CN104139592A - BOPP pre-coated basement membrane without primer coatings and preparation method thereof - Google Patents
BOPP pre-coated basement membrane without primer coatings and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a BOPP pre-coated basement membrane without primer coatings and a preparation method of the BOPP pre-coated basement membrane. The BOPP pre-coated basement membrane comprises a functional layer, a core layer and a lower surface layer. The core layer and the lower surface layer are both homo-polypropylene layers. The functional layer is linear low-density polyethylene formed by copolymerizing ethylene and high-grade Alpha-olefin. The three layers are extruded by a die head of a three-layer structure on an extruder and are subjected to curing forming and high-low-temperature alternate longitudinal drawing and transverse drawing, and then the BOPP pre-coated basement membrane is obtained, wherein the tension force of the BOPP pre-coated basement membrane ranges from 4.5 kg to 45 kg, and the thickness of the functional layer of the BOPP pre-coated basement membrane ranges from 1.7 Mum to 2 Mum. The BOPP pre-coated basement membrane without the primer coatings does not need to be subjected to corona treatment and primer treatment, the surface of the functional layer is directly coated with EVA, and then the pre-coated membrane can be obtained; accordingly, the pre-coating linear speed is increased, the primer coatings and a drying oven device required by preparing the pre-coated membrane are omitted, the downstream processing technology is more friendly to environment, and the cost is lower.
Description
Technical field
The present invention relates to a kind of processing film technical field, relate to particularly a kind of BOPP precoating basement membrane without silane coupling agent and preparation method thereof.
Background technology
Printing overlay film industry mainly contains that solvent-borne type films, water-based films and three kinds of techniques of pre-coating film, wherein solvent-borne type film because of pollute greatly and in process of production easily breaking out of fire eliminate gradually; Water-based is filmed and is met environmental requirement, and overlay film intensity is high, but in drying course, needs to consume a large amount of heat energy, is subject to its recombination velocity of moisture evaporation speed restriction simultaneously, and easily produces bubble in recombination process.And pre-coating film is owing to not needing binder, heat drying system, greatly simplified overlay film program, and easy to operate, production flexibility is large, solvent-free smell of while, non-environmental-pollution, more importantly can avoid the overlay film defects such as bubble, delamination, its finished product transparency utmost point advantages of higher completely.So the market prospects of pre-coating film are wide, the i.e. painting technology that replaces becomes main flow trend and is also inevitable.American-European countries has announced to ban use of to film at present, changes pre-coating film into.
At present domestic pre-coating film product is all common EVA type pre-coating film, and for the manual coating technique of low speed and the product that do not need to carry out rolling line, concavo-convex processing, common pre-coating film can meet the demands.But for using increasingly extensive fully automatic high-speed coating technique, and the product that carries out rolling line, concavo-convex processing after covering, common pre-coating film can show the quality problems such as foaming, delamination, has a strong impact on yield rate and the operating efficiency of overlay film.
In addition, current pre-coating film is used silane coupling agent more, and its production cost comprises the base materials such as BOPP, water-based coating fluid, EVA or LDPE, energy consumption and equipment, technique relative complex, and in producing, need ozone generator and corona, ozone also cannot be avoided equipment and operating personnel's injury.
Summary of the invention
The object of the invention is to improve the competitive advantage of following pre-coating film for pre-coating film the deficiencies in the prior art with from cost, the invention provides a kind of without silane coupling agent BOPP precoating basement membrane and preparation method thereof, this preparation method is safe and reliable, can reduce downstream producer processing cost and the pollution to environment.
The present invention has taked following technical scheme for achieving the above object:
Without a BOPP precoating basement membrane for silane coupling agent, comprise functional layer, sandwich layer and lower top layer, described sandwich layer and lower top layer are HOPP layer, the linear low density polyethylene (LLDPE) of described functional layer for being formed by ethene and high ' alpha ' olefin combined polymerization; The density of described low density polyethylene (LDPE) is that 0.9-0.91g/cm3, melt temperature are less than 130 ℃, melt index for being 3.6-4.2g/10min under 230 ℃ of temperature, pressure 2160g condition.
