WO2013129759A1 - Dustproof film - Google Patents
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- WO2013129759A1 WO2013129759A1 PCT/KR2012/010415 KR2012010415W WO2013129759A1 WO 2013129759 A1 WO2013129759 A1 WO 2013129759A1 KR 2012010415 W KR2012010415 W KR 2012010415W WO 2013129759 A1 WO2013129759 A1 WO 2013129759A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
Definitions
- 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.
- Wrap guard film is made of polypropylene and
- the wrap guard film it is a product that requires precise work so that wrinkles or bubbles are not generated.
- wrinkles or bubbles occur, water droplets are generated due to moisture inside, leaving debris on the surface of the vehicle.
- 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 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. Tyvek has been found to be useful in a variety of applications that take advantage of a well-combined combination of strength, tear resistance and permeability of the sheet as a spunbond fibrous sheet made of multiple flexifilment strands of oriented polyethylene film fibrils. .
- 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.
- (2010.05.26) includes (a) 10-30 wt% of linear low density polyethylene resin, (b) 20-35 wt% of medium density polyethylene resin, and (c) 45-55 wt% of calcium carbonate. To provide a fall prevention film excellent breathability. However, there is a need for a fall prevention film that is more flexible from the user and has less detachment of calcium carbonate.
- 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.
- 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. .
- 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.
- 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.
- Example 1 is a FE-SEM (1000 times) photograph of a film according to Example 1 of the present invention.
- Example 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.
- Example 3 is a FE-SEM (1000 times) photograph of the film according to Example 7 of the present invention.
- Example 7 of the present invention is attached to the automobile coating film and then removed again.
- 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, and the fallout
- the prevention film further comprises 1 to 10% by weight of a surfactant masterbatch comprising 20 to 40% by weight of surfactant and 60 to 80% by weight of low density polyethylene, a copolymer of ethylene and methacrylic acid, a copolymer of ethylene and acrylic acid It relates to an anti-fallout film further comprising 1 to 10% by weight of ionomer or stearic acid selected from.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 30 to 45% by weight more preferably 35 to 40% by weight is used.
- 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
- 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.
- 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 becomes too stiff so that
- the melt index can express the film strength required by the product in the range of 6.0 ⁇ 8.5g / 10min (190 °C, 2.16kg), density is 0.960 ⁇ 0.965, more preferably the melt index is 7.0 ⁇ 8.5g / 10min (190 °C, 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.
- the polyolefin-based elastomer is used to prevent desorption of inorganic particles and to increase flexibility
- the content of the polyolefin-based elastomer may be 3 to 20% by weight, more preferably 5 to 10% by weight.
- the content of the polyolefin-based elastomer may be 3 to 20% by weight, more preferably 5 to 10% by weight.
- the flexibility may be too high and the strength may be lowered.
- Tm melting temperature
- 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 elastomers include Dow
- 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.
- 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.
- the inorganic filler has an average particle diameter of 1.5 to 4.0 ⁇ m, more preferably 2.0 to
- Using a size of 3.0 mu m can produce an excellent breathable film without compromising the physical properties of the film. If the average particle diameter is less than 1.5 ⁇ m, good air permeability may not be obtained. If the average particle diameter is larger than 4.0 ⁇ m, tearing, pore formation, and strength decrease may occur during the film manufacturing process.
- the content of 40 to 55% by weight 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.
- 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.
- a 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.
- glycerin fatty acid ester Glycerin Fatty Acid Ester
- fatty amine salts Fatty Amine
- 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.
- 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.
- 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 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.
- 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.
- 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
- LDPE-1 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.
- MDPE-1 medium density polyethylene
- MDPE-1 SK General Chemical's RG300U having a melt index of 5.0 g / 10 min (190 ° C., 2.16 kg) and a density of 0.930 was used.
- HDPE-1 SK General Chemical's JH910 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 ⁇ m, Yabashi Korea, YK-1C) coated with stearic acid.
- LDPE-1 low density polyethylene
- MDPE-1 medium density polyethylene
- HDPE-1 high density polyethylene
- POE-1 polyolefin-based elastomer
- the pellets were melted at 240 ° C. in a T-die extruder to be formed into a film, and the film was preheated to 60 ° C. and stretched 1.5 times in the longitudinal direction between the drawing rollers in a longitudinal direction of 100 g / m 2.
- a phosphor film was obtained.
- the physical properties of the prepared film were measured and shown in Table 1 below. In addition, the surface of the produced film is 1000 times using FE-SEM
- FIG. 1 The enlarged photograph is shown in FIG. As shown in FIG. 1, the pore size was small and uniform, and the surface was smooth.
- Example 11 Example 12 LDPE-1 4 6 4 5 4 4 MDPE-1 30 30 30 40 40 38 HDPE-1 4 4 6 5 6 8 POE-1 10 15 20 10 10 10 10 Calcium carbonate 52 45 40 40 40 40 total 100 100 100 100 100 100 100 100 100 Tensile Strength (N / 25mm) MD 31 27 27 29 30 31 TD 15 15 16 17 17 17 % Elongation MD 179 191 217 188 182 176 TD 196 221 236 205 201 194 Water vapor permeability (g / m2 ⁇ day) 1600 1300 1000 1300 1300 1300 flexibility B A A B B B scratch radish radish radish radish radish Inorganic Particle Desorption none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none
- Example 2 The same conditions as in Example 1 except that the melt index is 1.0g / 10min (190 °C, 2.16kg), the density is 0.900 as a polyolefin elastomer using Lucene LC-100 (hereinafter referred to as POE-2) of LG Chem.
- POE-2 Lucene LC-100
- Table 3 The physical properties of the produced film were measured and shown in Table 3 below.
- 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.
- Example 14 Example 15 LDPE-1 4 6 4 MDPE-1 30 30 30 HDPE-1 4 4 6 POE-2 10 15 20 Calcium carbonate 52 45 40 total 100 100 100 Tensile Strength (N / 25mm) MD 31 27 27 TD 15 15 16 % Elongation MD 176 190 215 TD 194 218 232 Water vapor permeability (g / m2 ⁇ day) 1700 1400 1100 flexibility B A A scratch radish radish radish Inorganic Particle Desorption none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none
- LDPE-1 low density polyethylene
- 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.
- 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.
- Example 17 Example 18
- Example 19 LDPE-1 4 4 4 MDPE-1 30 30 31 30 HDPE-1 8 8 7 7 POE-1 3 3 3 3 3 3 Calcium carbonate 51 47 51 48 SM / B 4 8 - - Ionomer - - 4 8 total 100 100 100 100 100 Tensile Strength (N / 25mm) MD 32 31 32 32 TD 17 17 17 16 % Elongation MD 157 168 161 165 TD 166 176 172 177 Water vapor permeability (g / m2 ⁇ day) 2100 1700 2100 2000 flexibility B B B B scratch radish radish radish radish Inorganic Particle Desorption none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none none
- Example 1 Except for not using a polyolefin-based elastomer in Example 1
- a film was prepared in the same manner as 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.
