Antiskid type matting film and preparation method thereof

Abstract

The present application relates to the field of extinction film, in particular to a kind of antiskid extinction film and preparation method thereof, to solve the poor antiskid performance of existing extinction film, easily leading to packaging sliding, unstable stacking problem;The antiskid extinction film is composed of four-layer structure that anti-adhesion layer, support layer, connecting layer and extinction layer are sequentially stacked and co-extruded;The preparation method uses modified polypropylene, composite modified antiskid particle as modified raw material to modify the extinction layer of the lowermost layer of antiskid extinction film, uses modified polypropylene to improve the adhesion and flexibility of antiskid extinction film, uses composite modified antiskid particle to build composite rough structure, significantly increases the surface friction coefficient under the synergistic effect of the two, so as to give the excellent antiskid performance of antiskid extinction film, which can effectively prevent packaging sliding, stacking collapse.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of extinction film, in particular to a kind of anti-skid extinction film and preparation method thereof. BACKGROUND

[0002] After biaxially oriented polypropylene extinction film is compounded with plastic woven bag, it is widely used in the packaging field of food, chemical product, fertilizer, although the friction coefficient of biaxially oriented polypropylene extinction film is higher than that of ordinary light film, but when the product filled with granular is stacked, it is easy to cause packaging to slide, unstable stacking, and the phenomenon of sliding stack still appears, which limits its application in the scene requiring anti-skid performance.

[0003] Therefore, it has important practical application value to develop a kind of anti-skid extinction film and preparation method thereof. SUMMARY

[0004] In order to overcome the above technical problems, the purpose of the present application is to provide an anti-skid extinction film and preparation method thereof, which solves the problem of poor anti-skid performance of the existing extinction film, which easily leads to packaging sliding and unstable stacking.

[0005] The purpose of the present application can be realized by the following technical solutions:

[0006] In the first aspect, the present application provides an anti-skid extinction film, which is composed of four layers of structure of anti-adhesion layer, support layer, connecting layer and extinction layer, which are sequentially stacked and co-extruded;

[0007] The anti-adhesion layer comprises the following components by weight: polypropylene 94-98 parts, anti-adhesion masterbatch 2-6 parts;

[0008] The support layer comprises the following components by weight: polypropylene 97-99 parts, antistatic masterbatch 1-3 parts;

[0009] The component of the connecting layer is polypropylene;

[0010] The extinction layer comprises the following components by weight: extinction masterbatch 60-80 parts, copolymerized polyolefin 10-20 parts, modified polypropylene 15-20 parts, composite modified anti-skid particles 7-15 parts and C5 petroleum resin 5-10 parts;

[0011] The modified polypropylene is prepared by the following steps:

[0012] Step a1: isophorone diisocyanate, p-tert-butyl catechol and dibutyl tin dilaurate are added into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stirring is carried out at a temperature of 20-25℃ and a stirring speed of 200-300r / min for 10-20min, then acrylic acid-2-hydroxyethyl ester is added drop by drop while stirring at a temperature of 40-45℃, the dropping speed is controlled at 1-3 drops / s, after the dropping is completed, stirring is continued for 2-3h, after the reaction is completed, the reaction product is cooled to room temperature, and an isocyanate alkenyl compound is obtained;

[0013] Step a2: polypropylene, dicumyl peroxide, the isocyanate alkenyl compound and dimethylbenzene are added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, nitrogen is introduced for protection, stirring is carried out at a temperature of 20-25℃ and a stirring speed of 200-300r / min for 1-2h, then stirring is continued at a temperature of 120-130℃ for 3-4h, after the reaction is completed, the reaction product is cooled to room temperature, then it is poured into ethyl acetate, then it is left to precipitate for 30-60min, then vacuum filtration is carried out, the filter cake is placed in a vacuum drying oven, and drying is carried out at a temperature of 60-65℃ for 3-4h, and an isocyanate alkenyl grafted polypropylene is obtained;

[0014] Step a3: the isocyanate alkenyl grafted polypropylene, isophorone diisocyanate, melamine, dibutyl tin dilaurate, dimethyl sulfoxide and dimethylbenzene are added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, nitrogen is introduced for protection, stirring is carried out at a temperature of 20-25℃ and a stirring speed of 200-300r / min for 1-2h, then stirring is continued at a temperature of 80-90℃ for 3-4h, after the reaction is completed, the reaction product is poured into anhydrous acetone while hot, then it is left to precipitate for 30-60min, then vacuum filtration is carried out, the filter cake is placed in a vacuum drying oven, and drying is carried out at a temperature of 40-45℃ for 6-8h, and a modified polypropylene is obtained.

[0015] As a preferred embodiment of the present application, the thickness of the anti-adhesion layer is 1.0-1.5μm.

[0016] As a preferred embodiment of the present application, the thickness of the support layer is 10-15μm.

[0017] As a preferred embodiment of the present application, the thickness of the connecting layer is 0.5-1.0μm.

[0018] As a preferred embodiment of the present application, the thickness of the extinction layer is 2.0-3.0μm.

[0019] As a preferred embodiment of the present application, the usage ratio of the isophorone diisocyanate, p-tert-butyl catechol, dibutyl tin dilaurate and 2-hydroxyethyl acrylate in step a1 is 10 mmol: 0.01-0.02 g: 0.03-0.05 g: 10 mmol.