Further, the tension force of described BOPP precoating basement membrane is 4.5～45kg.
Another technical scheme of the present invention is to provide a kind of preparation method of the above-mentioned BOPP precoating basement membrane without silane coupling agent, comprises the following steps:
(1) by the thickness requirement of each layer, the material that forms functional layer, sandwich layer and lower top layer is added respectively in three extruders, by the die head co-extrusion of three-decker, extrude molten state sheet material, make the functional layer thickness in molten state sheet material reach 70～80 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.6～4.8 times of longitudinal stretchings;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 8～9 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the functional layer thickness in BOPP precoating basement membrane is 1.7～2 μ m.
Further, curing molding is carried on the back functional layer on air knife is attached to the cold roll surface slab of 25 ℃ and is carried out curing molding by air knife blast in described step (2).
Further, in described step (3), the alternate vertical withdrawing roll temperature control of high low temperature refers to that the temperature-control range of the steel rider contacting with lower top layer is 130 ℃～138 ℃; The temperature-control range of the Teflon roller contacting with functional layer is 80 ℃～88 ℃.
Further, the preheating section in described step (4) in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
Antistatic master batch or the anti-adhesion master batch that in the HOPP as sandwich layer and lower skin-material in the present invention, can also contain appropriate amount conventional in film production, to improve antistatic, the anti-adhesion performance of BOPP precoating basement membrane.
The BOPP precoating basement membrane of preparation of the present invention is as the base material of pre-coating film, and then applies EVA(ethylene-vinyl acetate copolymer on the surface of the functional layer of BOPP pre-coating film) melt, make pre-coating film.Therefore do not need BOPP precoating basement membrane to carry out corona and primary coat processing when making pre-coating film, and do not need ozone generator and sided corona treatment in producing yet, therefore can avoid the injury of ozone to equipment and operating personnel.
Compared with prior art, the present invention has following beneficial effect:
The winding tension of the BOPP precoating basement membrane that 1, prepared by the present invention is 4.5～45kg, the phenomenon such as curling, wrinkle that produce in the time of can effectively controlling without the rolling of silane coupling agent BOPP precoating basement membrane.
2, to take HOPP and linear low density polyethylene (LLDPE) be raw material in the present invention, by co-extrusion, slab, vertically draw, horizontal drawing with rolling make BOPP precoating basement membrane, it does not need sided corona treatment and primary coat, directly on the surface of its functional layer, apply EVA melt and obtain pre-coating film, thereby improved downstream precoating linear velocity, and save the required silane coupling agent of pre-coating film and baking oven equipment cost, the environmental protection more of the following process of processing technology, product and this product.
3, in BOPP precoating basement membrane of the present invention, functional layer is to adopt the linear low density polyethylene (LLDPE) formed by ethene and high ' alpha ' olefin combined polymerization to form, and its density is that 0.9-0.91g/cm3, melt temperature are less than 130 ℃, melt index for being 3.6-4.2g/10min under 230 ℃ of temperature, pressure 2160g condition.; This linear low density polyethylene (LLDPE) not only can be used for co-extrusion, and itself and EVA be bonding also can obtain larger peeling force value.
4, BOPP precoating basement membrane of the present invention is upper epidermis using the linear low density polyethylene (LLDPE) being formed by ethene and high ' alpha ' olefin combined polymerization as functional layer, and HOPP is as sandwich layer and lower top layer; Then by the die head co-extrusion of three-decker, extrude functional layer, sandwich layer and lower top layer, thereby the cohesive force that can effectively solve linear low density polyethylene (LLDPE) and HOPP is worth little problem.
5, the present invention, by the functional layer THICKNESS CONTROL in the molten state sheet material of coextrusion at 70～80 μ m, can reduce due to functional layer and the other two-layer thickness deviation causing because bulk density is different.
6, the present invention is carried on the back functional layer in air knife and is attached to 25 ℃ of cold roll surface slabs by air knife blast, can solve the problem of the uneven thickness that linear low density polyethylene (LLDPE) that melt temperature is lower produces in air knife air pressure current downflow; And contacting with cold roll surface can rapid curing linear low density polyethylene (LLDPE).
