CN102294867B - Optical-grade self-adhesive polyethylene protective film and preparation method thereof - Google Patents
Optical-grade self-adhesive polyethylene protective film and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to a preparation method of a self-adhesive polyethylene protective film with optical-grade transparency. The protective film of the invention comprises three layers of a self-adhesive layer, an interlayer, and a back-material layer, and is a composite film obtained by coextrusion film blowing. Thereinto, the self-adhesive layer accounts for 10%-20% of the composite film in thickness; the interlayer accounts for 60%-80% of the composite film in thickness; and the back-material layer accounts for 10%-20% of the composite film in thickness. The self-adhesive layer is compounded by low density polyethylene and metallocene low density polyethylene with a ratio of 20/80-40/60 wt%; the interlayer is compounded by low density polyethylene and medium density polyethylene with a ratio of 20/80-40/60 wt%; and the back-material layer is composed of low density polyethylene. Three coextrusion film blowing units are all single screw machines with a length-diameter ratio of 28; the plastification extrusion process adopts a supercritical nitrogen fluid conveying system; and the extrusion film blowing process is performed in a dust-free and clean workshop. With the method of the invention, a self-adhesive polyethylene protective film with optical-grade transparency can be prepared.
Description
Technical field
The present invention relates to a kind of preparation method of optical grade tack polyethylene protective film.
Technical background
As its name suggests, diaphragm is exactly a kind of film that is prone to the infringement surface that is used for protecting.The function of diaphragm be prevent protected substrate surface transport, assemble or process in the middle of suffer damage or pollute.Diaphragm can be attached to protected substrate surface always, when product is sent to the user, just is torn and abandons.Therefore, under the basic performance requirement: suitable and stable viscosity, tear easily, diaphragm tear the no cull in back, do not take a photograph, after the long-time applying, can not have bubble to float or alice, need have weatherability during outdoor use.Many electrical equipment, top-grade furniture, ornament materials are all used this diaphragm.
According to used cohesive material classification, diaphragm can be divided into gluing type diaphragm and tack diaphragm.Gluing type diaphragm is for use most diaphragm the most widely at present, and the scope of application comprises the high-tech diaphragm of low price traditional protection film and high additive value.Then there are solvent-borne type adhesion rubber agent (Solvent Type Rubber Based Adhesive), solvent-type acrylic sticker (Solvent Type Acrylic Based Adhesive), water soluble acrylic acid sticker (Aqueous Acrylic Based Adhesive) and silicone sticker (Silicone Based Adhesive) in sticker system commonly used.The tack diaphragm is common in high additive value and the diaphragm higher to quality requirements.This type of diaphragm is generally the co-extrusion polyethylene film of two-layer above (or three layers), and one side is used the tack material and need not to use sticker therein.Common tack material comprises EVA, ultra-low density polyethylene (Ultra Low Density Linear Low Density Polyethylene or ULDPE) or polyolefin plastomers resin (Polyolefin Plastomer or POP).
Along with the fast development of IT, electrical type industry and the exploitation of many emerging high-tech applications, can be increasing to the diaphragm demand of electronic product.Electronic applications develops into a new direction of using for polyethylene protective film.Because the economic and technical advantage that polyethylene is intrinsic, using polyethylene protective film at electronic applications has been trend of the times, and occupation rate of market also day by day promotes.Yet, therefore very strict requirement must be arranged to cleanliness factor, brilliant some level, thickness and the apparent mass (fineness) that covers diaphragm in the above because that the surface of electronic product parts is highly brittle is weak and responsive.Diaphragm must have very high cleanliness factor, ultra-thin thickness, must have very high transparency simultaneously, and product must reach the transparency of optical grade.Also require the surface of diaphragm very level and smooth in addition, be near minute surface, only in this way, could let the pressure that forms similar vacuum or Negative Pressure Difference between the surface both, increase applying power.