- Comparative Example 1 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 had a high moisture permeability, so that foreign matters in the dust could penetrate into the film, resulting in detachment of inorganic particles. Comparative Example 4 is poor in flexibility
- Fallout prevention film of the present invention is very excellent in flexibility, there is no detachment of the inorganic particles does not cause any problems such as inorganic particles attached to the car paint film or scratches when attached to the car paint film is very industrially available It is a high technology.
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Abstract
The present invention relates to a dustproof film used for protecting a coating film of a vehicle and, more particularly, to a dustproof film which has excellent moisture permeability and air permeability by comprising a polyethylene-based resin and a specific polyolefin-based elastomer, excellent flexibility, is not easily scratched, and is not attached to a coating film of a vehicle.
Description
본 발명은 자동차 도막 보호에 사용되는 낙진방지용 필름에 관한 것이다. 보다 구체적으로 폴리에틸렌계 수지와 특정 폴리올레핀계 엘라스토머를 포함하여 투습성, 투기성이 우수하고, 유연성이 우수하며, 스크래치 발생이 없고, 자동차 도막에 부착되지 않는 낙진방지용 필름에 관한 것이다.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.
자동차는 출고 시에 도장표면의 스크래치 방지 및 먼지 방지용 덮개로서 플라스틱필름을 씌워 표면을 보호하고 있는데, 현재까지는 대부분이 랩가드 필름(Wrap guard film)과 타이벡(TYVEK)"이라는 원단을 이용하고 있는 실정이다.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.
랩가드 필름(Wrap guard film)은 폴리프로필렌(Polypropylene)과Wrap guard film is made of polypropylene and
폴리에틸렌(Polyethylene)로 구성된 자기점착 필름으로 자동차 출고 시 차량표면에 완전히 밀착되도록 붙여 사용하는 필름이다. 랩가드 필름을 사용 시에는 주름이나 기포가 발생하지 않도록 정밀한 작업을 요하는 제품으로, 주름이나 기포가 발생하면 내부의 수분에 의한 수적이 발생하게 되어 차량의 표면에 잔해가 남게 된다. 또한 장시간 부착상태가 유지되면 산화가 진행되어 역시 차량의 표면에 흔적이 발생하게 되는 문제점이 있어왔다.A self-adhesive film made of polyethylene, which is used to adhere completely to the surface of a vehicle when it 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.
타이벡(TYVEK)은 듀폰사에서 제조하는 고밀도폴리에틸렌(High Density Polyethylene)을 직조하여 제조한 필름으로, 강도가 강하고, 물성의 변화가 적으며, 양력에 잘 견디며, 또한 직조한 것이어서 외부로 통하는 구멍이 많아 수분이 쉽게 증발하는 등의 장점을 가지는 것으로 알려져 있다. 타이벡에 대하여는 배향된 폴리에틸렌필름 피브릴의 다중 플랙시필라멘트 가닥으로 만들어진 스펀본디드 섬유상 시이트로서 시이트의 강도, 내인열성(tear resistance) 및 투과 특성의 잘 조합된 장점을 취하는 다양한 응용 분야에서 유용한 것으로 판명되었다.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. Tyvek has been found to be useful in a variety of applications that take advantage of a well-combined combination of strength, tear resistance and permeability of the sheet as a spunbond fibrous sheet made of multiple flexifilment strands of oriented polyethylene film fibrils. .
그러나 현재 시판되고 있는 타이벡은 가격이 비싸고, 구멍을 통해 먼지가 차체에 많이 흡착되고, 원단자체가 뻣뻣하여 차량에 덮어씌울 때 작업하기가 힘들고 또한 그로 인해 차체에 스크래치가 생성되기도 하는 단점이 있다.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.
이에 따라 본 출원인이 출원하여 등록된 우리나라 등록특허 제10-0961263호Accordingly, Korea Patent No. 10-0961263 is filed by the applicant
(2010.05.26)는 이러한 문제점을 해소하기 위하여 (a)선형저밀도폴리에틸렌수지 10 ~ 30중량%, (b)중밀도폴리에틸렌수지 20 ~ 35중량% 및 (c)탄산칼슘 45 ~ 55 중량%를 포함하는 통기성이 우수한 낙진방지용필름을 제공하였다. 그러나 사용자로부터 보다 유연성이 높고, 탄산칼슘의 탈리 현상이 적은 낙진방지용 필름에 대한 요구가 있다.(2010.05.26) includes (a) 10-30 wt% of linear low density polyethylene resin, (b) 20-35 wt% of medium density polyethylene resin, and (c) 45-55 wt% of calcium carbonate. To provide a fall prevention film excellent breathability. However, there is a need for a fall prevention film that is more flexible from the user and has less detachment of calcium carbonate.
본 발명은 종래 개발된 낙진방지용 필름에 비하여 유연성이 더욱 우수하고, 무기입자의 이탈 현상이 적은 낙진방지용 필름을 제공하는 것을 목적으로 한다.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.
또한 본 발명은 자동차 도막을 보호하기에 적합한 강도와 투습성, 투기성을 갖는 낙진방지용 필름을 제공하는 것을 목적으로 한다.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.
본 발명은 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량%를 포함하는 낙진방지용 필름에 관한 것이다.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.
또한, 본 발명은 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함하는 계면활성제 마스터배치를 1 ~ 10 중량% 더 포함하는 낙진방지용 필름에 관한 것이다.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.
또한, 본 발명은 에틸렌과 메타크릴산의 공중합체, 에틸렌과 아크릴산의 공중합체에서 선택되는 이오노머 또는 스테아릭산을 1 ~ 10 중량% 더 포함하는 낙진방지용 필름에 관한 것이다.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.
본 발명에 따른 낙진방지용 필름은 유연성이 매우 우수하며, 무기입자의 탈 리가 발생하지 않아 자동차 도막에 부착 시 무기입자가 자동차 도막에 부착되거나 스크래치가 발생하는 등의 문제가 전혀 없는 매우 우수한 효과가 있다.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. .
또한 본 발명에 따른 낙진방지용 필름은 투습성 및 투기성이 우수하고, 옥외폭로에 의한 색상이나 물성의 변화가 없으며 끈적임 또는 마찰력이 낮은 자동차 도막 보호용 폴리에틸렌필름을 제공할 수 있으며, 기계적 강도가 우수하면서도, 부드러운 탄성 특성을 가지는 낙진방지용 필름을 제공할 수 있다.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.
또한 본 발명은 신차의 운송도중에 차량의 도장표면에 오염물질이 묻거나 도장표면이 긁히는 것을 방지하는 목적의 필름을 제공할 수 있다.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.
도 1은 본 발명의 실시예 1에 따른 필름의 FE-SEM(1000배)사진이다.1 is a FE-SEM (1000 times) photograph of a film according to Example 1 of the present invention.
도 2는 본 발명의 실시예 1에 따른 필름을 자동차 도막에 부착한 후 다시 제거 하였을 때의 사진이다.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.
