KR101179249B1 - Dust proof film - Google Patents

Abstract

PURPOSE: An anti-dust film is provided to have excellent air permeation, moisture permeation and flexability, and to not generate scratch by comprising a polyethylene resin and a specific polyolefin-based elastomer. CONSTITUTION: An anti-dust film comprises 4-15 weight% of low density polyethylene, 30-45 weight% of medium density polyethylene, 4-8 weight% of high density polyethylene, 3-20 weight% of a polyolefin-based elastomer, and 40-55 weight% of inorganic filler. The anti-dust film additionally comprises 1-10 weight% of a surfactant master batch. The surfactant master batch comprises 20-40 weight% of surfactant and 60-80 weight% low density polyethylene. The polyolefin based elastomer has a melt index of 0.9-1.1 g/10min(190°C, 2.16 kg), and a density of 0.870-0.908 g/cm^3.

Description

Fallout prevention film {DUST PROOF FILM}

The present invention relates to a fallout prevention film used for automobile coating protection. More specifically, the present invention relates to a fallout prevention film including a polyethylene-based resin and a specific polyolefin-based elastomer, having excellent moisture permeability, air permeability, excellent flexibility, no scratch, and no adhesion to an automotive coating.

Automobiles are covered with plastic film to protect the surface of the paint surface from scratch and dust. At present, most of them use fabrics such as wrap guard film and tyvek. to be.

The wrap guard film is a self-adhesive film made of polypropylene and polyethylene, and is used to adhere completely to the surface of a vehicle when the vehicle is shipped. When using the wrap guard film, it is a product that requires precise work so that wrinkles or bubbles are not generated. When wrinkles or bubbles occur, water droplets are generated due to moisture inside, leaving debris on the surface of the vehicle. In addition, if the attachment state is maintained for a long time, the oxidation proceeds, there has been a problem that the trace on the surface of the vehicle also occurs.

Tyvek (TYVEK) is a woven film made by DuPont High Density Polyethylene, which has strong strength, little change in physical properties, resists lift, and is woven. Many are known to have advantages such as easy evaporation of moisture. For Tyvek, a spunbonded fibrous sheet made of multiple flexifilment strands of oriented polyethylene film fibrils has proved useful in a variety of applications that take advantage of the well-combined strength, tear resistance and permeability properties of the sheet. .

However, Tyvek, which is currently on the market, is expensive, has a lot of dust adsorbed through the body through the hole, the fabric itself is stiff and difficult to work when covering the vehicle, and there is also a disadvantage that the scratch is generated.

Accordingly, Korean Patent No. 10-0961263 (2010.05.26), which is filed and filed by the present applicant, relates to (a) 10 to 30% by weight of linear low density polyethylene resin, and (b) medium density polyethylene resin 20 to solve such problems. To provide a breathable excellent fall prevention film comprising ~ 35% by weight and (c) 45 ~ 55% by weight of calcium carbonate. However, there is a need for a fall prevention film that is more flexible from the user and has less detachment of calcium carbonate.

Korea Patent Registration No. 10-0961263 (2010.05.26)

An object of the present invention is to provide a fallout prevention film which is more excellent in flexibility than the conventionally developed fallout prevention film and has less detachment of inorganic particles.

It is another object of the present invention to provide a fall prevention film having strength, moisture permeability, and air permeability suitable for protecting an automobile coating film.

The present invention is a low-density polyethylene 4 to 15% by weight, medium-density polyethylene 30 to 45% by weight and high density polyethylene 4 to 8% by weight, polyolefin-based elastomer 3 to 20% by weight, inorganic filler 40 to 55% by weight of the inorganic filler It is about.

The present invention also relates to a fall prevention film further comprising 1 to 10% by weight of a surfactant masterbatch including 20 to 40% by weight of surfactant and 60 to 80% by weight of low density polyethylene.

The present invention also relates to a fallout prevention film further comprising 1 to 10% by weight of an ionomer or stearic acid selected from a copolymer of ethylene and methacrylic acid, a copolymer of ethylene and acrylic acid.

Fallout prevention film according to the present invention is very excellent in flexibility, there is no detachment of the inorganic particles does not occur there is a very excellent effect that there is no problem, such as inorganic particles are attached to the car paint film or scratches when attached to the car paint film. .