The tack polyethylene protective film of preparation all is to form through composite different polyolefine material at present.European patent EP 0592913 used material is the copolymer of undersaturated polar monomer and a-alkene.What U.S. Pat 6319353 adopted is the material of the copolymer of a-alkene.What EP0519278 and US5601917 used is polyisobutene material preparation diaphragm.What US4624991 described is a kind of cold drawn from mucous membrane, and its material comprises ethene and a-olefin copolymer, polyisobutene, random polypropylene, butadiene rubber and brombutyl.What French Patent (FRP) was described forms from mucous membrane oil boom thermoplastic elastic, polyolefin, polybutadiene or polybutene, and the carboxylic acid of partial esterification and polyalcohol are as additive.200410011040.2 of Chinese patents have adopted the coextrusion film blowing prepared to go out trilamellar membrane, and wherein self-adhesive layer adopts ethylene-vinyl acetate copolymer (EVA) to come tackify.
Can find out that from above the adhesion resin of current preparation tack diaphragm mainly is nonpolar polyisobutene, and the copolymer of ethene and polar monomer, comprise polyacrylic acid and ester class and ethylene-vinyl acetate copolymer.Polyisobutene has good tack, but the peeling force of diaphragm has a declining tendency in time.And utilize the copolymer polar group of ethene and polar monomer can damage to some extent to electronic component.Especially crucial is, the prepared diaphragm that goes out does not reach the transparency of optical grade.
Summary of the invention
The objective of the invention is to deficiency, a kind of preparation method of optical grade tack polyethylene protective film is provided to prior art.
The purpose of this invention is to provide the tack that a kind of new metallocene ldpe resin improves diaphragm; The plasticizing expressing technique of polyvinyl resin has adopted overcritical nitrogen fluid delivery system to reduce the brilliant point of film; The blown film production of extruding of diaphragm has used clean system to improve the cleanliness factor of diaphragm, makes the transparency of product reach the optics rank.
The optical grade tack polyethylene protective film of the present invention's preparation specifically can be realized through following scheme:
Polyethylene protective film of the present invention is to be made by three-layer co-extruded blown film.Wherein self-adhesive layer accounts for 10% ~ 20% of diaphragm gross thickness, and the viscosity from mucous membrane is provided, and guarantees the adhesive property of diaphragm; The intermediate layer accounts for 60% ~ 80% of diaphragm gross thickness, can ensure the effective combination between self-adhesive layer and the backing layer, improves the mechanical property of film; The backing layer accounts for 10% ~ 20% of diaphragm gross thickness, mainly is to guarantee excellent filming performance.
Self-adhesive layer is a core content of the present invention; The polyisobutene and the ethylene-vinyl acetate copolymer of report before its main component is different from; What adopt is that metallocene low density polyethylene (LDPE) and ldpe resin form in the ratio of coming 20/80 ~ 40/60wt% is composite; The self-adhesion performance of diaphragm is provided, regulates suitable self-adhesive layer viscosity, prevent that blown film from adding the man-hour self-adhesive layer and being difficult for peeling off.The optimum low density polyethylene (LDPE) and the compound proportion of metallocene low density polyethylene (LDPE) are 30/70wt%.Used resin is business-like blown film grade resins, and the melt flow rate (MFR) of low density polyethylene (LDPE) is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.924 kg/m
3, low density polyethylene (LDPE) can be selected for use but be not limited to Daqing petrochemical or raise the 2420H that sub-BASF is produced.The melt flow rate (MFR) of metallocene low density polyethylene (LDPE) is 0.8-1.3/10min, and density is 0.918 kg/m
3, the metallocene low density polyethylene (LDPE) can be selected for use but be not limited to the 1018HA that Exxon Mobil is produced.
The key component in intermediate layer is that low density polyethylene (LDPE) and medium density polyethylene resin form in the ratio of coming 20/80 ~ 40/60wt% is composite, ensures the effective combination between self-adhesive layer and the backing layer, improves the mechanical property of film.The optimum low density polyethylene (LDPE) and the compound proportion of medium density polyethylene are 30/70wt%.Used resin is business-like blown film grade resins, and the melt flow rate (MFR) of used low density polyethylene (LDPE) is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.930 kg/m
3, low density polyethylene (LDPE) can be selected for use but be not limited to Daqing petrochemical or raise the 2420H that sub-BASF is produced.The melt flow rate (MFR) of medium density polyethylene is 0.3 ~ 1.0g/10min, and density is 0.930 ~ 0.936kg/m
3Medium density polyethylene can be selected for use but be not limited to Exxon Mobil and produce 3505CH.
