KR101743703B1 - Easily separable heat shrinkable film - Google Patents
Easily separable heat shrinkable film Download PDFInfo
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- KR101743703B1 KR101743703B1 KR1020150167716A KR20150167716A KR101743703B1 KR 101743703 B1 KR101743703 B1 KR 101743703B1 KR 1020150167716 A KR1020150167716 A KR 1020150167716A KR 20150167716 A KR20150167716 A KR 20150167716A KR 101743703 B1 KR101743703 B1 KR 101743703B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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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
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
The present invention relates to a heat-shrinkable film, which has a high heat shrinkage ratio and a low specific gravity of 1 g / cm 3 or less, and thus can be usefully used as a label for a PET bottle, a film for coating, and a film for packing.
Description
The present invention relates to a heat-shrinkable film that can be easily separated, and the film has a high heat shrinkage ratio and a low specific gravity of 1 g / cm 3 or less, and thus can be usefully used as a label for a PET bottle or a coating film and a film for packing .
Although a polyvinyl chloride (PVC) film has been used as a heat shrinkable film, the PVC heat shrinkable film has a problem causing environmental pollution problem. Accordingly, the use of polyester heat shrinkable films which are environmentally friendly and have excellent heat resistance and high heat shrinkage has been increasing. The heat-shrinkable polyester film is widely used for packaging and labeling purposes in beverage containers such as PET bottles and other types of containers by utilizing the property of shrinking by heating. Conventionally, in order to label a cylindrical container such as a beverage container or the like, a polyester film is cut to a predetermined size, and then the container is rolled up, adhered to both ends with a solvent, and then covered with a container to shrink. Therefore, for effective labeling, the properties of the heat-shrinkable polyester film are very important.
On the other hand, the polyester heat-shrinkable film has a specific gravity of 1.0 g / cm < 3 > or more and thus has a problem in that it is difficult to separate the PET bottle from the PET bottle. Therefore, there is a desire for a heat-shrinkable polyester film having a specific gravity of 1 g / cm 3 or less and a high heat shrinkage ratio, which is easy to separate from the PET bottle, that is, recyclable.
Recently, heat-shrink laminated films having various configurations have been developed (U.S. Patent No. 6,861,125). However, the heat shrinkable laminated films heretofore known also fail to achieve easy separation from the container as described above.
Accordingly, an object of the present invention is to provide a container such as a PET bottle having a high heat shrinkage ratio and a specific gravity lower than that of water, and a heat shrinkable film which can be easily separated from water.
In order to achieve the above object,
As a laminated film having a three-layer structure of a first surface layer / a base layer / a second surface layer,
Wherein the first surface layer and the second surface layer each comprise a copolymerized polyester resin containing a dicarboxylic acid repeating unit and a diol repeating unit,
Wherein the base layer comprises a copolymerized olefin resin comprising a C 2 -5 alkylene repeating unit and a repeating unit represented by the following formula (1)
Wherein the substrate layer has a thickness of at least 4 times the sum of the thicknesses of the first surface layer and the second surface layer:
In Formula 1,
n is an integer of 1 to 4,
R is an alkenyl C 1 -4 alkoxycarbonyl, carboxyl or C 2 -10 Al.
The present invention also provides a laminated film having a three-layer structure of a first surface layer / a base layer / a second surface layer,
Wherein the first surface layer and the second surface layer each comprise a copolymerized polyester resin,
Said base layer comprising a copolymerized olefin resin,
Has a specific gravity of 1 g / cm < 3 &
And exhibits a heat shrinkage ratio of 35 to 90% in the longitudinal direction or the width direction when heat-treated at a temperature of 90 DEG C for 10 seconds.
The heat-shrinkable film of the present invention has a high heat shrinkage ratio and a specific gravity lower than that of water, so that it can be easily recycled since it is easily separated from a container such as a PET bottle and water. Furthermore, it has excellent solvent adhesive strength and can be usefully used as a label for a container such as a PET bottle or a film for coating and a film for packing.