[0020] As a preferred embodiment of the present application, the usage ratio of the polypropylene, dicumyl peroxide, isocyanate alkenyl compound and xylene in step a2 is 3 g: 0.3-0.5 g: 0.02-0.04 g: 30-40 mL.

[0021] As a preferred embodiment of the present application, the polypropylene in step a2 is homopolymer polypropylene HB28F.

[0022] As a preferred embodiment of the present application, the usage ratio of the isocyanate alkenyl grafted polypropylene, isophorone diisocyanate, melamine, dibutyl tin dilaurate, dimethyl sulfoxide and xylene in step a3 is 20 g: 10 mmol: 10 mmol: 0.1-0.2 g: 40-50 mL: 80-100 mL.

[0023] As a preferred embodiment of the present application, the composite modified anti-slip particles are prepared by the following steps:

[0024] The silicon carbide fiber, corundum and ethanol solution are added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, and protected by nitrogen, and stirred at a temperature of 20-25°C and a stirring rate of 200-300 r / min for 10-20 min, then adjusted to pH 8-9 with ammonia water, and then N-(2-aminoethyl)-3-aminopropyl trimethoxysilane is added and stirred for 20-30 min, and then heated to 60-70°C and stirred for 3-4 h, and then the reaction product is cooled to room temperature, and then vacuum filtered, and the filter cake is washed with distilled water for 2-3 times, and then placed in a vacuum drying oven and dried at a temperature of 60-65°C for 3-4 h to obtain the composite modified anti-slip particles.

[0025] As a preferred embodiment of the present application, the usage ratio of the silicon carbide fiber, corundum, ethanol solution and N-(2-aminoethyl)-3-aminopropyl trimethoxysilane is 3 g: 2.5-5.1 g: 60-70 mL: 1.3-4.5 g.

[0026] As a preferred embodiment of the present application, the silicon carbide fiber is KD-Ⅱ type silicon carbide fiber.

[0027] As a preferred embodiment of the present application, the average particle size of the corundum is 500 mesh.

[0028] As a preferred embodiment of the present application, the volume fraction of the ethanol solution is 85-90%.

[0029] As a preferred embodiment of the present application, the mass fraction of the ammonia water is 20-22%.

[0030] In a second aspect, the application provides a preparation method of the anti-skid matt film, comprising the following steps:

[0031] Step one: the raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer are respectively put into different extruders, and are melt-extruded under the conditions of a temperature of 220-250 DEG C and a screw rotation speed of 40-120 r / min, and the melt-extruded respectively is filtered through a 320-mesh filter, and then is converged and extruded in sequence in a four-layer structure die to obtain a composite film piece;

[0032] Step two: the composite film piece is subjected to longitudinal stretching, transverse stretching and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment and then is slitting to obtain the anti-skid matt film.

[0033] As a preferred embodiment of the present application, the temperature control during the longitudinal stretching is 90-135 DEG C, and the longitudinal stretching ratio is 4.5-5.5.

[0034] As a preferred embodiment of the present application, the temperature control during the transverse stretching is 150-175 DEG C, and the transverse stretching ratio is 8-10.

[0035] As a preferred embodiment of the present application, the corona treatment power of the corona treatment is 22-30 Wmin / m 2 .

[0036] Compared with the prior art, the application has the following beneficial effects:

[0037] An anti-skid matt film and a preparation method thereof, the raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer are respectively melt-extruded, and then are converged and extruded in sequence to obtain a composite film piece, the composite film piece is subjected to longitudinal stretching, transverse stretching and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment and then is slitting to obtain the anti-skid matt film; the preparation method uses modified polypropylene and composite modified anti-skid particles as modified raw materials to modify the matt layer of the lowermost layer of the anti-skid matt film, uses the modified polypropylene to improve the adhesion and flexibility of the anti-skid matt film, and uses the composite modified anti-skid particles to construct a composite rough structure, which significantly increases the surface friction coefficient under the synergistic action of the two, thereby endowing the anti-skid matt film with excellent anti-skid performance, which can effectively prevent the package from sliding and stacking collapse.

[0038] In the process of preparing the anti-skid matt film, a modified polypropylene is first prepared. Isophorone diisocyanate and 2-hydroxyethyl acrylate are reacted, and the isocyanate group on the isophorone diisocyanate reacts with the hydroxyl group on the 2-hydroxyethyl acrylate to obtain an isocyanate alkenyl compound containing an isocyanate group and an alkenyl group. Then, the polypropylene forms free radicals under the initiation of dicumyl peroxide, and then reacts with the alkenyl group on the isocyanate alkenyl compound, so as to introduce the isocyanate group into the molecular structure of the polypropylene, and obtain the isocyanate alkenyl grafted polypropylene. Then, the isocyanate alkenyl grafted polypropylene is treated with isophorone diisocyanate and melamine. The melamine has multiple amino groups, which can react with the isocyanate groups on the isocyanate alkenyl grafted polypropylene, so as to introduce a large number of amino groups, and then further react with the isophorone diisocyanate, so as to introduce a large number of isocyanate groups, and also realize the crosslinking degree between the polypropylenes. The modified polypropylene is obtained. The molecular structure of the modified polypropylene contains a large number of isocyanate groups. The introduction of the isocyanate groups increases the polarity of the polypropylene molecular chain, improves the surface energy of the film material and the compatibility with other additives, and also improves the bonding performance and flexibility of the polypropylene. When the film material is subjected to external friction force, the film material not only can be slightly bonded with external objects, but also can be slightly deformed with the anti-skid particles, so as to increase the “occlusion” area of the contact surface, and then improve the friction force.

