阅读说明：本技术 一种功能性pe基淋膜专用料及其制备方法和应用 (Special functional PE-based laminating material and preparation method and application thereof ) 是由 陈振树 杨友强 丁超 陈平绪 周日敏 李振华 魏金刚 陶俊浩 杨方强 许齐勇 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种功能性PE基淋膜专用料及其制备方法和应用,本发明以线性低密度聚乙烯为基体,以石油树脂和乙烯-醋酸乙烯共聚树脂复配进行界面增粘改性,不仅能显著提高PE基淋膜层与基材的粘结力,且淋膜层无麻面、褶皱、熔体破裂、均匀性差等外观缺陷,淋膜层还具有较高的韧性,可广泛应用于医疗防护、静电屏蔽场所等领域。(The invention discloses a functional PE-based laminating special material and a preparation method and application thereof, wherein linear low-density polyethylene is used as a matrix, and petroleum resin and ethylene-vinyl acetate copolymer resin are compounded to perform interface tackifying modification, so that the adhesive force of a PE-based laminating layer and a base material can be obviously improved, the laminating layer has no appearance defects such as pitted surface, wrinkles, melt fracture, poor uniformity and the like, and the laminating layer also has higher toughness, and can be widely applied to the fields of medical protection, electrostatic shielding places and the like.)

1. The functional PE-based material special for the laminating film is characterized by comprising the following components in parts by mass:

45-70 parts of linear low-density polyethylene;

5-8 parts of petroleum resin;

15-22 parts of ethylene-vinyl acetate copolymer resin;

wherein the melt flow rate of the ethylene-vinyl acetate copolymer resin is 2-8 g/10min at 190 ℃ under 2.16 kg.

2. The special functional PE-based laminating material as claimed in claim 1, which comprises the following components in parts by mass:

55-70 parts of linear low-density polyethylene;

6-8 parts of petroleum resin;

15-22 parts of ethylene-vinyl acetate copolymer resin.

3. The special functional PE-based laminating material as claimed in claim 1 or 2, wherein the petroleum resin is a carbon five petroleum resin and/or a carbon nine petroleum resin.

4. The special functional PE-based laminating material as claimed in claim 1, wherein the melt flow rate of the ethylene-vinyl acetate copolymer resin is 2-6 g/10min at 190 ℃ under 2.16 kg.

5. The special functional PE-based laminating material as claimed in claim 1, wherein the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer resin is 18-26%.

6. The special material for the functional PE-based laminating film according to claim 1, wherein the melt flow rate of the linear low-density polyethylene is 1-8 g/10min at 190 ℃ under 2.16 kg.

7. The special functional PE-based laminating material as claimed in claim 1, wherein the density of the linear low density polyethylene is 0.918-0.935 g/cm³。

8. The special functional PE-based laminating material as claimed in claim 1, further comprising one or more of a compatibilizer, a nanofiller, an antistatic agent, an antioxidant, and a processing aid.

9. The preparation method of the functional PE-based laminating special material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:

mixing low-density polyethylene, petroleum resin and ethylene-vinyl acetate copolymer resin uniformly, melting, extruding, granulating and drying to obtain the special PE-based laminating material, and adding the special PE-based laminating material and the low-density polyethylene together if a compatilizer, a nano filler, an antistatic agent, an antioxidant and a processing aid are contained.

10. The application of the special functional PE-based laminating material of any one of claims 1 to 8 in preparation of PE-based laminating films for medical protection or electrostatic shielding fields.

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a functional PE-based laminating special material and a preparation method and application thereof.

Background

Lamination, also known as extrusion coating, is a process in which a molten resinous material is cast onto a substrate, and then rapidly pressed and cooled to form the shape. For example, one or more polyethylene functional layers are usually laminated on a substrate such as a non-woven fabric, so that the substrate is endowed with high antistatic, antibacterial, waterproof, high toughness and other properties, and the polyethylene functional layer is widely applied to the fields of medical protection and electrostatic shielding.