도 3은 본 발명의 실시예 7에 따른 필름의 FE-SEM(1000배)사진이다.3 is a FE-SEM (1000 times) photograph of the film according to Example 7 of the present invention.
도 4는 본 발명의 실시예 7에 따른 필름을 자동차 도막에 부착한 후 다시 제거 하였을 때의 사진이다.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.
도 5는 본 발명의 비교예 1에 따른 필름의 FE-SEM(1000배)사진이다.5 is a FE-SEM (1000 times) photograph of the film according to Comparative Example 1 of the present invention.
도 6는 본 발명의 비교예 1에 따른 필름을 자동차 도막에 부착한 후 다시 제거 하였을 때의 사진이다.6 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.
본 발명은 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량%를 포함하며, 상기 낙진방지용 필름은 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함하는 계면활성제 마스터배치를 1 ~ 10 중량% 더 포함하며, 에틸렌과 메타크릴산의 공중합체, 에틸렌과 아크릴산의 공중합체에서 선택되는 이오노머 또는 스테아릭산을 1 ~ 10 중량% 더 포함하는 낙진방지용 필름에 관한 것이다.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, and the fallout The prevention film further comprises 1 to 10% by weight of a surfactant masterbatch comprising 20 to 40% by weight of surfactant and 60 to 80% by weight of low density polyethylene, a copolymer of ethylene and methacrylic acid, a copolymer of ethylene and acrylic acid It relates to an anti-fallout film further comprising 1 to 10% by weight of ionomer or stearic acid selected from.
이하는 본 발명에 대하여 보다 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 제 1 양태는 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량%를 포함한다.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.
본 발명의 제 2 양태는 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량% 및 계면활성제 마스터배치를 1 ~ 10 중량%를 포함한다. 이때 상기 계면활성제 마스터배치는 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함한다.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.
본 발명의 제 3 양태는 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량% 및 에틸렌과 메타크릴산의 공중합체, 에틸렌과 아크릴산의 공중합체에서 선택되는 이오노머 또는 스테아릭산을 1 ~ 10 중량%를 포함한다.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.
본 발명의 제 4 양태는 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량%, 계면활성제 마스터배치를 1 ~ 10 중량% 및 에틸렌과 메타크릴산의 공중합체, 에틸렌과 아크릴산의 공중합체에서 선택되는 이오노머 또는 스테아릭산을 1 ~ 10 중량%를 포함한다. 이때 상기 계면활성제 마스터배치는 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함한다.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.
상기 제 1 양태 내지 제 4 양태는 본 발명을 설명하기 위한 일 양태이며, 이들에 한정되는 것은 아니다.The said 1st-4th aspect is an aspect for demonstrating this invention, It is not limited to these.
이하는 본 발명의 각각의 구성요소에 대하여 보다 구체적으로 설명한다.Hereinafter, each component of the present invention will be described in more detail.
(저밀도폴리에틸렌)(Low density polyethylene)
본 발명에서 상기 저밀도폴리에틸렌은 유연성을 부여하고, 생산성을 향상하기 위하여 사용하는 것으로 4 ~ 15중량%의 범위로 사용하는 것이 목적으로 하는 물성을 만족할 수 있으므로 바람직하다. 보다 바람직하게는 6 ~ 8 중량%를 사용하는 것이 바람직하다. 4 중량% 미만으로 사용하는 경우는 작업성이 낮아져 생산성이 떨어지고, 15중량%를 초과하여 사용하는 경우는 물성이 감소되어 제품의 특성을 구현할수 없다.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.
보다 구체적으로는 멜트인덱스가 7.0 ~ 14.0g/10min(190℃, 2.16kg), 밀도가 0.915 ~ 0.920, 보다 바람직하게는 멜트인덱스가 7.5 ~ 7.7g/10min(190℃, 2.16kg), 밀도가 0.917 ~ 0.919인 것을 사용하는 것이 기계적인 물성이나 자외선에 의한 열화 등의 물성감소 등이 없는 필름을 제조할 수 있다. 이러한 저밀도폴리에틸렌의 상업화된 예로는 한화석유화학의 Grade 955 등이 있으며, 이에 제한되는 것은 아니다.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.
(중밀도폴리에틸렌)(Medium density polyethylene)
본 발명에서 상기 중밀도폴리에틸렌은 필름의 기계적인 물성을 부여하기 위하여 사용하는 것으로, 30 ~ 45 중량%, 보다 바람직하게는 35 ~ 40 중량%를 사용한다. 30 중량% 미만으로 사용하는 경우는 목적으로 하는 강도를 발현하기에 충분하지 않으며, 45 중량%를 초과하는 경우는 필름이 뻣뻣해지므로 목적으로 하는 유연성이 저하될 수 있다.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.
보다 구체적으로는 멜트인덱스가 2.0 ~ 5.0g/10min(190℃, 2.16kg), 밀도가 0.928 ~ 0.936인 범위의 것을 사용하여 기계적인 물성을 향상시킬 수 있으며, 더욱 바람직하게는 멜트인덱스가 3.0 ~ 5.0g/10min(190℃, 2.16kg), 밀도가 0.930 ~ 0.932인 범위의 것을 사용하는 것이 옥외 폭로에 의한 색상이나 물성의 변화가 적고, 목적으로 하는 무기입자의 탈리가 없는 필름을 제조할 수 있다. 이러한 중밀도폴리에틸렌의 상업화된 예로는 SK종합화학의 RG300U, FT-811 등이 있으며, 이들에 제한되는 것은 아니다.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.
(고밀도 폴리에틸렌)(High density polyethylene)
본 발명에서 상기 고밀도폴리에틸렌은 필름의 강도향상을 하기 위하여 사용되는 것으로, 그 함량은 4 ~ 8 중량%, 보다 바람직하게는 5 ~ 7 중량%를 사용하는 범위에서 상기 목적을 달성할 수 있다. 4 중량% 이하로 사용할 경우는 목표로 하는 강도를 구현할 수 없고, 8 중량% 이상으로 사용할 경우는 너무 뻣뻣해져서 차량표면에In 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 becomes too stiff so that
스크래치가 발생할 수 있다.Scratch can occur.
보다 구체적으로는 멜트인덱스가 6.0 ~ 8.5g/10min(190℃, 2.16kg), 밀도가 0.960 ~ 0.965인 범위에서 제품이 요구하는 필름 강도를 발현할 수 있으며, 보다 바람직하게는 멜트인덱스가 7.0 ~ 8.5g/10min(190℃, 2.16kg), 밀도가 0.962 ~ 0.963인 범위의 것을 사용하는 것이 좋다. 이러한 고밀도폴리에틸렌의 상업화된 예로는 SK종합화학의 JH910 등이 있으며, 이에 제한되는 것은 아니다.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.