In addition, the fall prevention film according to the present invention is excellent in moisture permeability and air permeability, there is no change in color or physical properties due to outdoor exposure and can provide a polyethylene film for protecting the automotive film with low stickiness or low friction, and excellent mechanical strength, soft It is possible to provide a fall prevention film having elastic properties.

In another aspect, the present invention can provide a film for the purpose of preventing contamination of the coating surface of the vehicle or scratching the coating surface during the transportation of the new vehicle.

1 is a FE-SEM (1000 times) photograph of a film according to Example 1 of the present invention.
2 is a photograph when the film according to Example 1 of the present invention is attached to an automobile paint film and then removed again.
3 is a FE-SEM (1000 times) photograph of the film according to Example 7 of the present invention.
4 is a photograph when the film according to Example 7 of the present invention is attached to the automobile coating film and then removed again.
5 is a FE-SEM (1000 times) photograph of the film according to Comparative Example 1 of the present invention.
4 is a photograph when the film according to Comparative Example 1 of the present invention is attached to an automobile coating film and then removed again.

Hereinafter, the present invention will be described in more detail.

The first aspect of the present invention comprises 4 to 15% by weight of low density polyethylene, 30 to 45% by weight of medium density polyethylene and 4 to 8% by weight of high density polyethylene, 3 to 20% by weight of polyolefin elastomer, 40 to 55% by weight of inorganic filler do.

The second aspect of the present invention is 4 to 15% by weight of low density polyethylene, 30 to 45% by weight of medium density polyethylene and 4 to 8% by weight of high density polyethylene, 3 to 20% by weight of polyolefin elastomer, 40 to 55% by weight of inorganic filler and interface Activator masterbatch comprises 1 to 10% by weight. In this case, the surfactant masterbatch includes 20 to 40 wt% of surfactant and 60 to 80 wt% of low density polyethylene.

The third aspect of the present invention is 4 to 15% by weight of low density polyethylene, 30 to 45% by weight of medium density polyethylene and 4 to 8% by weight of high density polyethylene, 3 to 20% by weight of polyolefin elastomer, 40 to 55% by weight of inorganic filler and ethylene 1 to 10% by weight of an ionomer or stearic acid selected from a copolymer of methacrylic acid, a copolymer of ethylene and acrylic acid.

The fourth aspect of the present invention is 4 to 15% by weight of low density polyethylene, 30 to 45% by weight of medium density polyethylene and 4 to 8% by weight of high density polyethylene, 3 to 20% by weight of polyolefin elastomer, 40 to 55% by weight of inorganic filler, interface The activator masterbatch comprises 1 to 10% by weight and 1 to 10% by weight of an ionomer or stearic acid selected from a copolymer of ethylene and methacrylic acid, a copolymer of ethylene and acrylic acid. In this case, the surfactant masterbatch includes 20 to 40 wt% of surfactant and 60 to 80 wt% of low density polyethylene.

The said 1st-4th aspect is an aspect for demonstrating this invention, It is not limited to these.

Hereinafter, each component of the present invention will be described in more detail.

(Low density polyethylene)

In the present invention, the low-density polyethylene is preferably used to provide flexibility and improve productivity, so that the low-density polyethylene can be used in the range of 4 to 15% by weight to satisfy the desired physical properties. More preferably 6 to 8% by weight is used. If the amount is less than 4% by weight, the workability is lowered and productivity is lowered. If it is used more than 15% by weight, the physical properties are reduced and the characteristics of the product cannot be realized.

More specifically, the melt index is 7.0 to 14.0 g / 10 min (190 ° C., 2.16 kg), the density is 0.915 to 0.920, and more preferably the melt index is 7.5 to 7.7 g / 10 min (190 ° C., 2.16 kg), and the density is The use of 0.917 to 0.919 can produce a film free of mechanical properties, physical properties such as deterioration due to ultraviolet rays, and the like. Commercialized examples of such low-density polyethylene include, but are not limited to, Grade 955 of Hanwha Chemical.

