film, be prepared according to the following steps：
The first step, each component in A, B, C layer is mixed respectively in proportion, and be uniformly dispersed by homogenizer；
Second step, by the raw material of tri- layers of A, B, C respectively by respective extruder melting extrusion, flows out by T-shaped mould head,
And non-stretched sheet material is cooled on sharp cooling roll, the wherein temperature of sharp cooling roll is 15~40 DEG C, and the thickness of non-stretched sheet material is
90~500 μm；
3rd step, by non-stretched sheet material after tank carries out damping, heating carries out transverse and longitudinal synchro-draw, wherein stretching
Temperature is 170~200 DEG C, and stretching ratio is 2.5*2.5~3.2*3.2；
4th step, by thermal finalization obtain it is described can laser marking two-way stretching polyamide film, wherein film thickness
Be 12~60 μm, can laser marking layer thickness be 10~30 μm.
Laser marking machine uses 10W CO 2 laser marking machines.
Embodiment 1
The composition of raw materials that three layers of film is made up of the material of following mass percentage content：A layers：Nylon 6 resin 99.5%,
Talcum powder 0.5%；B layers：Nylon 6 resin 99.2%, antimony oxide/metal oxide cladding silicate mixture 0.5%, firmly
Resin acid calcium 0.3%；C layers：Nylon 6 resin 100%.
Sample is prepared according to aforementioned preparation process, the gross thickness of film is obtained for 12 μm, wherein B thickness degree is 10 μm.
10W CO 2 laser marking machines setting power is 10%.
Embodiment 2
The composition of raw materials that three layers of film is made up of the material of following mass percentage content：A layers：Nylon 6 resin 99.2%,
Talcum powder 0.8%；B layers：Nylon 6 resin 99.5%, antimony oxide/metal oxide cladding silicate mixture 0.3%, firmly
Resin acid calcium 0.2%；C layers：Nylon 6 resin 100%.
Sample is prepared according to aforementioned preparation process, the gross thickness of film is obtained for 30 μm, wherein B thickness degree is 20 μm.
10W CO 2 laser marking machines setting power is 20%.
Embodiment 3
A layers：Nylon 6 resin 99.0%, talcum powder 1.0%；B layers：Nylon 6 resin 99.7%, antimony oxide/metal oxygen
Compound coats silicate mixture 0.1%, calcium stearate 0.2%；C layers：Nylon 6 resin 100%.
Sample is prepared according to aforementioned preparation process, the gross thickness of film is obtained for 60 μm, wherein B thickness degree is 30 μm.
10W CO 2 laser marking machines setting power is 30%.
Comparative example 1
In this comparative example, B layers without laser marking auxiliary agent, three layers of composition of raw materials is by following mass percentage content
Material composition：A layers：Nylon 6 resin 99.2%, silica 0.8%；B layers：Nylon 6 resin 100%；C layers：Nylon 6 resin
100%.
Sample is prepared according to aforementioned preparation process, the gross thickness for obtaining film is 15 μm.
10W CO 2 laser marking machines setting power is 40%.
Comparative example 2
In this comparative example, B layers without laser marking auxiliary agent, three layers of composition of raw materials is by following mass percentage content
Material composition：A layers：
Nylon 6 resin 99.2%, silica 0.8%；B layers：Nylon 6 resin 100%；C layers：Nylon 6 resin 100%.
Sample is prepared according to aforementioned preparation process, the gross thickness for obtaining film is 25 μm.
10W CO 2 laser marking machines setting power is 80%.
The Example Test Data of table 1
Knowable to upper table result, polyamide film can be allowed in relatively low work(by the formula at B layers in the middle of embodiment 1-3
Clear marking, and mark can be just produced to be only present in the middle of sandwich layer B layers under the laser marking machine of rate, will not in the middle of the A of top layer
There is mark, this causes that the mark is protected in the center section of film, with very strong scratch-resistant, corrosion resistance and false proof
Function, and in comparative example 1 and 2, even if cannot be also marked under laser marking machine at high power.
Claims (6)
1. one kind can laser marking two-way stretching polyamide film, it is characterised in that by A, B, C, tri- layers are constituted, and wherein A layers is outer
Layer adherent layer, B layer for can laser marking layer, C layers be polyamide internal layer；The composition of raw materials of each layer is by following mass percentage content
Material composition：A layers：Polyamide 99.0~99.5%, antitack agent 0.5~1%；B layers：Polyamide 99.2~99.8%, laser
Mark auxiliary agent 0.1~0.5%, dispersant 0.1~0.3%；C layers：Polyamide 100%.