(폴리올레핀계 엘라스토머)(Polyolefin Elastomer)
본 발명에서 상기 폴리올레핀계 엘라스토머는 무기입자의 탈리현상을 방지하고, 유연성을 높이기 위하여 사용되는 것으로, 그 함량은 3 ~ 20 중량%, 보다 바람직하게는 5 ~ 10 중량%를 사용하는 것이 좋다. 3 중량% 미만으로 사용하는 경우 목적으로 하는 무기입자의 탈리 및 유연성을 달성할 수 없으며, 20 중량%이상을 초과하여In 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 it is not possible to achieve the desorption and flexibility of the target inorganic particles, more than 20% by weight
사용하는 경우는 오히려 유연성이 너무 높아지고 강도가 저하될 수 있다.If used, the flexibility may be too high and the strength may be lowered.
보다 구체적으로는 용융온도(Tm)가 50℃ 이상인 것을 사용하는 것이 고온의 옥외 폭로 시 자동차 도막의 표면에 점착되는 현상을 방지할 수 있으므로 바람직하다. 보다 구체적으로는 용융온도(Tm)가 50 ~ 90℃ 인 것을 사용하는 것이 필름 제막이 용이하므로 바람직하다.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.
또한, 상기 폴리올레핀계 엘라스토머는 메탈로센계 촉매를 사용하여 중합된 에틸렌과 (C3~C15)의 알파-올레핀, 비공유 디엔 모노머와의 중합체 엘라스토머를 사용할 수 있으며, 멜트인덱스가 0.9 ~ 1.1g/10min(190℃, 2.16kg), 밀도가 0.870 ~ 0.908인 것을 사용하는 것이 목적으로 하는 유연성 및 무기입자의 이탈 방지효과가 우수하므로 바람직하다. 이러한 폴리올레핀계 엘라스토머의 상업화된 예로는 DowIn 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 elastomers include Dow
Chemical사의 Engage 8540, Engage 8100, LG화학사의 Lucene LC-100, Lucene LC-170 등이 있으며, 이들에 제한되는 것은 아니다.Chemicals Engage 8540, Engage 8100, LG Chemicals Lucene LC-100, Lucene LC-170 and the like, but are not limited to these.
(무기충전제)(Inorganic filler)
본 발명에서 상기 무기충전제는 필름 제조 시 연신과정에서 통기성 홀을 형성시킴으로서 통기성 및 투습성을 부여하기 위하여 사용되는 것으로, 코팅이 되어 있거나, 또는 코팅되지 않은 것을 모두 사용할 수 있다. 코팅이 안 된 무기충전제를 사용하는 경우 통기성이 향상되는 이점이 있으며, 코팅된 무기충전제를 사용하는 경우 작업성이 우수하여 필름의 기계적 특성이 우수하다.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.
구체적으로 예를 들면, 탄산칼슘, 실리카, 황산바륨, 황산마그네슘, 황산칼슘, 탈크, 카올린, 수산화알루미늄, 수산화마그네슘, 산화아연, 알루미나, 산화티탄, 마이카, 제올라이트, 규조토, 탄산마그네슘, 클레이에서 선택되는 어느 하나 또는 둘 이상의 혼합물을 사용할 수 있으며, 특히, 탄산칼슘을 사용하는 것이 바람직하다. 이때 상기 무기충전제는 평균 입경 1.5 내지 4.0㎛, 더욱 바람직하게는 2.0 내지Specifically, 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. At this time, the inorganic filler has an average particle diameter of 1.5 to 4.0㎛, more preferably 2.0 to
3.0㎛의 사이즈를 사용하는 것이 필름의 물성을 훼손시키지 않고 우수한 통기성 필름을 제조할 수 있다. 평균 입경이 1.5㎛ 미만인 경우에는 양호한 통기성을 얻을 수 없으며, 4.0㎛보다 큰 경우, 필름제조 과정에서 찢어짐, 구멍발생, 강도저하 등이 발생할 수 있다.Using a size of 3.0 mu m can produce an excellent breathable film 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.
그 함량은 40 ~ 55 중량%를 사용하는 것이 바람직하며, 상기 범위에서 목적으로 하는 투습도 및 통기성을 발현할 수 있다.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.
(계면활성제 마스터배치)(Surfactant Masterbatch)
본 발명은 필요에 따라 계면활성제 마스터배치를 추가하여 차량 표면과의 접촉을 줄여 대전방지성을 부여하고, 필름에서 발생되는 무기입자의 이탈을 줄일 수 있다. 계면활성제를 다른 수지들과 함께 용융압출하여 필름으로 제조하는 경우에는 혼련성이 나빠 고르게 분산되지 않고, 필름 표면으로 마이그레이션 되는 문제가 발생할 수 있으므로 본 발명에서는 마스터배치 형태로 제조하여 사용하는데 특징이 있다. 상기 계면활성제 마스터배치는 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함한다.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.
상기 계면활성제로는 일반적인 계면활성제라면 사용가능하나, 특히, 글리세린 지방산 에스테르(Glycerin Fatty Acid Ester), 지방성 아민염(Fatty Amine)를 단독 또는 홉합하여 사용하는 것이 바람직하며, 혼합하여 사용하는 경우는 1 ~ 99 : 99 ~ 1 중량비로 혼합하여 사용할 수 있다.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.
상기 저밀도폴리에틸렌은 앞서 설명한 저밀도폴리에틸렌과 동일한 것을 사용하거나, 또는 다른 것을 사용할 수 있다.The low density polyethylene may be the same as the low density polyethylene described above, or may be used.
상기 마스터배치는 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 컴파운딩하여 제조할 수 있으며, 구체적으로는 온도 150 ~ 210℃에서, 40 ~ 60 Bar의 압력으로 컴파운딩 하여 제조하는 것이 바람직하다.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.
상기 계면활성제 마스터배치의 함량은 1 ~ 10 중량%, 더욱 바람직하게는 4 ~ 8 중량% 범위로 사용할 수 있다. 상기 범위에서 목적으로 하는 무기입자의 이탈을 방지하고, 자동차 도막과의 접촉을 방지하는 효과가 우수하다.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.
(이오노머)(Ionomer)
본 발명은 필요에 따라 이오노머를 1 ~ 10 중량% 더 포함하는 것도 가능하다. 상기 이오노머는 에틸렌과 메타크릴산, 아크릴산과 에틸렌을 금속이온으로 이온가교시킨 공중합체인 것으로, 용융지수는 0.1 ~ 10g/10min(190 ℃, 2,160g)의 범위인 것이 바람직하다. 이오노머는 기계적 강도와 부드러운 탄성을 갖는 필름을 제조하기 위하여 사용할 수 있다. 또한, 이오노머를 추가하는 경우 탄산칼슘의 분산성을 더욱 향상시킬 수 있으므로 바람직하다. 1 중량% 미만으로 사용하는 경우는 그 효과가 미미하며, 10 중량%를 초과하여 사용하는 경우는 가격이 상승하므로 바람직하지 못하다.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.