(Medium density polyethylene)

In the present invention, the medium density polyethylene is used to impart mechanical properties of the film, and 30 to 45% by weight, more preferably 35 to 40% by weight is used. When used at less than 30% by weight is not enough to express the desired strength, when it exceeds 45% by weight, the film becomes stiff, the desired flexibility may be lowered.

More specifically, the mechanical properties can be improved by using a melt index in the range of 2.0 to 5.0 g / 10 min (190 ° C, 2.16 kg) and a density of 0.928 to 0.936, and more preferably, the melt index is 3.0 to The use of 5.0g / 10min (190 ° C, 2.16kg) and density ranges from 0.930 to 0.932 can produce a film with little change in color and physical properties due to outdoor exposure and without desorption of the target inorganic particles. have. Commercialized examples of such medium-density polyethylene include SK General Chemical's RG300U, FT-811, and the like, but are not limited thereto.

(High density polyethylene)

In the present invention, the high density polyethylene is used to improve the strength of the film, the content of which can achieve the above object in the range of 4 to 8% by weight, more preferably 5 to 7% by weight. If it is used at 4 wt% or less, the target strength cannot be achieved, and if it is used at 8 wt% or more, it may become too stiff, causing scratches on the surface of the vehicle.

More specifically, the melt index can express the film strength required by the product in the range of 6.0 ~ 8.5g / 10min (190 ℃, 2.16kg), density is 0.960 ~ 0.965, more preferably the melt index is 7.0 ~ 8.5g / 10min (190 ℃, 2.16kg), the density is in the range of 0.962 ~ 0.963 is good to use. Commercialized examples of such high-density polyethylene include, but are not limited to, JH910 of SK Global Chemical.

(Polyolefin Elastomer)

In the present invention, the polyolefin-based elastomer is used to prevent desorption of inorganic particles and to increase flexibility, and the content of the polyolefin-based elastomer may be 3 to 20% by weight, more preferably 5 to 10% by weight. When used in less than 3% by weight can not achieve the desorption and flexibility of the target inorganic particles, when used in excess of 20% by weight or more may be too high flexibility and strength may be lowered.

More specifically, it is preferable to use a melting temperature Tm of 50 ° C. or higher because it can prevent the phenomenon of sticking to the surface of the automobile coating film during high temperature outdoor exposure. More specifically, it is preferable to use a film having a melting temperature (Tm) of 50 to 90 ° C because film filming is easy.

In addition, the polyolefin elastomer may be a polymer elastomer of ethylene polymerized using a metallocene catalyst and an alpha-olefin of (C3 to C15) and a non-covalent diene monomer, and a melt index of 0.9 to 1.1 g / 10 min ( 190 ° C., 2.16 kg), and having a density of 0.870 to 0.908 is preferred because of its excellent flexibility and prevention of separation of inorganic particles. Commercialized examples of such polyolefin-based elastomers include Engage 8540, Engage 8100, Lucene LC-100, Lucene LC-170, etc. of Dow Chemical, but are not limited thereto.

(Inorganic filler)

In the present invention, the inorganic filler is used to impart breathability and moisture permeability by forming a breathable hole in the stretching process during film production, it can be used both coated or uncoated. In the case of using an inorganic filler that is not coated, the air permeability is improved, and when the coated inorganic filler is used, the workability is excellent and the mechanical properties of the film are excellent.

Specifically, for example, calcium carbonate, silica, barium sulfate, magnesium sulfate, calcium sulfate, talc, kaolin, aluminum hydroxide, magnesium hydroxide, zinc oxide, alumina, titanium oxide, mica, zeolite, diatomaceous earth, magnesium carbonate, clay It is possible to use any one or a mixture of two or more, in particular, it is preferable to use calcium carbonate. In this case, the inorganic filler may produce an excellent breathable film without using the average particle size of 1.5 to 4.0㎛, more preferably 2.0 to 3.0㎛ size without compromising the physical properties of the film. If the average particle diameter is less than 1.5 μm, good air permeability may not be obtained. If the average particle diameter is larger than 4.0 μm, tearing, pore formation, and strength decrease may occur during the film manufacturing process.

It is preferable to use the content of 40 to 55% by weight, and can express the desired moisture permeability and breathability in the above range.