[0039] In the process of preparing the anti-skid matt film, a composite modified anti-skid particle is also prepared. The silicon oxide on N- (2-aminoethyl) -3-aminopropyl trimethoxysilane is hydrolyzed into silanol and then grafted to the surface of the silicon carbide fiber and the emery, and a large number of amino groups and secondary amine groups are introduced, so as to obtain the composite modified anti-skid particle. The composite modified anti-skid particle utilizes the needle-like structure of the silicon carbide fiber and the granular structure of the emery to form a complementary rough surface, and constructs a “micro-convex-fiber interwoven” composite rough structure on the surface of the film material, which significantly increases the surface friction coefficient. After modification, the amino groups and the secondary amine groups can react with the isocyanate groups in the modified polypropylene, realize chemical anchoring, and ensure that the particles exist stably on the surface of the film material, so as to avoid the attenuation of the anti-skid performance caused by the particle falling off during use. BRIEF DESCRIPTION OF DRAWINGS

[0040] In order to facilitate the understanding of those skilled in the art, the present application will be further described below with reference to the accompanying drawings.

[0041] Figure 1 The structure of the anti-skid matt film of the present application is shown in the figure.

[0042] Figure 2The friction coefficient test results of the anti-skid type matt film of the present application embodiment 2-4 and comparative example 1-3 are shown in the schematic diagram. DETAILED DESCRIPTION

[0043] In order to make the person skilled in the art better understand the present application scheme, the technical scheme in the present application embodiment will be described clearly and completely below in combination with the drawings in the present application embodiment. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by the person skilled in the art without creative labor are within the scope of protection of the present application.

[0044] Embodiment 1:

[0045] Please refer to Figure 1 As shown in the figure, the present embodiment is an anti-skid type matt film, which is composed of four layers of structures of anti-adhesion layer, support layer, connecting layer and matt layer, which are sequentially stacked by co-extrusion;

[0046] Among them, the thickness of the anti-adhesion layer is 1.2 μm, the thickness of the support layer is 13 μm, the thickness of the connecting layer is 0.8 μm, and the thickness of the matt layer is 2.5 μm.

[0047] Embodiment 2:

[0048] The present embodiment is a preparation method of an anti-skid type matt film, which comprises the following steps:

[0049] Step S1: 10 mmol of isophorone diisocyanate, 0.01 g of p-tert-butyl catechol and 0.03 g of dibutyltin dilaurate were added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred at a temperature of 20℃ and a stirring rate of 200 r / min for 10 min, then 10 mmol of 2-hydroxyethyl acrylate was added dropwise while stirring at a temperature of 40℃, the dropping rate was controlled at 1 drop / s, and the reaction was continued to stir for 2 h after the addition was completed. After the reaction was completed, the reaction product was cooled to room temperature to obtain an isocyanate alkenyl compound;

[0050] Step S2: 3g of homopolymer polypropylene HB28F, 0.3g of dicumyl peroxide, 0.02g of isocyanate alkenyl compound and 30mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 20℃ and a stirring rate of 200r / min for 1h, then continued to be stirred at a temperature of 120℃ for 3h, after the reaction was completed, the reaction product was cooled to room temperature, then poured into ethyl acetate, then precipitated for 30min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 60℃ for 3h, to obtain isocyanate alkenyl grafted polypropylene;

[0051] Step S3: 20g of isocyanate alkenyl grafted polypropylene, 10mmol of isophorone diisocyanate, 10mmol of melamine, 0.1g of dibutyltin dilaurate, 40mL of dimethyl sulfoxide and 80mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 20℃ and a stirring rate of 200r / min for 1h, then continued to be stirred at a temperature of 80℃ for 3h, after the reaction was completed, the reaction product was poured into anhydrous acetone while hot, then precipitated for 30min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 40℃ for 6h, to obtain modified polypropylene;

[0052] Step S4: 3g of KD-Ⅱ type silicon carbide fiber, 2.5g of corundum with an average particle size of 500 mesh and 60mL of 85% ethanol solution were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 20℃ and a stirring rate of 200r / min for 10min, then adjusted to pH 8 with 20% ammonia water, then added 1.3g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and continued to stir for 20min, then continued to be stirred at a temperature of 60℃ for 3h, after the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, the filter cake was washed with distilled water for 2 times, then placed in a vacuum drying oven, dried at a temperature of 60℃ for 3h, to obtain composite modified anti-slip particles;

[0053] Step S5: the raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer were weighed according to the weight parts, respectively, for standby;

[0054] The anti-adhesion layer comprises the following components by weight: 94 parts of polypropylene, 2 parts of anti-adhesion masterbatch; wherein the polypropylene is homopolymer polypropylene HB28F; the anti-adhesion masterbatch is Suzhou Constap AB 6018 PP;

[0055] The support layer comprises the following components by weight: 97 parts of polypropylene and 1 part of antistatic masterbatch; the polypropylene is polypropylene T28F; and the antistatic masterbatch is Suzhou Constap PP-HC AT 4030.