(스테아릭산)(Stearic acid)
본 발명은 필요에 따라 폴리에틸렌 수지와 무기충전제의 혼련성을 향상시키고, 기타 첨가제와의 혼련성을 향상시키기 위해서 스테아린산 또는 그의 염을 더 추가하여 사용할 수 있다. 바람직하게는 1 ~ 10 중량%를 사용하는 것이 혼련성이 향상되므로 바람직하다.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.
(기타 첨가제)(Other additives)
또한 본 발명의 상기 필름에는 별도의 언급을 하지 않아도 필름에 통상적으로 사용되는 백색안료, UV 안정제, 산화 방지제, 자외선 흡수제, 습윤제, 향료 및 윤활제로부터 선택된 적어도 하나의 첨가제 성분을 추가할 수 있으며, 그 사용량은 전체 함량 중 7중량%를 초과하지 않도록 하는 것이 바람직하다. 보다 바람직하게는 3 ~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 중량%를 사용한다.6% by weight is used.
이하는 본 발명의 구체적인 설명을 위하여 일예를 들어 설명하는 바, 본 발명이 하기 실시예에 한정되는 것은 아니다.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.
이하 물성은 하기 방법에 의해 측정하였다.Hereinafter, physical properties were measured by the following method.
1) 인장강도(N/25mm)1) Tensile strength (N / 25mm)
인스트론(Instron)사의 만능재료 시험기를 사용하여, 너비 25mm, 길이 100mm의 필름 조각을 20mm/min의 신장속도에서 시험하였다. 파단시의 강도와 신장율을 기계방향(MD)와 가로 방향(CD)에 대하여 측정하였다.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) 신율(%)2) Elongation (%)
인스트론(Instron)사의 만능재료 시험기를 사용하여, 너비 25mm, 길이 100mm의 필름 조각을 20mm/min의 신장속도에서 시험하였다. 파단시의 강도와 신장율을 기계방향(MD)와 가로 방향(CD)에 대하여 측정하였다.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) 투습도(g/㎡ㆍday)3) Water vapor permeability (g / ㎡ · day)
ASTM E 96-63에 따라 측정하였다.It was measured according to ASTM E 96-63.
4) 유연성4) flexibility
감촉으로 평가하여 A = 매우 유연하고 평활함, B = 유연하고 평활함, C = 단단하고 거칠음으로 나타내었다.The texture was evaluated as A = very flexible and smooth, B = flexible and smooth, C = hard and rough.
5) 스크래치5) Scratch
자동차 도막에 부착시키고, 1m 높이에서 축구공을 자유낙하 시켰다. 이 과정을 10회 반복한 후 필름을 벗겨내어 도막을 육안으로 스크래치 발생여부를 관찰 하였다.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.
[실시예 1]Example 1
저밀도폴리에틸렌으로 멜트인덱스가 7.7g/10min(190℃, 2.16kg), 밀도가 0.919인 한화석유화학, Grade 955(이하, LDPE-1)를 사용하였다.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.
중밀도폴리에틸렌으로 멜트인덱스가 5.0g/10min(190℃, 2.16kg), 밀도가 0.930인 SK종합화학의 RG300U(이하, MDPE-1)를 사용하였다.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.
고밀도폴리에틸렌으로 멜트인덱스가 8.5g/10min(190℃, 2.16kg), 밀도가 0.962인 SK종합화학의 JH910(이하, HDPE-1)을 사용하였다.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.
폴리올레핀계 엘라스토머로 멜트인덱스가 1.0g/10min(190℃, 2.16kg), 밀도가 0.870인 Dow Chemical사의 Engage 8100(이하, POE-1)을 사용하였다.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.
무기충전제는 스테아릭산으로 코팅된 탄산칼슘(평균입경 1.5㎛, Yabashi Korea, YK-1C)을 사용하였다.Inorganic filler was used calcium carbonate (average particle size 1.5㎛, Yabashi Korea, YK-1C) coated with stearic acid.
상기 저밀도폴리에틸렌(LDPE-1) 6 중량%, 중밀도폴리에틸렌(MDPE-1) 30 중량%, 고밀도폴리에틸렌(HDPE-1) 5 중량%, 폴리올레핀계 엘라스토머(POE-1) 5 중량% 및 탄산칼슘 54 중량%를 헨셀믹서에 투입한 후, 2축 혼련기로 220℃에서 약 3 분간 혼련한 뒤 펠렛으로 제조하였다.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.
상기 펠렛을 T-다이 압출기에서 240℃에서 용융시켜 필름으로 성형하고, 이 필름을 60℃로 가열된 예열로울러가 연신로울러 사이에서 종방향으로 1.5배 횡방향으로 1배 연신하여 평량이 100g/㎡인 필름을 얻었다. 제조된 필름의 물성을 측정하여 하기 표 1에 기재하였다. 또한, 제조된 필름의 표면을 FE-SEM을 이용하여 1000배로The pellets were melted at 240 ° C. in a T-die extruder to be formed into a film, and the film was preheated to 60 ° C. and stretched 1.5 times in the longitudinal direction between the drawing rollers in a longitudinal direction of 100 g / m 2. A phosphor film was obtained. The physical properties of the prepared film were measured and shown in Table 1 below. In addition, the surface of the produced film is 1000 times using FE-SEM
확대한 사진을 도 1에 나타내었다. 도 1에서 보이는 바와 같이 기공의 크기가 작고 균일하며, 표면이 매끄러운 것을 확인할 수 있었다.The enlarged photograph is shown in FIG. As shown in FIG. 1, the pore size was small and uniform, and the surface was smooth.
또한, 상기 필름을 자동차의 앞쪽 보닛 부분 도막에 부착시킨 후, 물 500ml를 필름위에 부어 탈리에 대한 가혹조건을 부여하였다. 이후 야외에서 10시간 동안 방치하였다. 이후 자동차의 도막을 벗겨낸 후의 사진을 도 2에 나타내었다. 도 2에서 보이는 바와 같이 탄산칼슘의 표면 탈리 현상이 전혀 발생하지 않는 것을 확인하였In 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.
다.All.
[실시예 2 ~ 6][Examples 2 to 6]
하기 표 1과 같이, 함량범위를 달리한 것을 제외하고는 실시예 1과 동일한 원료를 사용하여 동일한 방법으로 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 1에 기재하였다.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.