Chinese patent CN101161736A (published Japanese 2008.4.16) discloses a special coating resin composition for polypropylene heavy-duty flexible freight bags, which is prepared from polypropylene, polyethylene, petroleum resin and the like to prepare a special coating material with strong bonding force and water and moisture resistance, but the petroleum resin is used as a tackifier, so that the phenomena of extrusion surge, roller adhesion, melt fracture and the like are easy to occur in the production process of laminating, and the prepared laminating film surface can have pitted surfaces and folds, thereby generating a large amount of waste products. Therefore, the development of a special material for laminating film can lead the film surface of the prepared laminating film to be bright, avoid the phenomena of pitted surface and wrinkle, ensure good adhesion with a base material (non-woven fabric and the like), and become a hotspot and difficulty of the industry.

Disclosure of Invention

The invention aims to solve the technical problem that the defects and the defects that the film surface of the film is flabby and wrinkled due to the phenomena of surging, roller sticking, melt fracture and the like in the film preparation process of the existing film coating material are overcome, and the special functional PE-based film coating material is provided, is used for the film coating production, does not have the phenomena of surging, roller sticking and melt fracture, has bright film surface and no flabby and wrinkle, and has good cohesiveness with a base material (non-woven fabric and the like).

The invention also aims to provide a preparation method of the special functional PE-based laminating material.

The invention also aims to provide application of the special functional PE-based laminating material.

The above purpose of the invention is realized by the following technical scheme:

a functional PE-based laminating special material comprises the following components in parts by mass:

45-70 parts of linear low-density polyethylene;

5-8 parts of petroleum resin;

15-22 parts of ethylene-vinyl acetate copolymer resin;

wherein the melt flow rate of the ethylene-vinyl acetate copolymer resin is 2-8 g/10min at 190 ℃ under 2.16 kg.

The invention adopts linear low-density polyethylene as a matrix, has better ductility, film forming property, puncture resistance and higher toughness, utilizes the compounding of petroleum resin and ethylene-vinyl acetate copolymer resin (EVA) to perform interface tackifying modification, can obviously improve the binding power of a PE-based laminating layer and a base material, has stable extrusion, no phenomena of extrusion surge, melt fracture and the like, does not generate pitted surface and wrinkles on the laminating film surface, has bright appearance, and has good synergistic action of the petroleum resin and the ethylene-vinyl acetate copolymer resin, and the toughness of the laminating film is improved.

Preferably, the composition is prepared from the following components in parts by mass:

55-70 parts of linear low-density polyethylene;

6-8 parts of petroleum resin;

15-22 parts of ethylene-vinyl acetate copolymer resin.

Preferably, the melt flow rate of the ethylene-vinyl acetate copolymer resin is 2-6 g/10min at 190 ℃ under 2.16 kg.

The method for testing the melt flow rate of the ethylene-vinyl acetate copolymer resin comprises the following steps: the test was carried out according to GB/T3682-.

Preferably, the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer resin is 18-26%.

Preferably, the petroleum resin is a carbon five petroleum resin and/or a carbon nine petroleum resin.

Preferably, the average molecular weight of the petroleum resin is 1000-3000.

Preferably, the melt flow rate of the linear low density polyethylene is 1-8 g/10min at 190 ℃ under 2.16 kg.

More preferably, the linear low density polyethylene has a melt flow rate of 2 to 7g/10min at 190 ℃ under 2.16 kg.

Preferably, the linear low density polyethylene has a density of 0.918-0.935 g/cm³。

Preferably, the tensile strength of the linear low density polyethylene is 14-26 MPa.

Preferably, the composite material further comprises one or more of a compatilizer, a nano filler, an antistatic agent, an antioxidant and a processing aid.

Preferably, the environment-friendly composite material further comprises 4-8 parts of a compatilizer, 0-20 parts of a nano filler, 0.5-2 parts of an antioxidant and 1-2 parts of a processing aid by mass.

The nano filler provided by the invention comprises one or more of nano calcium carbonate, nano talcum powder and nano barium sulfate.

Preferably, the mesh number of the nano filler is 2000-5000 meshes.