2. according to claim 1 can laser marking two-way stretching polyamide film, it is characterised in that the polyamide is
It is nylon 6 (PA6), polyhexamethylene adipamide (PA66), nylon 1010 (PA1010), poly- 11 lactams (PA11), poly-
Lauric lactam (PA12), nylon 46 (PA46), polyhexamethylene sebacamide (PA610), the acyl of poly- dodecane two oneself two
Amine (PA612), acyl dodecane lauryl amine (PA1212) of poly- dodecane two, poly-m-phenylene adipamide (MXD6), poly- terephthaldehyde
At least one in acyl nonamethylene diamine (PA9T), poly- hexamethylene terephthalamide (PA6T)；Preferably nylon 6 (PA6).
3. according to claim 1 can laser marking two-way stretching polyamide film, it is characterised in that described laser is beaten
Mark auxiliary agent is TiO2 coated micas, TiO2/SiO2 mixed oxides, antimony oxide, antimony oxide/metal oxide cladding
At least one in silicate mixture, copolymer of methyl methacrylatestyrene/barium sulfate mixture；Preferably three oxygen
Change two antimony/metal oxide cladding silicate mixture, particle diameter is 0.1~2 μm.
4. according to claim 1 can laser marking two-way stretching polyamide film, it is characterised in that described dispersant
For vinyl bis-stearamides, glyceryl monostearate, glyceryl tristearate, barium stearate, zinc stearate, calcium stearate,
At least one in magnesium stearate, Tissuemat E.
5. according to claim 1 can laser marking two-way stretching polyamide film, it is characterised in that described antitack agent
For in talcum powder, silica, calcium carbonate, glass microballoon, clay, diatomite, aluminum oxide, magnesia, Almasilate at least
It is a kind of.
6. it is a kind of can laser marking two-way stretching polyamide film preparation method, carry out according to the following steps：
The first step, each component in A, B, C layer is mixed respectively in proportion, and be uniformly dispersed by homogenizer；
Second step, by the raw material of tri- layers of A, B, C respectively by respective extruder melting extrusion, flows out by T-shaped mould head, and
Be cooled into non-stretched sheet material on sharp cooling roll, wherein the temperature of sharp cooling roll is 15~40 DEG C, the thickness of non-stretched sheet material for 90~
500μm；
3rd step, by non-stretched sheet material after tank carries out damping, heating carries out transverse and longitudinal synchro-draw, wherein draft temperature
It it is 170~200 DEG C, stretching ratio is 2.5*2.5~3.2*3.2；
4th step, by thermal finalization obtain it is described can laser marking two-way stretching polyamide film, wherein film thickness is 12
~60 μm, can laser marking layer thickness be 10~30 μm.
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| CN201611113016.9A CN106739365A (en) | 2016-12-06 | 2016-12-06 | One kind can laser marking two-way stretching polyamide film and preparation method thereof |
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| CN201611113016.9A CN106739365A (en) | 2016-12-06 | 2016-12-06 | One kind can laser marking two-way stretching polyamide film and preparation method thereof |
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| JP2017213875A (en) * | 2016-04-28 | 2017-12-07 | 三菱ケミカル株式会社 | Heat-shrinkable laminated film |
| CN110958927A (en) * | 2017-07-18 | 2020-04-03 | 住友电工烧结合金株式会社 | Sintered article and laser marking method for sintered article |
| CN111590992A (en) * | 2020-06-16 | 2020-08-28 | 昆山运城塑业有限公司 | High-temperature-resistant easy-to-peel biaxially oriented nylon film and preparation method thereof |
| CN115214214A (en) * | 2022-06-27 | 2022-10-21 | 昆山运城塑业有限公司 | Stretch-resistant biaxially oriented polyamide film and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017213875A (en) * | 2016-04-28 | 2017-12-07 | 三菱ケミカル株式会社 | Heat-shrinkable laminated film |
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| CN110958927B (en) * | 2017-07-18 | 2022-02-01 | 住友电工烧结合金株式会社 | Sintered article and laser marking method for sintered article |
| CN111590992A (en) * | 2020-06-16 | 2020-08-28 | 昆山运城塑业有限公司 | High-temperature-resistant easy-to-peel biaxially oriented nylon film and preparation method thereof |
| CN115214214A (en) * | 2022-06-27 | 2022-10-21 | 昆山运城塑业有限公司 | Stretch-resistant biaxially oriented polyamide film and preparation method thereof |
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