7, longitudinal stretching of the present invention adopts the alternate temperature control of high low temperature, the HOPP layer contact steel rider on lower top layer, 130 ℃～138 ℃ of its temperature-control range, the functional layer contact Teflon roller of upper epidermis, 80 ℃～88 ℃ of its temperature-control range, thus can take into account without longitudinal mechanical performance of silane coupling agent BOPP precoating basement membrane and the roll banding that the solves linear low density polyethylene (LLDPE) layer problem of growing dim.
8, after cross directional stretch, the thickness of functional layer is 1.7～2 μ m, can take into account without the horizontal mechanical performance of silane coupling agent BOPP precoating basement membrane and the problem of thickness evenness.
The specific embodiment
The embodiment of the following stated, is only preferred embodiment of the present invention, not the present invention is done to any type of restriction.Any simple modification, equivalent variations and modification that every foundation technology of the present invention and method essence are done above embodiment, all still belong in the scope of technology of the present invention and method scheme.
In embodiment, the sandwich layer of BOPP precoating basement membrane and the material on lower top layer are HOPP below, the linear low density polyethylene (LLDPE) that the material of its functional layer (being upper epidermis) is formed by ethene and high ' alpha ' olefin combined polymerization, the density of linear low density polyethylene (LLDPE) is that 0.9-0.91g/cm3, melt temperature are less than 130 ℃, melt index for being 3.6-4.2g/10min under 230 ℃ of temperature, pressure 2160g condition.。
embodiment 1
The material on sandwich layer and lower top layer is HOPP; Functional layer material is that the melt temperature that formed by ethene and high ' alpha ' olefin combined polymerization is that 98 ℃, melt index are 3.8g/min(230 ℃, 2160g), the density linear low density polyethylene (LLDPE) that is 0.9g/cm3;
(1) by the thickness requirement of each layer, the HOPP that forms linear low density polyethylene (LLDPE), formation sandwich layer and the lower top layer of functional layer is weighed respectively and added in three extruders, die head co-extrusion by three-decker is extruded, at die head lip, form molten state sheet material, make the functional layer thickness in molten state sheet material reach 70 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller, wherein functional layer is carried on the back on air knife is attached to the cold roll surface slab of 25 ℃ by air knife blast;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.6 times of longitudinal stretchings; Wherein descend the temperature-control range of the steel rider of top layer contact to be 130 ℃ ℃; The temperature-control range of the Teflon roller contacting with functional layer is 80 ℃ ℃;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 8 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the functional layer thickness in BOPP precoating basement membrane is 1.7 μ m; Wherein the preheating section in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
(5) cooled BOPP precoating basement membrane is carried out to rolling, winding tension is 4.5kg.
embodiment 2
Sandwich layer is HOPP and antistatic master batch, lower top layer is HOPP and anti-adhesion master batch, functional layer is the linear low density polyethylene (LLDPE) being formed by ethene and high ' alpha ' olefin combined polymerization, 98 ℃ of the melt temperatures of linear low density polyethylene (LLDPE), melt index 3.8g/min(230 ℃, 2160g), density 0.91g/cm3.
(1) by the thickness requirement of each layer, the HOPP that forms linear low density polyethylene (LLDPE), formation sandwich layer and the lower top layer of functional layer is weighed respectively and added in three extruders, die head co-extrusion by three-decker is extruded, at die head lip, form molten state sheet material, make the functional layer thickness in molten state sheet material reach 80 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller, wherein functional layer is carried on the back on air knife is attached to the cold roll surface slab of 25 ℃ by air knife blast;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.8 times of longitudinal stretchings; Wherein descending the temperature-control range of the steel rider of top layer contact is 138 ℃; The temperature-control range of the Teflon roller contacting with functional layer is 88 ℃;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 9 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the functional layer thickness in BOPP precoating basement membrane is 2 μ m; Wherein the preheating section in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
(5) cooled BOPP precoating basement membrane is carried out to rolling, winding tension is 45kg.