(Surfactant Masterbatch)

The present invention can add a surfactant masterbatch as needed to reduce contact with the vehicle surface to give antistatic properties, it is possible to reduce the release of inorganic particles generated in the film. When the surfactant is melt-extruded together with other resins to produce a film, the kneading property is poorly dispersed, and the problem of migration to the film surface may occur. . The surfactant masterbatch comprises 20 to 40 wt% of surfactant and 60 to 80 wt% of low density polyethylene.

The surfactant may be used as long as it is a general surfactant, in particular, glycerin fatty acid ester (Glycerin Fatty Acid Ester), fatty amine salts (Fatty Amine) is preferably used alone or in combination, when used in combination 1 ~ 99: 99 ~ 1 can be used by mixing in the weight ratio.

The low density polyethylene may be the same as the low density polyethylene described above, or may be used.

The masterbatch may be prepared by compounding 20 to 40% by weight of surfactant and 60 to 80% by weight of low density polyethylene, and specifically, prepared by compounding at a pressure of 40 to 60 Bar at a temperature of 150 to 210 ° C. It is preferable.

The content of the surfactant masterbatch may be used in the range of 1 to 10% by weight, more preferably 4 to 8% by weight. It is excellent in the effect which prevents detachment of the target inorganic particle in the said range, and prevents contact with the automobile coating film.

(Ionomer)

The present invention may further comprise 1 to 10% by weight of ionomer, if necessary. The ionomer is a copolymer obtained by ion-crosslinking ethylene and methacrylic acid, acrylic acid and ethylene with metal ions, and the melt index is preferably in the range of 0.1 to 10 g / 10 min (190 ° C., 2,160 g). Ionomers can be used to produce films having mechanical strength and soft elasticity. In addition, the addition of the ionomer is preferable because the dispersibility of calcium carbonate can be further improved. If the amount is less than 1% by weight, the effect is insignificant, and if it is used more than 10% by weight, the price increases, which is not preferable.

(Stearic acid)

According to the present invention, stearic acid or a salt thereof may be further used to improve the kneading property of the polyethylene resin and the inorganic filler and to improve the kneading property with other additives. Preferably using 1 to 10% by weight is preferable because the kneading properties are improved.

(Other additives)

In addition, the film of the present invention may add at least one additive component selected from white pigments, UV stabilizers, antioxidants, ultraviolet absorbers, wetting agents, fragrances and lubricants conventionally used in the film, unless otherwise noted. It is desirable that the amount used does not exceed 7% by weight of the total content. More preferably, 3 to 6% by weight is used.

Hereinafter, the present invention will be described by way of example for specific description of the present invention, but the present invention is not limited to the following examples.

Hereinafter, physical properties were measured by the following method.

1) Tensile strength (N / 25mm)

Using an Instron universal testing machine, a 25 mm wide, 100 mm long piece of film was tested at an elongation rate of 20 mm / min. The strength and elongation at break were measured in the machine direction (MD) and in the transverse direction (CD).

2) Elongation (%)

Using an Instron universal testing machine, a 25 mm wide, 100 mm long piece of film was tested at an elongation rate of 20 mm / min. The strength and elongation at break were measured in the machine direction (MD) and in the transverse direction (CD).

3) Water vapor permeability (g / ㎡? Day)

It was measured according to ASTM E 96-63.

4) flexibility

The texture was evaluated as A = very flexible and smooth, B = flexible and smooth, C = hard and rough.

5) Scratch

It was attached to the car's film and the soccer ball was dropped freely at 1m height. After repeating this process 10 times, the film was peeled off and the coating was visually observed for scratches.

Example 1

As low-density polyethylene, Hanwha Chemical, Grade 955 (hereinafter referred to as LDPE-1) having a melt index of 7.7 g / 10 min (190 ° C., 2.16 kg) and a density of 0.919, was used.

As the medium density polyethylene, SK General Chemical's RG300U (hereinafter referred to as MDPE-1) having a melt index of 5.0 g / 10 min (190 ° C., 2.16 kg) and a density of 0.930 was used.

As a high density polyethylene, SK General Chemical's JH910 (hereinafter, HDPE-1) having a melt index of 8.5 g / 10 min (190 ° C., 2.16 kg) and a density of 0.962 was used.