In addition, in the case of an olefinic material, the copolymerization olefin resin used for the substrate layer of the heat shrinkable film of the present invention causes a delamination phenomenon due to low compatibility with the polyester resin, It is excellent in compatibility and does not cause delamination phenomenon in lamination and does not pyrolyse at high temperature. Therefore, it shows excellent lamination stability even in the case of polyester resin and pneumatic shipment.
1 is a cross-sectional view showing a heat-shrinkable film according to an embodiment of the present invention (10: heat shrink film, 11: first surface layer, 12: base layer, 13: second surface layer).
The heat-shrinkable film of the present invention is a laminated film having a three-layer structure of a first surface layer / a base layer / a second surface layer, wherein the first surface layer and the second surface layer each comprise a copolymerization product comprising a dicarboxylic acid repeating unit and a diol repeat unit And a copolymer resin comprising a polyester resin, wherein the base layer comprises a C 2 -5 alkylene repeating unit and a repeating unit represented by the following formula (1), wherein the base layer comprises a first surface layer and a second surface layer Thickness of at least four times the sum of the thicknesses:
[Chemical Formula 1]
In Formula 1,
n is an integer of 1 to 4,
R is an alkenyl C 1 -4 alkoxycarbonyl, carboxyl or C 2 -10 Al.
1, the
The first surface layer and the second surface layer include a copolymer polyester resin. More specifically, the first surface layer and the second surface layer include a copolymer polyester resin as a main component. The first surface layer and the second surface layer may contain 85% or more by weight of the copolymer polyester resin. More specifically, the first surface layer and the second surface layer may contain 95 wt% or more of a copolymer polyester resin. More specifically, the first surface layer and the second surface layer may contain 99 wt% or more of copolymerized polyester resin.
The copolymer polyester resin includes a diol repeating unit and a dicarboxylic acid repeating unit. More specifically, the copolymer polyester resin may be composed of a diol repeating unit and a dicarboxylic acid repeating unit. More specifically, the copolymer polyester resin may contain about 95 mol% or more of a diol repeating unit and a dicarboxylic acid repeating unit.
The diol repeating unit and the dicarboxylic acid repeating unit may be polymerized after the transesterification reaction to form the copolymer polyester resin.
Specific examples of the diol repeating unit include ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, 1,3-propanediol, 1,2-octanediol, 1,3-octane 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol) 1,3-propanediol, 2,2-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl- , 1-dimethyl-1,5-pentanediol, and mixtures thereof.
The diol repeating unit may include ethylene glycol in an amount of 60 mol% or more. More specifically, the diol repeat unit may comprise from 1 to 30 mol% of neopentyl glycol, from 60 to 98 mol% of ethylene glycol repeating units and from 0.5 to 10 mol% of diethylene glycol repeat units. More specifically, the diol repeat unit may comprise from 9 to 30 mole percent neopentyl glycol repeat units, from 69 to 90 mole percent ethylene glycol repeat units, and from 1 to 5 mole percent diethylene glycol repeat units.
Specific examples of the dicarboxylic acid repeating unit include aromatic dicarboxylic acids such as terephthalic acid, dimethylterephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid; Alicyclic dicarboxylic acid; Esters thereof; And mixtures thereof.
The above-mentioned dicarboxylic acid repeating unit may contain 70 mol% or more aromatic dicarboxylic acid. More specifically, the dicarboxylic acid repeating unit may contain 70 mol% or more of terephthalic acid. More specifically, the dicarboxylic acid repeating unit may include at least 80 mol% of terephthalic acid repeating units. More specifically, the dicarboxylic acid repeating unit may include 90 mol% or more of terephthalic acid repeating units. More specifically, the dicarboxylic acid repeating unit may contain 95 mol% or more of terephthalic acid repeating units. The dicarboxylic acid repeating unit may include 70 to 90 mol% of terephthalic acid repeating units and 10 to 30 mol% of isophthalic acid repeating units. More specifically, the dicarboxylic acid repeating unit may include 75 to 90 mol% of terephthalic acid repeating units and 10 to 25 mol% of isophthalic acid repeating units.
The copolymer polyester resin may be a copolymerized polyethylene terephthalate resin.
The intrinsic viscosity of the copolymer polyester resin may be 0.55 dl / g to 0.75 dl / g, more specifically 0.6 dl / g to 0.7 dl / g.