[0056] The connecting layer comprises polypropylene; the polypropylene is F5005B from Yanshan Petrochemical.

[0057] The matt layer comprises the following components by weight: 60 parts of matt masterbatch, 10 parts of copolymerized polyolefin, 15 parts of modified polypropylene, 7 parts of composite modified anti-slip particles and 5 parts of C5 petroleum resin; the matt masterbatch is DUL8260PP from Best Technology; the copolymerized polyolefin is EVA DQDJ-1868 from Japan Unicar; and the C5 petroleum resin is SJ1304 from Shanghai Jinshan.

[0058] Step S6: The raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 220℃ and the screw rotation speed is 40r / min; the melt-extruded materials are filtered through a 320-mesh filter; and then the materials are sequentially combined and extruded in a four-layer structure die to obtain a composite film.

[0059] Step S7: The composite film is longitudinally stretched, transversely stretched and subjected to corona treatment to obtain a mother roll film; the mother roll film is subjected to aging treatment, and then is cut to obtain an anti-slip matt film; in the longitudinal stretching process, the temperature is controlled to be 90℃ and the longitudinal stretching ratio is 4.5; in the transverse stretching process, the temperature is controlled to be 150℃ and the transverse stretching ratio is 8; and the power of the corona treatment is 22Wmin / m 2 .

[0060] Embodiment 3

[0061] The embodiment is a preparation method of an anti-slip matt film, comprising the following steps:

[0062] Step S1: 10mmol of isophorone diisocyanate, 0.015g of p-tert-butyl catechol and 0.04g of dibutyltin dilaurate are added into a three-necked flask which is provided with a stirrer, a thermometer and a constant-pressure dropping funnel; the reaction is stirred under the condition that the temperature is 22℃ and the stirring speed is 250r / min for 15min; then 10mmol of 2-hydroxyethyl acrylate is added dropwise under the condition that the temperature is increased to 42℃ and the reaction is stirred; the dropping speed is controlled to be 2 drops / s; after the dropping is completed, the reaction is continuously stirred for 2.5h; after the reaction is completed, the reaction product is cooled to room temperature to obtain an isocyanate alkenyl compound.

[0063] Step S2: 3g of homopolymer polypropylene HB28F, 0.4g of dicumyl peroxide, 0.03g of isocyanate alkenyl compound and 35mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 22℃ and a stirring rate of 250r / min for 1.5h, then continued to be stirred at a temperature of 125℃ for 3.5h, after the reaction was completed, the reaction product was cooled to room temperature, then poured into ethyl acetate, then precipitated for 45min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 62℃ for 3.5h, to obtain isocyanate alkenyl grafted polypropylene;

[0064] Step S3: 20g of isocyanate alkenyl grafted polypropylene, 10mmol of isophorone diisocyanate, 10mmol of melamine, 0.15g of dibutyltin dilaurate, 45mL of dimethyl sulfoxide and 90mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 22℃ and a stirring rate of 250r / min for 1.5h, then continued to be stirred at a temperature of 85℃ for 3.5h, after the reaction was completed, the reaction product was poured into anhydrous acetone while hot, then precipitated for 45min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 42℃ for 7h, to obtain modified polypropylene;

[0065] Step S4: 3g of KD-Ⅱ type silicon carbide fiber, 3.8g of corundum with an average particle size of 500 mesh and 65mL of 88% ethanol solution were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 22℃ and a stirring rate of 250r / min for 15min, then adjusted to pH 8.5 with 21% ammonia water, then added 2.9g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and continued to stir for 25min, then continued to be stirred at a temperature of 65℃ for 3.5h, after the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, the filter cake was washed with distilled water for 2 times, then placed in a vacuum drying oven, dried at a temperature of 62℃ for 3.5h, to obtain composite modified anti-skid particles;

[0066] Step S5: the raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer were weighed according to the weight parts, respectively, for standby;

[0067] The anti-adhesion layer comprises the following components by weight: 96 parts of polypropylene, 4 parts of anti-adhesion masterbatch; wherein the polypropylene is homopolymer polypropylene HB28F; the anti-adhesion masterbatch is Suzhou Constap AB 6018 PP;

[0068] The support layer comprises the following components by weight: 98 parts of polypropylene, 2 parts of antistatic masterbatch; wherein the polypropylene is polypropylene T28F; the antistatic masterbatch is Suzhou Constap PP-HC 4030;

[0069] The connecting layer comprises the following components by weight: 98 parts of polypropylene, 2 parts of antistatic masterbatch; wherein the polypropylene is polypropylene T28F; the antistatic masterbatch is Suzhou Constap PP-HC 4030;

[0070] The matt layer comprises the following components by weight: 70 parts of matt masterbatch, 15 parts of copolymerized polyolefin, 18 parts of modified polypropylene, 11 parts of composite modified anti-slip particles, and 8 parts of C5 petroleum resin; wherein the matt masterbatch is Best Technology DUL8260PP; the copolymerized polyolefin is Japan Unic EVA DQDJ-1868; and the C5 petroleum resin is Shanghai Jinshan C5 petroleum resin SJ1304;