Precoating basement membrane main performance is as table 1.
embodiment 3
HOPP is as sandwich layer and lower top layer, by ethene and high ' alpha ' olefin combined polymerization, forming linear low density polyethylene (LLDPE) is functional layer as upper epidermis, 113 ℃ of the melt temperatures of linear low density polyethylene (LLDPE), melt index 3.6g/min(230 ℃, 2160g), density 0.907g/cm3.
(1) by the thickness requirement of each layer, the HOPP that forms linear low density polyethylene (LLDPE), formation sandwich layer and the lower top layer of functional layer is weighed respectively and added in three extruders, die head co-extrusion by three-decker is extruded, at die head lip, form molten state sheet material, make the functional layer thickness in molten state sheet material reach 74 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller, wherein functional layer is carried on the back on air knife is attached to the cold roll surface slab of 25 ℃ by air knife blast;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.7 times of longitudinal stretchings; Wherein descending the temperature-control range of the steel rider of top layer contact is 134 ℃; The temperature-control range of the Teflon roller contacting with functional layer is 85 ℃;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 8.2 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the functional layer thickness in BOPP precoating basement membrane is 1.8 μ m; Wherein the preheating section in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
(5) cooled BOPP precoating basement membrane is carried out to rolling, winding tension is 15kg.
The main performance of precoating basement membrane is as table 1.
embodiment 4
HOPP is as sandwich layer and lower top layer, the linear low density polyethylene (LLDPE) of two kinds of different performances is functional layer as upper epidermis after mixing in SP0:SP1=4:1 ratio, wherein 113 ℃ of the melt temperatures of 80%SP0, melt index 3.6g/min(230 ℃, 2160g), density 0.907g/cm3; 98 ℃ of the melt temperatures of 20%SP1, melt index 4.2g/min(230 ℃, 2160g), density 0.903g/cm3.
(1) by the thickness requirement of each layer, the HOPP that forms linear low density polyethylene (LLDPE), formation sandwich layer and the lower top layer of functional layer is weighed respectively and added in three extruders, die head co-extrusion by three-decker is extruded, at die head lip, form molten state sheet material, make the functional layer thickness in molten state sheet material reach 77 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller, wherein functional layer is carried on the back on air knife is attached to the cold roll surface slab of 25 ℃ by air knife blast;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.8 times of longitudinal stretchings; Wherein descending the temperature-control range of the steel rider of top layer contact is 136 ℃; The temperature-control range of the Teflon roller contacting with functional layer is 86 ℃;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 8.7 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the functional layer thickness in BOPP precoating basement membrane is 1.9 μ m; Wherein the preheating section in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
(5) cooled BOPP precoating basement membrane is carried out to rolling, winding tension is 30kg.
The main performance of precoating basement membrane is as table 1.
comparative example:
Select the common EVA type precoating basement membrane of the conventional Suzhou Kun Ling production of existing market as a comparison case.
According to relevant criterion, detect respectively hot strength, and the performances such as peel strength, mist degree and thermal contraction of EVA after laminating of the precoating basement membrane in embodiment 2-4 and comparative example, its examination criteria and data are as shown in table 1 below:
From upper table 1, can find out, the present invention, by the standby precoating basement membrane of die head co-extrusion of three-decker, has improved the cohesive force between each layer, thereby has improved the hot strength of precoating basement membrane, and the hot strength of embodiment 2-3 is obviously better than comparative example.In addition precoating basement membrane as the base material of pre-coating film apply after EVA melt with EVA after peel strength reach 1.4-1.7N/15mm, obviously than comparative example 0.4 N/15mm, exceed 3-4 doubly.
In addition, precoating basement membrane of the present invention does not need BOPP precoating basement membrane to carry out corona and primary coat processing when making pre-coating film; And in producing, do not need ozone generator and sided corona treatment, therefore can avoid the injury of ozone to equipment and operating personnel yet.
Above embodiment is not limited only to protection scope of the present invention, all based on fundamental idea of the invention, modify or change all belong to protection scope of the present invention.