The key component of backing layer is that pure low density polyethylene (LDPE) is formed, and mainly is to guarantee excellent filming performance.Used resin is business-like blown film grade resins, and the melt flow rate (MFR) of used low density polyethylene (LDPE) is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.925 kg/m
3, low density polyethylene (LDPE) can be selected for use but be not limited to Daqing petrochemical or raise the 2420H that sub-BASF is produced.
In order to reduce the brilliant point of polyvinyl resin, improve the transparency of diaphragm, adopted overcritical nitrogen fluid delivery system at the plasticizing expressing technique of polyvinyl resin, reduce the brilliant point of polyvinyl resin, can improve the transparency of diaphragm.
In order further to improve diaphragm surface smooth degree, improve the transparency of diaphragm, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning, has used clean system in process of production, makes the transparency of diaphragm reach optical grade.
The diaphragm for preparing according to said components, composition and preparation method has excellent tack and good mechanical performance, machine-shaping easily, and the transparency can reach the optics rank, can be used in the protection on the sophisticated electronics surface of electronic applications.
Description of drawings
Fig. 1 is that optical grade tack polyethylene protective film of the present invention is produced sketch map.
Fig. 2 is the optical grade tack polyethylene protective film that the present invention makes.
The specific embodiment
Below through embodiment the present invention is described further.Under the prerequisite that guarantees mechanical property, light transmittance is high more good more with viscosity, and expression material combination property is good more.
Embodiment 1:
Get the backing layer resin of the low density polyethylene (LDPE) 2420H of Daqing petrochemical production as diaphragm; Get 30 parts of the low density polyethylene (LDPE) 2420H that Daqing petrochemical produces, 70 parts of intermediate layer resins of medium density polyethylene 3505CH that Exxon Mobil is produced as diaphragm; Get 30 parts of the low density polyethylene (LDPE) 2420H that Daqing petrochemical produces, 70 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1018HA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 195 ℃, and 180 ℃, 175 ℃, 160 ℃, 110 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 15MPa, and longitudinal tensile strength is greater than 25MPa, and the longitudinal fracture percentage elongation is greater than 200%, and the transverse breakage percentage elongation is greater than 400%, and the light transmittance of diaphragm is 84%, and cleanliness factor reaches optical grade.Resulting diaphragm has enough viscosity, can be used in the surface protection of electronic device.
Embodiment 2:
Get and raise low density polyethylene (LDPE) 2420H that sub-BASF produces backing layer resin as diaphragm; Get and raise 30 parts of the low density polyethylene (LDPE) 2420H that sub-BASF produces, 70 parts of intermediate layer resins of medium density polyethylene 3505CH that Exxon Mobil is produced as diaphragm; Get and raise 30 parts of the low density polyethylene (LDPE) 2420H that sub-BASF produces, 70 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1018HA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 195 ℃, and 180 ℃, 175 ℃, 160 ℃, 110 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 15MPa, and longitudinal tensile strength is greater than 25MPa, and the longitudinal fracture percentage elongation is greater than 200%, and the transverse breakage percentage elongation is greater than 400%, and the light transmittance of diaphragm is 85%, and cleanliness factor reaches optical grade.Resulting diaphragm has enough viscosity, can be used in the surface protection of electronic device.
Embodiment 3:
Get the backing layer resin of the low density polyethylene (LDPE) 410E of DOW Chemical production as diaphragm; Get low density polyethylene (LDPE) 100BW30 part that Exxon Mobil is produced, 70 parts of intermediate layer resins of medium density polyethylene 6910AA that Britain BP produces as diaphragm; Get 30 parts of the low density polyethylene (LDPE) 410E that DOW Chemical produces, 70 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1318CA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 190 ℃, and 180 ℃, 170 ℃, 155 ℃, 100 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 15MPa, and longitudinal tensile strength is greater than 25MPa, and the longitudinal fracture percentage elongation is greater than 200%, and the transverse breakage percentage elongation is greater than 500%, and the light transmittance of diaphragm is 93%, and cleanliness factor reaches optical grade.Resulting diaphragm has extremely excellent viscosity, possesses the good comprehensive performance, can be used in the surface protection of electronic device.