표 1 (단위 : 중량%)
Table 1 (Unit: weight%)
실시예1 | 실시예2 | 실시예3 | 실시예4 | 실시예5 | 실시예6 | ||
LDPE-1 | 6 | 4 | 10 | 15 | 6 | 4 | |
MDPE-1 | 30 | 30 | 30 | 30 | 40 | 45 | |
HDPE-1 | 5 | 8 | 5 | 5 | 4 | 5 | |
POE-1 | 5 | 3 | 5 | 5 | 3 | 6 | |
탄산칼슘 | 54 | 55 | 50 | 45 | 47 | 40 | |
총합 | 100 | 100 | 100 | 100 | 100 | 100 | |
인장강도(N/25㎜) | MD | 31 | 32 | 29 | 28 | 31 | 29 |
TD | 15 | 14 | 15 | 16 | 16 | 17 | |
신율(%) | MD | 161 | 149 | 167 | 168 | 163 | 172 |
TD | 172 | 161 | 178 | 185 | 178 | 189 | |
투습도(g/㎡ㆍday) | 2200 | 2600 | 1800 | 1600 | 1700 | 1400 | |
유연성 | B | B | B | B | B | B | |
스크래치 | 무 | 무 | 무 | 무 | 무 | 무 | |
무기입자 탈리현상 | 없음 | 없음 | 없음 | 없음 | 없음 | 없음 |
Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | ||
LDPE-1 | 6 | 4 | 10 | 15 | 6 | 4 | |
MDPE-1 | 30 | 30 | 30 | 30 | 40 | 45 | |
HDPE-1 | 5 | 8 | 5 | 5 | 4 | 5 | |
POE-1 | 5 | 3 | 5 | 5 | 3 | 6 | |
Calcium carbonate | 54 | 55 | 50 | 45 | 47 | 40 | |
total | 100 | 100 | 100 | 100 | 100 | 100 | |
Tensile Strength (N / 25㎜) | MD | 31 | 32 | 29 | 28 | 31 | 29 |
TD | 15 | 14 | 15 | 16 | 16 | 17 | |
% Elongation | MD | 161 | 149 | 167 | 168 | 163 | 172 |
TD | 172 | 161 | 178 | 185 | 178 | 189 | |
Water vapor permeability (g / ㎡ · day) | 2200 | 2600 | 1800 | 1600 | 1700 | 1400 | |
flexibility | B | B | B | B | B | B | |
scratch | radish | radish | radish | radish | radish | radish | |
Inorganic Particle Desorption | none | none | none | none | none | none |
상기 표 1에서 보이는 바와 같이, 본 발명에 따른 실시예에서는 스크래치가 우수하고, 무기입자의 이탈이 발생하지 않은 것을 확인하였다.As shown in Table 1, in the embodiment according to the present invention was confirmed that the scratch is excellent, the separation of the inorganic particles did not occur.
[실시예 7 ~ 12]EXAMPLES 7-12
하기 표 2와 같이, 함량범위를 달리한 것을 제외하고는 실시예 1과 동일한 원료를 사용하여 동일한 방법으로 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 2에 기재하였다.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.
표 2 (단위 : 중량%)
TABLE 2 (Unit: weight%)
실시예7 | 실시예8 | 실시예9 | 실시예10 | 실시예11 | 실시예12 | ||
LDPE-1 | 4 | 6 | 4 | 5 | 4 | 4 | |
MDPE-1 | 30 | 30 | 30 | 40 | 40 | 38 | |
HDPE-1 | 4 | 4 | 6 | 5 | 6 | 8 | |
POE-1 | 10 | 15 | 20 | 10 | 10 | 10 | |
탄산칼슘 | 52 | 45 | 40 | 40 | 40 | 40 | |
총합 | 100 | 100 | 100 | 100 | 100 | 100 | |
인장강도(N/25mm) | MD | 31 | 27 | 27 | 29 | 30 | 31 |
TD | 15 | 15 | 16 | 17 | 17 | 17 | |
신율(%) | MD | 179 | 191 | 217 | 188 | 182 | 176 |
TD | 196 | 221 | 236 | 205 | 201 | 194 | |
투습도(g/㎡ㆍday) | 1600 | 1300 | 1000 | 1300 | 1300 | 1300 | |
유연성 | B | A | A | B | B | B | |
스크래치 | 무 | 무 | 무 | 무 | 무 | 무 | |
무기입자 탈리현상 | 없음 | 없음 | 없음 | 없음 | 없음 | 없음 |
Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | ||
LDPE-1 | 4 | 6 | 4 | 5 | 4 | 4 | |
MDPE-1 | 30 | 30 | 30 | 40 | 40 | 38 | |
HDPE-1 | 4 | 4 | 6 | 5 | 6 | 8 | |
POE-1 | 10 | 15 | 20 | 10 | 10 | 10 | |
Calcium carbonate | 52 | 45 | 40 | 40 | 40 | 40 | |
total | 100 | 100 | 100 | 100 | 100 | 100 | |
Tensile Strength (N / 25mm) | MD | 31 | 27 | 27 | 29 | 30 | 31 |
TD | 15 | 15 | 16 | 17 | 17 | 17 | |
% Elongation | MD | 179 | 191 | 217 | 188 | 182 | 176 |
TD | 196 | 221 | 236 | 205 | 201 | 194 | |
Water vapor permeability (g / ㎡ · day) | 1600 | 1300 | 1000 | 1300 | 1300 | 1300 | |
flexibility | B | A | A | B | B | B | |
scratch | radish | radish | radish | radish | radish | radish | |
Inorganic Particle Desorption | none | none | none | none | none | none |
상기 표 2에서 보이는 바와 같이, 무기입자의 이탈이 전혀 발생하지 않으며, 유연성이 우수하고, 강도, 투습도가 우수함을 확인하였다.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.
[실시예 13]Example 13
폴리올레핀계 엘라스토머로 멜트인덱스가 1.0g/10min(190℃, 2.16kg), 밀도가 0.900인 LG화학사의 Lucene LC-100(이하, POE-2)을 사용한 것을 제외하고는 상기 실시예 1과 동일한 조건으로 실험하였다. 제조된 필름의 물성을 측정하여 하기 표 3에 기재하였다. 또한, 제조된 필름의 표면을 FE-SEM을 이용하여 1000배로 확대한 사진을 도 3에 나타내었다. 도 3에서 보이는 바와 같이 기공의 크기가 작고 균일하며, 표면이 매끄러운 것을 확인할 수 있었다.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.
또한, 상기 필름을 자동차의 앞쪽 보닛 부분 도막에 부착시킨 후, 물 500ml를 필름위에 부어 탈리에 대한 가혹조건을 부여하였다. 이후 야외에서 10시간 동안 방치하였다. 이후 자동차의 도막을 벗겨낸 후의 사진을 도 4에 나타내었다. 도 4에서 보이는 바와 같이 탄산칼슘의 표면 탈리 현상이 전혀 발생하지 않는 것을 확인하였다.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.
[실시예 14 ~ 15][Examples 14 to 15]
하기 표 3과 같이, 함량범위를 달리한 것을 제외하고는 실시예 13과 동일한 원료를 사용하여 동일한 방법으로 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 3에 기재하였다.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.