[0071] Step S6: The raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 235°C and the screw rotation speed is 80r / min, and the melt-extruded materials are filtered through a 320-mesh filter, and then are sequentially combined and extruded in a four-layer structure die to obtain a composite film;

[0072] Step S7: The composite film is subjected to longitudinal stretching, transverse stretching and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment, and then is cut to obtain an anti-slip matt film; wherein the temperature is controlled to be 110°C and the longitudinal stretching ratio is 5.0 during the longitudinal stretching; the temperature is controlled to be 160°C and the transverse stretching ratio is 9 during the transverse stretching; and the corona treatment power is 26Wmin / m 2 .

[0073] Example 4:

[0074] The embodiment is a preparation method of an anti-slip matt film, comprising the following steps:

[0075] Step S1: 10mmol of isophorone diisocyanate, 0.02g of p-tert-butyl catechol and 0.05g of dibutyltin dilaurate are added to a three-necked flask equipped with a stirrer, a thermometer and a constant-pressure dropping funnel, and are stirred under the condition that the temperature is 25°C and the stirring speed is 300r / min for 20min, and then 10mmol of 2-hydroxyethyl acrylate is added dropwise under the condition that the temperature is increased to 45°C and the stirring speed is 300r / min, the dropping speed is controlled to be 3 drops / s, and the reaction is continued to stir for 3h after the dropping is completed, and the reaction product is cooled to room temperature to obtain an isocyanate alkenyl compound;

[0076] Step S2: 3g of homopolymer polypropylene HB28F, 0.5g of dicumyl peroxide, 0.04g of isocyanate alkenyl compound and 40mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 25℃ and a stirring rate of 300r / min for 2h, then heated to 130℃ and continued to stir for 4h, after the reaction was completed, the reaction product was cooled to room temperature, then poured into ethyl acetate, then precipitated for 60min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 65℃ for 4h, to obtain isocyanate alkenyl grafted polypropylene;

[0077] Step S3: 20g of isocyanate alkenyl grafted polypropylene, 10mmol of isophorone diisocyanate, 10mmol of melamine, 0.2g of dibutyltin dilaurate, 50mL of dimethyl sulfoxide and 100mL of xylene were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 25℃ and a stirring rate of 300r / min for 2h, then heated to 90℃ and continued to stir for 4h, after the reaction was completed, the reaction product was poured into anhydrous acetone while hot, then precipitated for 60min, then vacuum filtered, the filter cake was placed in a vacuum drying oven, dried at a temperature of 45℃ for 8h, to obtain modified polypropylene;

[0078] Step S4: 3g of KD-Ⅱ type silicon carbide fiber, 5.1g of corundum with an average particle size of 500 mesh and 70mL of 90% ethanol solution were added into a three-necked flask equipped with a stirrer, a thermometer and a gas inlet tube, protected by nitrogen, stirred at a temperature of 25℃ and a stirring rate of 300r / min for 20min, then adjusted to pH 9 with 22% ammonia water, then added 4.5g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and continued to stir for 30min, then heated to 70℃ and continued to stir for 4h, after the reaction was completed, the reaction product was cooled to room temperature, then vacuum filtered, the filter cake was washed with distilled water for 3 times, then placed in a vacuum drying oven, dried at a temperature of 65℃ for 4h, to obtain composite modified anti-skid particles;

[0079] Step S5: the raw materials of the anti-blocking layer, the support layer, the connecting layer and the matt layer were weighed according to the weight parts, respectively, for standby;

[0080] The anti-blocking layer comprises the following components by weight: 98 parts of polypropylene, 6 parts of anti-blocking masterbatch; wherein the polypropylene is homopolymer polypropylene HB28F; the anti-blocking masterbatch is Suzhou Constap AB 6018 PP;

[0081] The support layer comprises the following components by weight: 99 parts of polypropylene, and 3 parts of antistatic masterbatch; the polypropylene is polypropylene T28F; and the antistatic masterbatch is Suzhou Constap AT 4030 PP-HC.

[0082] The connecting layer comprises polypropylene; the polypropylene is Dushanzhi TF1007.

[0083] The matt layer comprises the following components by weight: 80 parts of matt masterbatch, 20 parts of copolymerized polyolefin, 20 parts of modified polypropylene, 15 parts of composite modified anti-slip particles, and 10 parts of C5 petroleum resin; the matt masterbatch is Bestech DUL8260PP; the copolymerized polyolefin is Japanese Unicar EVA DQDJ-1868; and the C5 petroleum resin is Shanghai Jinshan C5 petroleum resin SJ1304.

[0084] Step S6: The raw materials of the anti-adhesion layer, the support layer, the connecting layer, and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 250°C and the screw rotation speed is 120 r / min, and the melt-extruded materials are filtered through a 320-mesh filter, and then are sequentially combined and extruded in a four-layer structure die to obtain a composite film.