Embodiment 4:
Get the backing layer resin of the low density polyethylene (LDPE) 410E of DOW Chemical production as diaphragm; Get low density polyethylene (LDPE) alkene 100BW20 part that Exxon Mobil is produced, 80 parts of intermediate layer resins of medium density polyethylene 6910AA that Britain BP produces as diaphragm; Get 30 parts of the low density polyethylene (LDPE) 410E that DOW Chemical produces, 70 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1318CA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 190 ℃, and 180 ℃, 170 ℃, 155 ℃, 100 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 20MPa, and longitudinal tensile strength is greater than 30MPa, and the longitudinal fracture percentage elongation is greater than 150%, and the transverse breakage percentage elongation is greater than 350%, and the light transmittance of diaphragm is 89%, and cleanliness factor reaches optical grade.Resulting diaphragm has enough viscosity, can be used in the surface protection of electronic device.
Embodiment 5:
Get the backing layer resin of the low density polyethylene (LDPE) 410E of DOW Chemical production as diaphragm; Get low density polyethylene (LDPE) 100BW40 part that Exxon Mobil is produced, 60 parts of intermediate layer resins of medium density polyethylene 6910AA that Britain BP produces as diaphragm; Get 30 parts of the low density polyethylene (LDPE) 410E that DOW Chemical produces, 70 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1318CA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 190 ℃, and 180 ℃, 170 ℃, 155 ℃, 100 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 10MPa, and longitudinal tensile strength is greater than 20MPa, and the longitudinal fracture percentage elongation is greater than 300%, and the transverse breakage percentage elongation is greater than 500%, and the light transmittance of diaphragm is 90%, and cleanliness factor reaches optical grade.Resulting diaphragm has extraordinary viscosity, can be used in the surface protection of electronic device.
Embodiment 6:
Get the backing layer resin of the low density polyethylene (LDPE) 410E of DOW Chemical production as diaphragm; Get low density polyethylene (LDPE) 100BW30 part that Exxon Mobil is produced, 70 parts of intermediate layer resins of medium density polyethylene 6910AA that Britain BP produces as diaphragm; Get 20 parts of the low density polyethylene (LDPE) 410E that DOW Chemical produces, 80 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1318CA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 190 ℃, and 180 ℃, 170 ℃, 155 ℃, 100 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 15MPa, and longitudinal tensile strength is greater than 25MPa, and the longitudinal fracture percentage elongation is greater than 200%, and the transverse breakage percentage elongation is greater than 400%, and the light transmittance of diaphragm is 89%, and cleanliness factor reaches optical grade.Resulting diaphragm has enough viscosity, can be used in the surface protection of electronic device.
Embodiment 7:
Get the backing layer resin of the low density polyethylene (LDPE) 410E of DOW Chemical production as diaphragm; Get low density polyethylene (LDPE) 100BW30 part that Exxon Mobil is produced, 70 parts of intermediate layer resins of medium density polyethylene 6910AA that Britain BP produces as diaphragm; Get 40 parts of the low density polyethylene (LDPE) 410E that DOW Chemical produces, 60 parts of self-adhesive layer resins of metallocene low density polyethylene (LDPE) 1318CA that Exxon Mobil is produced as diaphragm.
Three-layer resin adopts overcritical nitrogen fluid delivery system technology through three extruder coextrusion when extruding, three machines are 5 sections heating, and the temperature from head to 5 sections of charging apertures is set to: 190 ℃, and 180 ℃, 170 ℃, 155 ℃, 100 ℃.Carry out blown film after extruding and obtain three layers of composite protection film, the blown film process of extruding of being carried out is all carried out in the factory building of dustless cleaning.
The prepared diaphragm transverse tensile strength that obtains is greater than 10MPa, and longitudinal tensile strength is greater than 20MPa, and the longitudinal fracture percentage elongation is greater than 200%, and the transverse breakage percentage elongation is greater than 400%, and the light transmittance of diaphragm is 90%, and cleanliness factor reaches optical grade.Resulting diaphragm has good viscosity, can be used in the surface protection of electronic device.
Claims (9)
1. optical grade tack polyethylene protective film; It is characterized in that comprising self-adhesive layer, intermediate layer and backing layer; Self-adhesive layer is made up of according to weight ratio 20/80 ~ 40/60 low density polyethylene (LDPE) and metallocene low density polyethylene (LDPE); The intermediate layer is made up of by weight 20/80 ~ 40/60 low density polyethylene (LDPE) and medium density polyethylene, and the backing layer is made up of low density polyethylene (LDPE).
2. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that said self-adhesive layer, intermediate layer and backing layer account for 10% ~ 20%, 60% ~ 80% and 10% ~ 20% of diaphragm gross thickness respectively.
3. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that the melt flow rate (MFR) of the low density polyethylene (LDPE) that said self-adhesive layer uses is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.924 kg/m
3
4. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that the melt flow rate (MFR) of the metallocene low density polyethylene (LDPE) that said self-adhesive layer uses is 0.8-1.3/10min, and density is 0.918 kg/m
3
5. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that the melt flow rate (MFR) of the low density polyethylene (LDPE) that use in said intermediate layer is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.930 kg/m
3
6. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that the melt flow rate (MFR) of the medium density polyethylene that use in said intermediate layer is 0.3 ~ 1.0g/10min, and density is 0.930 ~ 0.936kg/m
3
7. optical grade tack polyethylene protective film as claimed in claim 1 is characterized in that the melt flow rate (MFR) of the low density polyethylene (LDPE) that said backing layer uses is 1.8 ~ 2.5g/10min, and density is 0.920 ~ 0.925 kg/m
3
8. as the described optical grade tack of above-mentioned arbitrary claim polyethylene protective film, it is characterized in that said self-adhesive layer is made up of according to weight ratio 30/70 low density polyethylene (LDPE) and metallocene low density polyethylene (LDPE); Said intermediate layer is made up of by weight 30/70 low density polyethylene (LDPE) and medium density polyethylene.
9. the preparation method of an optical grade tack polyethylene protective film as claimed in claim 1; The blown film processing method is extruded in employing; It is characterized in that the said blown film process of extruding has adopted overcritical nitrogen fluid delivery system, produce and in clean production system, carry out.
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| CN103173152A (en) * | 2013-02-26 | 2013-06-26 | 昆山韩保胶带科技有限公司 | Low-viscosity self-adhesion PE (polyethylene) static protective film |
| CN103587197B (en) * | 2013-11-25 | 2015-10-28 | 东莞市尼的科技股份有限公司 | A kind of PE diaphragm and manufacture craft thereof |
| CN104497900B (en) * | 2014-12-01 | 2016-09-28 | 张家港康得新光电材料有限公司 | A kind of adhesive protecting film and the application in bonding protection bright finish PC plate thereof |
| CN104789143B (en) * | 2015-03-24 | 2017-08-29 | 昆山金华安电子科技有限公司 | A kind of polypropylene dedicated diaphragm of light guide plate smooth surface |
| CN108381888A (en) * | 2018-02-10 | 2018-08-10 | 六安联众工业自动化技术有限公司 | A kind of production technology of household electrical appliances color steel adhesive protecting film |
| CN111098476A (en) * | 2018-10-25 | 2020-05-05 | 南通超微净化包装技术有限公司 | Production process of high-purity high-density polyethylene plastic barrel |
| CN111483203A (en) * | 2020-04-21 | 2020-08-04 | 珠海徐太日用品有限公司 | High-barrier packaging film with self-adhesion function and preparation method thereof |
| CN114083856B (en) * | 2021-12-07 | 2023-08-11 | 江门市华龙膜材股份有限公司 | High-temperature-resistant self-adhesive pure polyethylene protective film and preparation method thereof |
| CN114347612B (en) * | 2022-01-13 | 2023-08-11 | 江门市华龙膜材股份有限公司 | Polyethylene protective film and preparation method and application thereof |
| CN114347613B (en) * | 2022-01-13 | 2023-06-20 | 江门市华龙膜材股份有限公司 | Microcrystal point high-transparency self-adhesive polyethylene protective film and preparation method thereof |
| CN115926658B (en) * | 2022-12-29 | 2023-09-22 | 广东金榜膜业科技有限公司 | Environment-friendly transparent self-adhesive film and preparation method thereof |
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| US20040146226A1 (en) * | 2003-01-24 | 2004-07-29 | Wolak Paul Zygmunt | Foldover condiment package film |
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| CN201006864Y (en) * | 2007-02-05 | 2008-01-16 | 广州市啊啦棒建材有限公司 | High molecule adhesive bonding film |
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