Engage 8100 (hereinafter referred to as POE-1) manufactured by Dow Chemical Co., Ltd., having a melt index of 1.0 g / 10 min (190 ° C., 2.16 kg) and a density of 0.870, was used as a polyolefin elastomer.

Inorganic filler was used calcium carbonate (average particle size 1.5㎛, Yabashi Korea, YK-1C) coated with stearic acid.

The low density polyethylene (LDPE-1) 6% by weight, medium density polyethylene (MDPE-1) 30% by weight, high density polyethylene (HDPE-1) 5% by weight, polyolefin-based elastomer (POE-1) 5% by weight and calcium carbonate 54 After the weight% was added to the Henschel mixer, the mixture was kneaded at 220 ° C. for about 3 minutes with a biaxial kneader to prepare pellets.

The pellets were melted at 240 ° C. in a T-die extruder to be formed into a film, and the film was stretched 1.5 times in the longitudinal direction between the preheat roller and the draw roller heated to 60 ° C. in a longitudinal direction of 100 g / m 2. A film was obtained. The physical properties of the prepared film were measured and shown in Table 1 below. In addition, the photograph of the surface of the prepared film magnified 1000 times using FE-SEM is shown in FIG. As shown in FIG. 1, the pore size was small and uniform, and the surface was smooth.

In addition, after attaching the film to the front bonnet coating of the vehicle, 500 ml of water was poured on the film to impart harsh conditions for detachment. Then left for 10 hours in the open air. Since the photograph after peeling off the coating film of the automobile is shown in FIG. As shown in FIG. 2, it was confirmed that no surface detachment phenomenon of calcium carbonate occurred.

[Examples 2 to 6]

As shown in Table 1, except for changing the content range was prepared in the same manner using the same raw material as in Example 1. The physical properties of the prepared film were measured and shown in Table 1 below.

[Table 1] (unit:% by weight)

As shown in Table 1, in the embodiment according to the present invention was confirmed that the scratch does not occur, the strength, moisture permeability is excellent, and the separation of the inorganic particles did not occur.

EXAMPLES 7-12

As shown in Table 2, except for changing the content range was prepared in the same manner using the same raw material as in Example 1. The physical properties of the produced film were measured and shown in Table 2 below.

[Table 2] (Unit: weight%)

As shown in Table 2, the separation of the inorganic particles do not occur at all, it was confirmed that the flexibility, excellent strength, excellent moisture permeability.

[Example 13]

The same conditions as in Example 1 except that the melt index is 1.0g / 10min (190 ℃, 2.16kg), the density is 0.900 as a polyolefin elastomer using Lucene LC-100 (hereinafter referred to as POE-2) of LG Chem. Experiment with. The physical properties of the produced film were measured and shown in Table 3 below. In addition, a photograph in which the surface of the prepared film was enlarged 1000 times using FE-SEM is shown in FIG. 3. As shown in FIG. 3, the pore size was small and uniform, and the surface was smooth.

In addition, after attaching the film to the front bonnet coating of the vehicle, 500 ml of water was poured on the film to impart harsh conditions for detachment. Then left for 10 hours in the open air. Since the photograph after peeling off the coating film of the automobile is shown in FIG. As shown in FIG. 4, it was confirmed that no surface detachment phenomenon of calcium carbonate occurred.

[Examples 14 to 15]

As shown in Table 3, except for changing the content range was prepared in the same manner using the same raw material as in Example 13. The physical properties of the produced film were measured and shown in Table 3 below.

[Table 3] (Unit: weight%)

As shown in Table 3, it was confirmed that the flexibility of the film is improved as the content of the polyolefin-based elastomer is increased.

[Examples 16 to 17]

A masterbatch was prepared by compounding 20% by weight of surfactant (glycerin fatty acid ester: fatty amine salt = 3: 7 weight ratio) and 80% by weight of low density polyethylene (LDPE-1) in the surfactant masterbatch. B)

A film was prepared in the same manner as in Example 1, except that the masterbatch was used in the content of Table 4 below. The physical properties of the prepared film were measured and shown in Table 4 below.

[Examples 18 to 19]

As ionomer, Surlyn 1601 manufactured by DuPont with a melt index of 1.3 g / 10 min (190 ° C., 2.16 Kg) and a density of 0.940 g / cm 3 was used.