[0085] Step S7: The composite film is subjected to longitudinal stretching, transverse stretching, and corona treatment to obtain a mother roll film, the mother roll film is subjected to aging treatment, and then is cut to obtain an anti-slip matt film; in the process of longitudinal stretching, the temperature is controlled to be 135°C, and the longitudinal stretching ratio is 5.5; in the process of transverse stretching, the temperature is controlled to be 175°C, and the transverse stretching ratio is 10; the power of the corona treatment is 30 Wmin / m 2 .

[0086] Comparative Example 1

[0087] The present comparative example is a preparation method of an anti-slip matt film, comprising the following steps:

[0088] Step S1: The raw materials of the anti-adhesion layer, the support layer, the connecting layer, and the matt layer are respectively weighed according to weight parts, and are reserved.

[0089] The anti-adhesion layer comprises the following components by weight: 98 parts of polypropylene, and 6 parts of anti-adhesion masterbatch; the polypropylene is homopolymerized polypropylene HB28F; and the anti-adhesion masterbatch is Suzhou Constap AB 6018 PP.

[0090] The support layer comprises the following components by weight: 99 parts of polypropylene, and 3 parts of antistatic masterbatch; the polypropylene is polypropylene T28F; and the antistatic masterbatch is Suzhou Constap AT 4030 PP-HC.

[0091] The component of the connecting layer is polypropylene; the polypropylene is Dushanzhi Petrochemical TF1007;

[0092] The matt layer comprises the following components by weight: 80 parts of matt masterbatch, 20 parts of copolymerized polyolefin, 20 parts of polypropylene, and 10 parts of C5 petroleum resin; the matt masterbatch is Best Technology DUL8260PP; the copolymerized polyolefin is Japan Unicar EVA DQDJ-1868; the polypropylene is homopolymerized polypropylene HB28F; and the C5 petroleum resin is Shanghai Jinshan C5 petroleum resin SJ1304;

[0093] Step S2: The raw materials of the anti-adhesion layer, the supporting layer, the connecting layer, and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 250°C and the screw rotation speed is 120 r / min, and the melt-extruded materials are filtered through a 320-mesh filter, and then are sequentially combined and extruded in a four-layer structure die to obtain a composite film;

[0094] Step S3: The composite film is subjected to longitudinal stretching, transverse stretching, and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment, and then is cut to obtain the anti-slip matt film; in the process of longitudinal stretching, the temperature is controlled to be 135°C and the longitudinal stretching ratio is 5.5; in the process of transverse stretching, the temperature is controlled to be 175°C and the transverse stretching ratio is 10; the power of the corona treatment is 30 Wmin / m 2 .

[0095] Comparative Example 2

[0096] The present comparative example is a preparation method of an anti-slip matt film, comprising the following steps:

[0097] Step S1: 3 g of KD-Ⅱ type silicon carbide fiber, 5.1 g of diamond with an average particle size of 500 mesh, and 70 mL of ethanol solution with a volume fraction of 90% are added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet pipe, nitrogen is introduced for protection, and stirring is performed under the condition that the temperature is 25°C and the stirring speed is 300 r / min for 20 min, then the pH value is adjusted to 9 by using ammonia water with a mass fraction of 22%, then 4.5 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is added and stirring is continued for 30 min, then the temperature is increased to 70°C and stirring is continued for 4 h, after the reaction is completed, the reaction product is cooled to room temperature, then vacuum filtration is performed, the filter cake is washed with distilled water for 3 times, and then is placed in a vacuum drying oven and dried at a temperature of 65°C for 4 h to obtain composite modified anti-slip particles;

[0098] Step S2: The raw materials of the anti-adhesion layer, the supporting layer, the connecting layer, and the matt layer are respectively weighed according to the weight parts, and are reserved.

[0099] The anti-adhesion layer comprises the following components by weight: 98 parts of polypropylene, 6 parts of anti-adhesion masterbatch; wherein the polypropylene is homopolymer polypropylene HB28F; the anti-adhesion masterbatch is Suzhou Constap AB 6018 PP;

[0100] The support layer comprises the following components by weight: 99 parts of polypropylene, 3 parts of anti-static masterbatch; wherein the polypropylene is polypropylene T28F; the anti-static masterbatch is Suzhou Constap AT 4030 PP-HC;

[0101] The connecting layer comprises the following components by weight: 99 parts of polypropylene, 3 parts of anti-static masterbatch; wherein the polypropylene is polypropylene T28F; the anti-static masterbatch is Suzhou Constap AT 4030 PP-HC;

[0102] The matt layer comprises the following components by weight: 80 parts of matt masterbatch, 20 parts of copolymer polyolefin, 20 parts of polypropylene, 15 parts of composite modified anti-slip particles and 10 parts of C5 petroleum resin; wherein the matt masterbatch is Best Technology DUL8260PP; the copolymer polyolefin is Japan Unicar EVA DQDJ-1868; the polypropylene is homopolymer polypropylene HB28F; the C5 petroleum resin is Shanghai Jinshan C5 petroleum resin SJ1304;

[0103] Step S3: The raw materials of the anti-adhesion layer, the support layer, the connecting layer and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 250℃ and the screw rotation speed is 120r / min, and the melt-extruded respectively is filtered through a 320-mesh filter, and then is converged and extruded in sequence in a four-layer structure die to obtain a composite film piece;

[0104] Step S4: The composite film piece is subjected to longitudinal stretching, transverse stretching and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment, and then is cut to obtain an anti-slip matt film; wherein the temperature is controlled to be 135℃ and the longitudinal stretching ratio is 5.5 during the longitudinal stretching; the temperature is controlled to be 175℃ and the transverse stretching ratio is 10 during the transverse stretching; the corona treatment power is 30Wmin / m 2 .