Claims (6)
1. without a BOPP precoating basement membrane for silane coupling agent, it is characterized in that: comprise functional layer, sandwich layer and lower top layer, described sandwich layer and lower top layer are HOPP layer the linear low density polyethylene (LLDPE) of described functional layer for being formed by ethene and high ' alpha ' olefin combined polymerization; The density of described low density polyethylene (LDPE) is that 0.9-0.91g/cm3, melt temperature are less than 130 ℃, melt index for being 3.6-4.2g/10min under 230 ℃ of temperature, pressure 2160g condition.
2. the BOPP precoating basement membrane without silane coupling agent according to claim 1, is characterized in that: the tension force of described BOPP precoating basement membrane is 4.5～45kg.
3. the preparation method of the BOPP precoating basement membrane without silane coupling agent as described in claim 1-2 any one: it is characterized in that: comprise the following steps:
(1) by the thickness requirement of each layer, the material that forms functional layer, sandwich layer and lower top layer is added respectively in three extruders, by the die head co-extrusion of three-decker, extrude molten state sheet material, make the functional layer thickness in molten state sheet material reach 70～80 μ m;
(2) the molten state sheet material of extruding is cured to moulding by air knife blast and cold roller;
(3) sheet material of curing molding is sent in longitudinal stretching machine and adopted the alternate vertical withdrawing roll temperature control of high low temperature, realize 4.6～4.8 times of longitudinal stretchings;
(4) sheet material of longitudinal stretching machine outlet is sent in transverse drawing mill again, by preheating, stretching, sizing and cooling 8～9 times of the cross directional stretch of realizing, obtained BOPP precoating basement membrane, the layer thickness in BOPP precoating basement membrane is 1.7～2 μ m.
4. preparation method according to claim 3: it is characterized in that: in described step (2), curing molding is carried on the back functional layer on air knife is attached to the cold roll surface slab of 25 ℃ and carried out curing molding by air knife blast.
5. preparation method according to claim 3: it is characterized in that: in described step (3), the alternate vertical withdrawing roll temperature control of high low temperature refers to that the temperature-control range of the steel rider contacting with lower top layer is 130 ℃～138 ℃; The temperature-control range of the Teflon roller contacting with functional layer is 80 ℃～88 ℃.
6. preparation method according to claim 3: it is characterized in that: the preheating section in described step (4) in transverse drawing mill has 5th district, and its temperature is 175 ℃～180 ℃; Stretch section has 5th district, and its temperature is 153 ℃; Sizing Duan You 5th district, its temperature is 158 ℃; Cooling section has 2nd district, and it is undertaken cooling by natural wind.
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| CN106833424A (en) * | 2017-03-22 | 2017-06-13 | 北京康得新功能材料有限公司 | Outer spreading type Antistatic type pre-coating film and its production method |
| CN109367180A (en) * | 2018-10-16 | 2019-02-22 | 福建师范大学福清分校 | A base film for a primer-free and VOCs-free pre-coating film and a preparation method thereof |
| CN109572124A (en) * | 2018-11-24 | 2019-04-05 | 福融辉实业（福建）有限公司 | Bottomless painting composite membrane of one kind and preparation method thereof |
| CN111690330A (en) * | 2020-05-07 | 2020-09-22 | 安徽国风塑业股份有限公司 | Primer-free double-sided adhesive layer polypropylene pre-coating film and preparation method thereof |
| CN114456726A (en) * | 2021-12-28 | 2022-05-10 | 安徽国风塑业股份有限公司 | A kind of BOPP digital pre-coating film for low temperature embossing and preparation method thereof |
| CN114736412A (en) * | 2022-04-06 | 2022-07-12 | 安徽国风新材料股份有限公司 | Coating type BOPP (biaxially-oriented Polypropylene) embossable pre-coated film and preparation method thereof |
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| CN106833424A (en) * | 2017-03-22 | 2017-06-13 | 北京康得新功能材料有限公司 | Outer spreading type Antistatic type pre-coating film and its production method |
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| CN114824505A (en) * | 2022-04-06 | 2022-07-29 | 苏州时代华景新能源有限公司 | Manufacturing process and production line system for zero deformation of winding type battery |
| CN114824505B (en) * | 2022-04-06 | 2023-11-03 | 苏州时代华景新能源有限公司 | Manufacturing process of zero deformation of winding type battery and production line system thereof |
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Application publication date: 20141112 |