The compatilizer provided by the invention comprises one or more of polyethylene grafted maleic anhydride, polyethylene grafted acrylic acid, polyvinyl acetate grafted maleic anhydride, polyethylene grafted methyl methacrylate and polyethylene grafted glycidyl methacrylate.

The compatilizer of the invention includes, but is not limited to, 1:2 hindered phenolic antioxidants and phosphite antioxidants.

The processing aid provided by the invention comprises one or more of a dispersing agent and a lubricating agent.

The dispersing agent provided by the invention comprises one or more of but not limited to a fluorine-containing auxiliary agent, a polyethylene lubricant and a stearic acid lubricant, namely an amide lubricant. The dispersant has smooth effect.

The lubricant of the invention comprises one or more of but is not limited to PE wax (617A), vinyl bis stearamide (EBS B50) and pentaerythritol esters (LOXIOL P861/3.5).

The antistatic agent of the invention includes but is not limited to one or more of stearamidopropyl dimethyl-beta-hydroxyethyl quaternary ammonium nitrate (antistatic agent SN), (3-lauramidopropyl) trimethyl ammonium methyl sulfate (antistatic agent LS), N-bis (2-hydroxyethyl) -N- (3 '-dodecyloxy-2' -hydroxypropyl) methyl ammonium methyl sulfate (antistatic agent 609).

The antioxidants of the present invention include, but are not limited to, combinations of hindered phenolic antioxidants and phosphite antioxidants.

The invention protects the preparation method of the special PE-based laminating material, which comprises the following steps:

mixing low-density polyethylene, petroleum resin and ethylene-vinyl acetate copolymer resin uniformly, melting, extruding, granulating and drying to obtain the special PE-based laminating material, and adding the special PE-based laminating material and the low-density polyethylene together if a compatilizer, a nano filler, an antistatic agent, an antioxidant and a processing aid are contained.

Preferably, the melt extrusion adopts a double-screw extruder, and the length-diameter ratio of screws is 40: 1-48: 1.

Preferably, the strands are uniformly extruded from the die after undergoing a solid conveying section, a melting section, a natural venting section, a mixing section, and vacuum venting in a twin-screw extruder.

Preferably, the vacuum negative pressure value of the vacuum exhaust section is-0.07 to-0.12 MPa.

Preferably, the temperature of each temperature zone of the granulation is 160-200 ℃, the temperature of the screen changer and the temperature of the machine head are 200-210 ℃, and the mesh number of the screen changer is 60-80 meshes.

Preferably, the drying temperature is 85-100 ℃, and the drying time is 1-3 h.

The invention also protects the application of the special PE-based laminating material in the preparation of PE-based laminating films in the field of medical protection or electrostatic shielding.

Compared with the prior art, the invention has the beneficial effects that:

the invention takes linear low-density polyethylene as a matrix, and takes petroleum resin and ethylene-vinyl acetate copolymer resin for compounding to perform interface tackifying modification, so that the adhesive force between the PE-based laminated film layer and the base material can be obviously improved, the phenomena of surging, roller sticking, melt fracture and the like can not occur in the processing process, the laminated film layer has no appearance defects of pitted surface, wrinkles and the like, and the laminated film layer also has higher toughness, and can be widely applied to the fields of medical protection, electrostatic shielding places and the like.

Detailed Description

The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.

Materials used in the examples and comparative examples:

linear low density polyethylene a: the melt flow rate of the polycarbonate was 190 ℃, 2.16kg was 2g/10min, and the density was 0.918g/cm under the designation LLDPE DFDA7042³The tensile strength is 18MPa, and the product is purchased from China petrochemical industry.

Linear low density polyethylene B: LLDPE EXCEED 3518PA, melt flow rate at 190 ℃, 2.16kg of 3.5g/10min, density of 0.918g/cm³Tensile strength of 22MPa, purchased from Exxon chemical.

Petroleum resin A: carbon nine petroleum resin, the brand number Pht-T1120, the average molecular weight of the petroleum resin is 1000-3000, the softening point is 115 ℃, and the Nanjing sea flag environmental protection science and technology company Limited.