[0105] Comparative Example 3:

[0106] The present comparative example is a preparation method of an anti-slip matt film, comprising the following steps:

[0107] Step S1: 10 mmol of isophorone diisocyanate, 0.02 g of p-tert-butyl catechol, and 0.05 g of dibutyl tin dilaurate were added to a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel, and stirred at a temperature of 25°C and a stirring rate of 300 r / min for 20 min, after which 10 mmol of 2-hydroxyethyl acrylate was added dropwise while stirring at a temperature of 45°C, with the dropping rate controlled at 3 drops / s, and the reaction was continued to stir for 3 h after the addition was completed, and the reaction product was cooled to room temperature after the reaction was completed, to obtain an isocyanate alkenyl compound;

[0108] Step S2: 3 g of homopolypropylene HB28F, 0.5 g of dicumyl peroxide, 0.04 g of the isocyanate alkenyl compound, and 40 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen, and stirred at a temperature of 25°C and a stirring rate of 300 r / min for 2 h, after which the temperature was raised to 130°C and the reaction was continued to stir for 4 h, and the reaction product was cooled to room temperature after the reaction was completed, and then poured into ethyl acetate, and then left to precipitate for 60 min, and then vacuum-filtered, and the filter cake was placed in a vacuum drying oven and dried at a temperature of 65°C for 4 h, to obtain an isocyanate alkenyl grafted polypropylene;

[0109] Step S3: 20 g of the isocyanate alkenyl grafted polypropylene, 10 mmol of isophorone diisocyanate, 10 mmol of melamine, 0.2 g of dibutyl tin dilaurate, 50 mL of dimethyl sulfoxide, and 100 mL of xylene were added to a three-necked flask equipped with a stirrer, a thermometer, and a gas inlet tube, and protected by nitrogen, and stirred at a temperature of 25°C and a stirring rate of 300 r / min for 2 h, after which the temperature was raised to 90°C and the reaction was continued to stir for 4 h, and the reaction product was poured into anhydrous acetone while hot after the reaction was completed, and then left to precipitate for 60 min, and then vacuum-filtered, and the filter cake was placed in a vacuum drying oven and dried at a temperature of 45°C for 8 h, to obtain a modified polypropylene;

[0110] Step S4: the raw materials for the anti-blocking layer, the support layer, the connecting layer, and the matting layer were weighed according to the weight parts, respectively, and reserved;

[0111] The anti-blocking layer comprises the following components in parts by weight: 98 parts of polypropylene, and 6 parts of an anti-blocking master batch; the polypropylene is homopolypropylene HB28F; and the anti-blocking master batch is Suzhou Constap AB 6018 PP.

[0112] The support layer comprises the following components in parts by weight: 99 parts of polypropylene, and 3 parts of an antistatic master batch; the polypropylene is polypropylene T28F; and the antistatic master batch is Suzhou Constap AT 4030 PP-HC.

[0113] The component of the connecting layer is polypropylene; the polypropylene is Dushanzhi Petrochemical TF1007;

[0114] The matt layer comprises the following components by weight: 80 parts of matt masterbatch, 20 parts of copolymerized polyolefin, 20 parts of modified polypropylene and 10 parts of C5 petroleum resin; the matt masterbatch is Bestech DUL8260PP; the copolymerized polyolefin is Japanese Unicar EVA DQDJ-1868; and the C5 petroleum resin is Shanghai Jinshan C5 petroleum resin SJ1304;

[0115] Step S5: The raw materials of the anti-adhesion layer, the supporting layer, the connecting layer and the matt layer are respectively put into different extruders, and are melt-extruded under the condition that the temperature is 250℃ and the screw rotation speed is 120r / min, and the melt-extruded materials are filtered through a 320-mesh filter, and then are sequentially combined and extruded in a four-layer structure die to obtain a composite film;

[0116] Step S6: The composite film is subjected to longitudinal stretching, transverse stretching and corona treatment to obtain a mother roll film, and the mother roll film is subjected to aging treatment, and then is cut to obtain the anti-slip matt film; in the process of longitudinal stretching, the temperature is controlled to be 135℃ and the longitudinal stretching ratio is 5.5; in the process of transverse stretching, the temperature is controlled to be 175℃ and the transverse stretching ratio is 10; the power of the corona treatment is 30Wmin / m 2 .

[0117] Performance test

[0118] The anti-slip matt films of Examples 2-4 and Comparative Examples 1-3 are tested for the friction coefficient according to GB / T 10006-2021, and the test position is the matt layer of the anti-slip matt film, and the test results are shown in Table 1. Figure 2

[0119] Referring to Table 1, Figure 2 it can be known from the comparison between Examples 2-4 and Comparative Examples 1-3 that the use of modified polypropylene and the addition of composite modified anti-slip particles to the modified polypropylene can significantly improve the friction coefficient of the anti-slip matt film, and thus significantly improve the anti-slip effect.