표 3 (단위 : 중량%)
TABLE 3 (Unit: weight%)
실시예13 | 실시예14 | 실시예15 | ||
LDPE-1 | 4 | 6 | 4 | |
MDPE-1 | 30 | 30 | 30 | |
HDPE-1 | 4 | 4 | 6 | |
POE-2 | 10 | 15 | 20 | |
탄산칼슘 | 52 | 45 | 40 | |
총합 | 100 | 100 | 100 | |
인장강도(N/25mm) | MD | 31 | 27 | 27 |
TD | 15 | 15 | 16 | |
신율(%) | MD | 176 | 190 | 215 |
TD | 194 | 218 | 232 | |
투습도(g/㎡ㆍday) | 1700 | 1400 | 1100 | |
유연성 | B | A | A | |
스크래치 | 무 | 무 | 무 | |
무기입자 탈리현상 | 없음 | 없음 | 없음 |
Example 13 | Example 14 | Example 15 | ||
LDPE-1 | 4 | 6 | 4 | |
MDPE-1 | 30 | 30 | 30 | |
HDPE-1 | 4 | 4 | 6 | |
POE-2 | 10 | 15 | 20 | |
Calcium carbonate | 52 | 45 | 40 | |
total | 100 | 100 | 100 | |
Tensile Strength (N / 25mm) | MD | 31 | 27 | 27 |
TD | 15 | 15 | 16 | |
% Elongation | MD | 176 | 190 | 215 |
TD | 194 | 218 | 232 | |
Water vapor permeability (g / ㎡ · day) | 1700 | 1400 | 1100 | |
flexibility | B | A | A | |
scratch | radish | radish | radish | |
Inorganic Particle Desorption | none | none | none |
상기 표 3에서 보이는 바와 같이, 폴리올레핀계 엘라스토머의 함량이 증가함에 따라 필름의 유연성이 향상됨을 확인하였다.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.
[실시예 16 ~ 17][Examples 16 to 17]
계면활성제 마스터배치로 계면활성제(글리세린 지방산 에스테르 : 지방성 아민염 = 3 : 7 중량비) 20 중량%와 저밀도폴리에틸렌(LDPE-1) 80 중량%를 컴파운딩하여 마스터배치를 제조하였다.(이하, S-M/B라 함)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)
상기 마스터배치를 하기 표 4의 함량으로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 4에 나타내었다.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.
[실시예 18 ~ 19][Examples 18 to 19]
이오노머로 용융지수 1.3 g/10min(190 ℃, 2.16 Kg), 밀도 0.940 g/㎤인 듀폰사의 Surlyn 1601을 사용하였다.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.
상기 이오노머를 하기 표 4의 함량으로 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 필름을 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 4에 나타내었다.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.
표 4 (단위 : 중량%)
Table 4 (Unit: weight%)
실시예16 | 실시예17 | 실시예18 | 실시예19 | ||
LDPE-1 | 4 | 4 | 4 | 4 | |
MDPE-1 | 30 | 30 | 31 | 30 | |
HDPE-1 | 8 | 8 | 7 | 7 | |
POE-1 | 3 | 3 | 3 | 3 | |
탄산칼슘 | 51 | 47 | 51 | 48 | |
S-M/B | 4 | 8 | - | - | |
이오노머 | - | - | 4 | 8 | |
총합 | 100 | 100 | 100 | 100 | |
인장강도(N/25mm) | MD | 32 | 31 | 32 | 32 |
TD | 17 | 17 | 17 | 16 | |
신율(%) | MD | 157 | 168 | 161 | 165 |
TD | 166 | 176 | 172 | 177 | |
투습도(g/㎡ㆍday) | 2100 | 1700 | 2100 | 2000 | |
유연성 | B | B | B | B | |
스크래치 | 무 | 무 | 무 | 무 | |
무기입자 탈리현상 | 없음 | 없음 | 없음 | 없음 |
Example 16 | Example 17 | Example 18 | Example 19 | ||
LDPE-1 | 4 | 4 | 4 | 4 | |
MDPE-1 | 30 | 30 | 31 | 30 | |
HDPE-1 | 8 | 8 | 7 | 7 | |
POE-1 | 3 | 3 | 3 | 3 | |
Calcium carbonate | 51 | 47 | 51 | 48 | |
SM / B | 4 | 8 | - | - | |
Ionomer | - | - | 4 | 8 | |
total | 100 | 100 | 100 | 100 | |
Tensile Strength (N / 25mm) | MD | 32 | 31 | 32 | 32 |
TD | 17 | 17 | 17 | 16 | |
% Elongation | MD | 157 | 168 | 161 | 165 |
TD | 166 | 176 | 172 | 177 | |
Water vapor permeability (g / ㎡ · day) | 2100 | 1700 | 2100 | 2000 | |
flexibility | B | B | B | B | |
scratch | radish | radish | radish | radish | |
Inorganic Particle Desorption | none | none | none | none |
상기 표 4에서 보이는 바와 같이, 계면활성제 마스터배치 또는 이오노머를 포함하는 경우 물성의 균일성이 높아지고 더욱 향상되는 것을 알 수 있었다.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.
[비교예 1]Comparative Example 1
상기 실시예 1에서 폴리올레핀계 엘라스토머를 사용하지 않은 것을 제외하고는 실Except for not using a polyolefin-based elastomer in Example 1
시예 1과 동일하게 필름을 제조하였다. 제조된 필름의 물성을 측정하여 하기 표 5에 나타내었다. 제조된 필름의 표면을 FE-SEM을 이용하여 1000배로 확대한 사진을 도 5에 나타내었다. 도 5에서 보이는 바와 같이 불균일한 크기의 기공이 형성되었으며, 표면이 매끄럽지 않은 것을 확인할 수 있었다.A film was prepared in the same manner as 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.
또한, 상기 필름을 자동차의 앞쪽 보닛 부분 도막에 부착시킨 후, 물 500ml를 필름위에 부어 탈리에 대한 가혹조건을 부여하였다. 이후 야외에서 10시간 동안 방치하였다. 이후 자동차의 도막을 벗겨낸 후의 사진을 도 6에 나타내었다. 도 6에서 보이는 바와 같이 탄산칼슘의 표면 탈리 현상이 발생하여, 흰선 및 물결무늬와 같은 탈리 현상이 관찰되었다.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.
[비교예 2 ~ 6][Comparative Examples 2 to 6]
하기 표 5와 같은 조성으로 필름을 제조하고, 그 물성을 하기 표 4에 기재하였다.To prepare a film with a composition as shown in Table 5, the physical properties are shown in Table 4 below.