Petroleum resin B: carbon five petroleum resin, the brand number of H5-1153, the average molecular weight of the petroleum resin is 1000-3000, the softening point is 118 ℃, and the Nanjing sea flag environmental protection science and technology company Limited.

Ethylene-vinyl acetate copolymer resin a: the EVA V6110M has a melt flow rate of 190 deg.C, 2.16kg of 6g/10min, a vinyl acetate content of 26% in EVA, and Yangzibasfu.

Ethylene-vinyl acetate copolymer resin B: the trade mark EVA360, the melt flow rate is 190 deg.C, 2.16kg is 2g/10min, the mass content of vinyl acetate in EVA is 25%, Japan three-well.

Ethylene-vinyl acetate copolymer resin C: the trade mark EVA450, the melt flow rate is 190 deg.C, 2.16kg is 8g/10min, the mass content of vinyl acetate in EVA is 18%, DuPont in USA.

Ethylene-vinyl acetate copolymer resin D: the trade mark EVA7140F, the melt flow rate is 190 deg.C, 2.16kg is 0.7g/10min, the mass content of vinyl acetate in EVA is 14%, Taisox Taiwan plastic.

Ethylene-vinyl acetate copolymer resin E: the trade mark EVA7620M, melt flow rate at 190 deg.C, 2.16kg at 9g/10min, mass content of vinyl acetate in EVA at 9%, Taisox Taiwan. A compatilizer: polyethylene grafted maleic anhydride (MC218), available from Nippon Corp, Inc.

Nano filler A: nanometer calcium carbonate (FilmLink 520) with 3000 meshes, Sanfeng chemical Co., Ltd, Dongguan city.

Nano filler B: nanometer talcum powder (TYT-777A) with 3000 mesh size, Xiamen Haichuan Dada Industrial and trade Co.

Antioxidant: the hindered phenol antioxidant is 1010, and the phosphite antioxidant 168, 1010/168 is 1:2 by mass ratio.

Antistatic agent: cyanostatic antistatic agent (CYASTAT 609), Xiamen Haichuan Gongmao GmbH.

Dispersing agent: a fluorinated assistant (FX-5911), Xiamen Haichuan Industrial and trade Co., Ltd.

Examples 1 to 6

The functional PE-based material special for the laminating film comprises the following components in parts by mass as shown in Table 1:

TABLE 1 Components and parts by mass of PE-based material specially for laminated films prepared in each example

Raw material	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
								Linear low density polyethylene A	70	67		55		50
Linear low density polyethylene B			67		45		50
								Petroleum resin A	2	6	4	5		8
Petroleum resin B	3		3		6		5
								Ethylene-vinyl acetate copolymer resin A		12		15		22
Ethylene-vinyl acetate copolymer resin B	10				17
								Ethylene-vinyl acetate copolymer resin C			14				22
Compatibilizer MC218	4	6	8	4	8	5	4
								Nano-filler A	8	5	0	5			15
Nanofiller B				10	20	10
								Antioxidant 1010/168	1	2	1	2	1	2	2
Antistatic agent 609	1	1	1	2	2	1.5	1
								Dispersant FX-5911	1	1	2	2	1	1.5	1
Total parts of	100	100	100	100	100	100	100

Comparative examples 1 to 11

Table 2 Components and parts by mass of PE-based laminating special material prepared in various proportions

The preparation method of the PE-based laminating special material comprises the following steps:

s1, weighing formula materials in proportion, and putting the materials into a high-speed mixer for 60 s;

s2, uniformly metering and feeding the mixed material obtained in the step S1 into a double-screw extruder through a metering pump, wherein the temperature of each temperature zone of the double-screw extrusion granulation is 160, 180, 200 and 210 ℃ (one to nine zones), the temperature of a screen changer and a machine head is 200 and 210 ℃, and the mesh number of a filter screen of the screen changer is 80 meshes; after the materials pass through a solid conveying section, a melting section, a natural exhaust section, a mixing section and vacuum exhaust in a double screw, uniformly extruding material strips from a die head, wherein the vacuum negative pressure value of the vacuum exhaust section is less than or equal to-0.07 MPa; then water cooling, dewatering, granulating, sieving, and drying on line (drying temperature 85 deg.C, drying time 3h) to obtain the PE-based material special for laminating.