[0120] In the description of the present specification, the description referring to the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.​

[0121] The above merely illustrates and explains the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or replace them with similar ways, as long as they do not deviate from the application or exceed the scope defined in the present application, which shall belong to the protection scope of the present application.

Claims

1. A non-slip matte film, characterized in that, It consists of a four-layer structure formed by co-extrusion of an anti-adhesion layer, a support layer, a connecting layer and a matte layer in sequence; The anti-blocking layer comprises the following components in parts by weight: 94-98 parts of polypropylene and 2-6 parts of anti-blocking masterbatch; The support layer comprises the following components in parts by weight: 97-99 parts of polypropylene and 1-3 parts of antistatic masterbatch; The component of the connecting layer is polypropylene; The matte layer comprises the following components by weight: 60-80 parts of matte masterbatch, 10-20 parts of copolymer polyolefin, 15-20 parts of modified polypropylene, 7-15 parts of composite modified anti-slip particles, and 5-10 parts of C5 petroleum resin. The modified polypropylene is prepared by the following steps: Step a1: Isophorone diisocyanate, p-tert-butylcatechol and dibutyltin dilaurate were stirred and reacted, and then 2-hydroxyethyl acrylate was added dropwise and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled to obtain the isocyanate alkenyl compound. Step a2: Polypropylene, dicumyl peroxide, isocyanate alkenyl compound and xylene are stirred and reacted. After the reaction is completed, the reaction product is cooled and then poured into ethyl acetate. After standing to precipitate, it is then filtered under vacuum and the filter cake is dried to obtain isocyanate alkenyl grafted polypropylene. Step a3: Isocyanate-grafted polypropylene, isophorone diisocyanate, melamine, dibutyltin dilaurate, dimethyl sulfoxide and xylene are stirred and reacted. After the reaction is completed, the reaction product is poured into anhydrous acetone while hot, then allowed to stand to precipitate, and then vacuum filtered. The filter cake is dried to obtain modified polypropylene.

2. The anti-slip matte film according to claim 1, characterized in that, The thickness of the anti-adhesion layer is 1.0-1.5 μm, the thickness of the support layer is 10-15 μm, the thickness of the connecting layer is 0.5-1.0 μm, and the thickness of the matting layer is 2.0-3.0 μm.

3. The anti-slip matte film according to claim 1, characterized in that, The ratio of isophorone diisocyanate, p-tert-butylcatechol, dibutyltin dilaurate, and 2-hydroxyethyl acrylate in step a1 is 10 mmol: 0.01-0.02 g: 0.03-0.05 g: 10 mmol.

4. The anti-slip matte film according to claim 1, characterized in that, In step a2, the ratio of polypropylene, dicumyl peroxide, isocyanate alkenyl compound, and xylene is 3g:0.3-0.5g:0.02-0.04g:30-40mL; the polypropylene is homopolymer polypropylene HB28F.

5. The anti-slip matte film according to claim 1, characterized in that, The ratio of isocyanate-alkenyl-grafted polypropylene, isophorone diisocyanate, melamine, dibutyltin dilaurate, dimethyl sulfoxide, and xylene in step a3 is 20g:10mmol:10mmol:0.1-0.2g:40-50mL:80-100mL.

6. The anti-slip matte film according to claim 1, characterized in that, The composite modified anti-slip particles are prepared by the following steps: Silicon carbide fiber, corundum, and ethanol solution were stirred and reacted. The pH was then adjusted with ammonia. N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was added and the reaction was continued with stirring. After the reaction was completed, the reaction product was cooled and then vacuum filtered. The filter cake was washed and dried to obtain composite modified anti-slip particles.

7. The anti-slip matte film according to claim 6, characterized in that, The ratio of silicon carbide fiber, corundum, ethanol solution, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane is 3g:2.5-5.1g:60-70mL:1.3-4.5g.

8. The anti-slip matte film according to claim 6, characterized in that, The silicon carbide fiber is a KD-II type silicon carbide fiber; The average particle size of the corundum is 500 mesh; The volume fraction of the ethanol solution is 85-90%; The mass fraction of the ammonia water is 20-22%.

9. A method for preparing an anti-slip matte film as described in any one of claims 1-8, characterized in that, Includes the following steps: Step 1: The raw materials for the anti-adhesion layer, support layer, connecting layer and matte layer are fed into different extruders and melt-extruded at a temperature of 220-250℃ and a screw speed of 40-120r / min. The extruded melts are filtered through a 320-mesh filter and then extruded in sequence through a four-layer die to obtain a composite film. Step 2: The composite film is stretched longitudinally, stretched laterally, and subjected to corona treatment to obtain a master roll film. The master roll film is then subjected to aging treatment and cut to obtain an anti-slip matte film.

10. The method for preparing an anti-slip matte film according to claim 9, characterized in that, During the longitudinal stretching process, the temperature is controlled at 90-135℃ and the longitudinal stretching ratio is 4.5-5.5; during the transverse stretching process, the temperature is controlled at 150-175℃ and the transverse stretching ratio is 8-10; the corona treatment power is 22-30 Wmin / m. 2 .

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