표 5 (단위 : 중량%)
Table 5 (Unit: weight%)
비교예1 | 비교예2 | 비교예3 | 비교예4 | 비교예5 | 비교예6 | ||
LDPE-1 | 7 | 45 | - | - | 4 | 4 | |
MDPE-1 | 30 | - | 45 | - | 50 | 30 | |
HDPE-1 | 8 | - | - | 45 | 8 | 1 | |
POE-1 | - | - | - | - | 3 | 25 | |
탄산칼슘 | 55 | 55 | 55 | 55 | 35 | 40 | |
총합 | 100 | 100 | 100 | 100 | 100 | 100 | |
인장강도(N/25mm) | MD | 31 | 25 | 32 | 37 | 36 | 32 |
TD | 15 | 14 | 15 | 13 | 17 | 16 | |
신율(%) | MD | 134 | 141 | 139 | 124 | 193 | 241 |
TD | 145 | 148 | 146 | 130 | 212 | 265 | |
투습도(g/㎡ㆍday) | 3400 | 3100 | 3500 | 3800 | 500 | 300 | |
유연성 | B | B | B | C | B | A | |
스크래치 | 무 | 무 | 무 | 유 | 무 | 무 | |
무기입자 탈리현상 | 있음 | 있음 | 있음 | 있음 | 있음 | 있음 |
Comparative Example 1 | Comparative Example 2 | Comparative Example 3 | Comparative Example 4 | Comparative Example 5 | Comparative Example 6 | ||
LDPE-1 | 7 | 45 | - | - | 4 | 4 | |
MDPE-1 | 30 | - | 45 | - | 50 | 30 | |
HDPE-1 | 8 | - | - | 45 | 8 | One | |
POE-1 | - | - | - | - | 3 | 25 | |
Calcium carbonate | 55 | 55 | 55 | 55 | 35 | 40 | |
total | 100 | 100 | 100 | 100 | 100 | 100 | |
Tensile Strength (N / 25mm) | MD | 31 | 25 | 32 | 37 | 36 | 32 |
TD | 15 | 14 | 15 | 13 | 17 | 16 | |
% Elongation | MD | 134 | 141 | 139 | 124 | 193 | 241 |
TD | 145 | 148 | 146 | 130 | 212 | 265 | |
Water vapor permeability (g / ㎡ · day) | 3400 | 3100 | 3500 | 3800 | 500 | 300 | |
flexibility | B | B | B | C | B | A | |
scratch | radish | radish | radish | U | radish | radish | |
Inorganic Particle Desorption | has exist | has exist | has exist | has exist | has exist | has exist |
상기 표 5에서 보이는 바와 같이, 비교예 1은 투습도가 너무 높아 먼지 등의 이물질이 필름 내부로 침투할 가능성이 있고, 무기입자의 탈리 현상이 발생하였다. 비교예 2 내지 비교예 3 역시 투습도가 너무 높아 먼지의 이물질이 필름 내부로 침투할 가능성이 있고, 무기입자의 탈리 현상이 발생하였다. 비교예 4는 유연성이 나쁘 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 had a high moisture permeability, so that foreign matters in the dust could penetrate into the film, resulting in detachment of inorganic particles. Comparative Example 4 is poor in flexibility
고, 스크래치가 발생하였다. 비교예 5 및 비교예 6은 투습도가 너무 낮아 필름이 자동차 도막에 부착되고, 통기성을 부여하기에 부적합하며, 이러한 낮은 통기성으로 인해 무기입자의 탈리현상이 발생하고, 자동차 도막의 표면에 얼룩이 발생하는 것을 알 수 있었다.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.
본 발명의 낙진방지용 필름은 유연성이 매우 우수하며, 무기입자의 탈 리가 발생하지 않아 자동차 도막에 부착 시 무기입자가 자동차 도막에 부착되거나 스크래치가 발생하는 등의 문제가 전혀 없으므로 산업상 이용가능성이 매우 높은 기술인 것이다. Fallout prevention film of the present invention is very excellent in flexibility, there is no detachment of the inorganic particles does not cause any problems such as inorganic particles attached to the car paint film or scratches when attached to the car paint film is very industrially available It is a high technology.
Claims (8)
- 저밀도폴리에틸렌 4 ~ 15 중량%, 중밀도폴리에틸렌 30 ~ 45 중량% 및 고밀도 폴리에틸렌 4 ~ 8 중량%, 폴리올레핀계 엘라스토머 3 ~ 20 중량%, 무기충전제 40 ~ 55 중량%를 포함하는 낙진방지용 필름.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.
- 제 1항에 있어서,The method of claim 1,상기 낙진방지용 필름은 계면활성제 마스터배치 1 ~ 10 중량%를 더 포함하며, 상기 계면활성제 마스터배치는 계면활성제 20 ~ 40 중량%와 저밀도폴리에틸렌 60 ~ 80 중량%를 포함하는 낙진방지용 필름.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.
- 제 1항에 있어서,The method of claim 1,상기 저밀도폴리에틸렌은 멜트인덱스가 7.0 ~ 14.0g/10min(190℃, 2.16kg), 밀도가 0.915 ~ 0.920g/㎤이고, 상기 중밀도폴리에틸렌은 멜트인덱스가 2.0 ~ 5.0g/10minThe low density polyethylene has a melt index of 7.0 to 14.0 g / 10 min (190 ° C., 2.16 kg), 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℃, 2.16kg), 밀도가 0.928 ~ 0.936g/㎤이고, 상기 고밀도폴리에틸렌은 멜트인덱스가 6.0 ~ 8.5g/10min(190℃, 2.16kg), 밀도가 0.960 ~ 0.965g/㎤인 낙진방지용 필름.(190 ° C, 2.16kg), density is 0.928 ~ 0.936g / cm3, the high density polyethylene has a melt index of 6.0 ~ 8.5g / 10min (190 ° C, 2.16kg), density of 0.960 ~ 0.965g / cm3 for fallout prevention film.
- 제 1항에 있어서,The method of claim 1,상기 폴리올레핀계 엘라스토머는 용융온도(Tm)가 50℃ 이상인 것인 낙진방지용 필름.The polyolefin-based elastomer is a fall prevention film that the melting temperature (Tm) is 50 ℃ or more.
- 제 4항에 있어서,The method of claim 4, wherein상기 폴리올레핀계 엘라스토머는 메탈로센계 촉매를 사용하여 중합된 에틸렌과 (C3~C15)의 알파-올레핀, 비공유 디엔 모노머와의 중합체 엘라스토머인 낙진방지용 필름.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.
- 제 5항에 있어서,The method of claim 5,상기 폴리올레핀계 엘라스토머는 멜트인덱스가 0.9 ~ 1.1g/10min(190℃, 2.16kg), 밀도가 0.870 ~ 0.908g/㎤인 것인 낙진방지용 필름.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.
- 제 1항에 있어서,The method of claim 1,상기 무기충전제는 탄산칼슘, 실리카, 황산바륨, 황산마그네슘, 황산칼슘, 탈크, 카올린, 수산화알루미늄, 수산화마그네슘, 산화아연, 알루미나, 산화티탄, 마이카, 제올라이트, 규조토, 탄산마그네슘, 클레이에서 선택되는 어느 하나 또는 둘 이상의 혼합물인 낙진방지용 필름.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.
- 제 1항 또는 제 2항에 있어서,The method according to claim 1 or 2,상기 낙진방지용필름은 에틸렌과 메타크릴산의 공중합체, 에틸렌과 아크릴산의 공중합체에서 선택되는 이오노머 또는 스테아릭산을 1 ~ 10 중량% 더 포함하는 낙진방지용 필름.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, and a copolymer of ethylene and acrylic acid.
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CN114702741B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | Low-density polyethylene material and preparation method and application thereof |
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