Applications of

The preparation method of the PE-based special material for the laminating film comprises the following steps:

putting the prepared special functional PE-based laminating material into a single-screw extruder, uniformly pumping the material to a die cavity after melting and plasticizing and impurity removal and filtration of a melt, uniformly extruding the material from an outlet of a die head after pressure accumulation in the die cavity, bonding the extruded melt with non-woven fabrics through thermal bonding, and forming a laminating layer on the non-woven fabrics; the single screw extrusion temperature is 210 ℃; the mesh number of the filter screens for filtering impurities is 80, 200 and 30, and the thickness of the film coating layer can be adjusted and controlled by adjusting the rotating speed of the screw rod.

Performance testing

1. Testing method of special material for laminating

(1) Tensile strength, transverse elongation: the measurement was carried out according to the measurement method of GB/T1040.3-2006;

(2) extrusion appearance: 5g of the material is put into a melt flow tester, preheated at 190 ℃ for 4 minutes, then a weight with a load of 21.6kg is put on the melt flow tester to extrude the material under the load condition, and the appearance of the extruded strip is observed.

(3) Bonding condition: selecting a square plate mold with 100mm x 2mm, sticking the non-woven fabric in an injection mold cavity, melting, extruding and injecting the materials at the same injection pressure and speed, sticking the non-woven fabric on the square plate, and judging the bonding performance by observing and testing the bonding condition of the square plate and the non-woven fabric.

2. Test results

Table 3 results of performance test of each example

Test items

Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Example 7

Tensile Strength (, MPa)

26.7

25.9

26.4

26.5

26.1

26

25.5

Transverse elongation (%)

876

869

892

863

850

855

876

Extruded appearance

Light brightness

Light brightness

Light brightness

Light brightness

Light brightness

Light brightness

Light brightness

Bonding condition

Firm and firm

Firm and firm

Firm and firm

Firm and firm

Firm and firm

Firm and firm

Firm and firm

TABLE 4 comparative Performance test results

As can be seen from tables 3 and 4, by using the PE-based functional material special for laminating of the embodiments of the invention, the appearance of the laminated film is bright and the adhesion is firm; the PE-based special material for the laminating film has high mechanical strength and high toughness, most of the mechanical properties of the PE-based special material for the laminating film of the comparative examples 1-7 are equivalent to those of the embodiment, but appearance defects such as pitted surfaces, wrinkles and the like occur in the laminating process, and even melt fracture occurs in the comparative example 3, wherein the content of petroleum resin is changed in the comparative example 1, and wrinkles occur in the laminating film; the comparative example 2 reduces the content of EVA, the bonding is not firm, and the lamination has a pitted surface; comparative example 3 the low melt index EVA was replaced and the content of EVA was increased by 2 parts, resulting in melt fracture and no sticking; comparative example 4 the content of 4 parts of EVA was increased on the basis of comparative example 2, and as a result, pitted surface still appeared; comparative example 5 no EVA was added, the laminated film appeared wrinkled and did not stick; comparative example 6 no petroleum resin was added, and wrinkles appeared in the laminated film; comparative example 7 reducing the LLDPE content and increasing the EVA content on the basis of comparative example 6 results in more severe film lamination wrinkles; comparative examples 8 and 9, the EVA melt index selected was less than 1g/10min, resulting in melt fracture and no sticking; comparative examples 10 and 11, EVA melt selected to be greater than 8g/10min, the lamination was strong but wrinkles appeared. Therefore, the special PE-based functional laminating material prepared by the invention has the advantages of no defects in the appearance of the prepared film, firm bonding with the base material, good toughness and applicability to the fields of medical protection and electrostatic shielding.

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.