A film was prepared in the same manner as in Example 1, except that the ionomer was used in the following Table 4. The physical properties of the prepared film were measured and shown in Table 4 below.

[Table 4] (Unit: weight%)

As shown in Table 4, when including a surfactant masterbatch or ionomer it was found that the uniformity of physical properties is increased and further improved.

Comparative Example 1

A film was prepared in the same manner as in Example 1, except that the polyolefin-based elastomer was not used in Example 1. The physical properties of the produced film were measured and shown in Table 5 below. 5 shows a photograph in which the surface of the prepared film is enlarged 1000 times by using FE-SEM. As shown in FIG. 5, pores of non-uniform size were formed, and it was confirmed that the surface was not smooth.

In addition, after attaching the film to the front bonnet coating of the vehicle, 500 ml of water was poured on the film to impart harsh conditions for detachment. Then left for 10 hours in the open air. Since the photograph after peeling off the coating film of the automobile is shown in FIG. As shown in FIG. 6, the surface detachment phenomenon of calcium carbonate occurred, and the detachment phenomenon such as white line and wave pattern was observed.

[Comparative Examples 2 to 6]

To prepare a film with a composition as shown in Table 5, the physical properties are shown in Table 4 below.

[Table 5] (Unit: weight%)

As shown in Table 5, in Comparative Example 1, the moisture permeability is so high that foreign matters such as dust may penetrate into the film, and desorption of inorganic particles occurs. Comparative Examples 2 to 3 also have a high moisture permeability, there is a possibility that the foreign matter infiltrates into the film, the desorption phenomenon of the inorganic particles occurred. In Comparative Example 4, the flexibility was poor, and scratches occurred. In Comparative Examples 5 and 6, the moisture permeability is so low that the film adheres to the automotive coating film and is not suitable for imparting air permeability. Such low breathability causes desorption of inorganic particles and stains on the surface of the automotive coating film. I could see that.

Claims (8)

A fall prevention film comprising 4 to 15% by weight of low density polyethylene, 30 to 45% by weight of medium density polyethylene, 4 to 8% by weight of high density polyethylene, 3 to 20% by weight of polyolefin elastomer, and 40 to 55% by weight of inorganic filler. The method of claim 1,
The fallout prevention film further comprises 1 to 10% by weight of a surfactant masterbatch, wherein the surfactant masterbatch is a fallout prevention film comprising 20 to 40% by weight of surfactant and 60 to 80% by weight of low density polyethylene. The method of claim 1,
The low density polyethylene has a melt index of 7.0 to 14.0 g / 10 min (190 ° C., 2.16 kg) and a density of 0.915 to 0.920 g / cm 3, and the medium density polyethylene has a melt index of 2.0 to 5.0 g / 10 min (190 ° C., 2.16 kg). kg), the density is 0.928 ~ 0.936g / cm 3, the high density polyethylene has a melt index of 6.0 ~ 8.5g / 10min (190 ℃, 2.16kg), density of 0.960 ~ 0.965g / cm 3 fall prevention film. The method of claim 1,
The polyolefin-based elastomer is a fall prevention film that the melting temperature (Tm) is 50 ℃ or more. The method of claim 4, wherein
The polyolefin-based elastomer is a fall prevention film which is a polymer elastomer of ethylene polymerized using a metallocene catalyst and an alpha-olefin of (C3 to C15) and a non-covalent diene monomer. 6. The method of claim 5,
The polyolefin-based elastomer has a melt index of 0.9 ~ 1.1g / 10min (190 ℃, 2.16kg), the density of 0.870 ~ 0.908g / cm 3 fall prevention film. The method of claim 1,
The inorganic filler is any one selected from calcium carbonate, silica, barium sulfate, magnesium sulfate, calcium sulfate, talc, kaolin, aluminum hydroxide, magnesium hydroxide, zinc oxide, alumina, titanium oxide, mica, zeolite, diatomaceous earth, magnesium carbonate, clay Fallout prevention film that is one or more than two. 3. The method according to claim 1 or 2,
The fallout prevention film further comprises 1 to 10% by weight of an ionomer or stearic acid selected from a copolymer of ethylene and methacrylic acid, a copolymer of ethylene and acrylic acid.

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