The first surface layer and the second surface layer may be the same or different.
The first surface layer and the second surface layer can compensate for the weakening of the adhesive force due to the organic solvent caused by the crystallization occurring in the printing process (excellent seaming property by maintaining high solvent adhesion).
The base layer comprises a copolymerized olefin resin. More specifically, the base layer contains a copolymerized olefin resin as a main component. The base layer may comprise at least 85% by weight of the copolymerized olefin resin. More specifically, the substrate layer may comprise at least 95% by weight of the copolymerized olefin resin. More specifically, the base layer may comprise at least 99% by weight of the copolymerized olefin resin.
The copolymerized olefin resin includes a C 2 -5 alkylene repeating unit and a repeating unit represented by the formula (1). More specifically, the copolymerized olefin resin may consist entirely of a C 2 -5 alkylene repeating unit and a repeating unit represented by the formula (1). More specifically, the copolymerized olefin resin may contain at least 95 mol% of a C 2 -5 alkylene repeating unit and a repeating unit represented by the formula (1). More specifically, the copolymerized olefin resin may include a repeating unit represented by the following formula (2).
In Formula 2,
m is an integer from 2,500 to 3,300,
l is an integer from 120 to 280,
R 1 is C 1 -4 alkoxy-carbonyl.
The C 2 -5 alkylene repeating unit and the repeating unit represented by the formula (1) may be polymerized in a conventional manner to form the copolymer polyolefin resin.
The copolymerized olefin resin may contain 5 to 40 mol% of the repeating unit represented by the formula (1) and 60 to 95 mol% of the C 2 -5 alkylene repeating unit. More specifically, the copolymerized olefin resin may include 10 to 35 mol% of the repeating unit represented by the formula (1) and 65 to 90 mol% of the C 2 -5 alkylene repeating unit. More specifically, the copolymerized olefin resin may contain 15 to 30 mol% of the repeating unit represented by the formula (1) and 70 to 85 mol% of the C 2-5 alkylene repeating unit.
The C 2 -5 alkylene repeating unit may specifically be an ethylene repeating unit.
In the general formula (1), R may specifically be methoxycarbonyl, ethoxycarbonyl or butoxycarbonyl. That is, the repeating unit represented by the formula (1) may be methyl acrylate, ethyl acrylate or butyl acrylate repeating unit.
The copolymerized olefin resin may be specifically poly (ethylene-co-butyl acrylate) (poly (ethylene-co-butyl acrylate)).
The weight average molecular weight of the copolymerized olefin resin may be 80,000 to 120,000, more specifically 90,000 to 110,000.
The copolymerized olefin resin not only serves to lower the specific gravity of the film but also has excellent compatibility with the polyester resin and does not cause delamination at the time of lamination and has an advantage of not being thermally decomposed at a high temperature so that when copolymerized with a polyester resin And exhibits excellent lamination stability.
The heat-shrinkable film of the present invention has a structure in which a first surface layer, a base layer and a second surface layer are sequentially laminated, and they can be extruded simultaneously by a co-extrusion process and then drawn.
The heat shrinkable film may have a first surface layer, a substrate layer, and a second surface layer in a thickness ratio of 1: 8 to 100: 1, more specifically, 1: 8 to 40: 1. When the thickness ratio is within the above range, the specific gravity of the film can be made 1 g / cm 3 or less, and the film can be easily recycled by easy separation from the applied container and water.
The thickness of the heat shrinkable film may be 12 to 150 占 퐉, more specifically 12 to 50 占 퐉.
The heat-shrinkable film may exhibit a high heat shrinkage rate of 35 to 90%, more specifically 50 to 75% in the longitudinal or width direction when heat-treated at a temperature of 90 DEG C for 10 seconds.
The heat shrinkable film of the present invention can be added within a range that does not impair the effects of the present invention, such as a polymerization catalyst, a dispersant, an antiblocking agent, an electrostatic agent, an antistatic agent, an antioxidant, a heat stabilizer, For example, 0.001 to 10.0% by weight based on the total weight of the heat shrinkable film.
The heat shrinkable film of the present invention is a laminated film having a three-layer structure of a first surface layer / a base layer / a second surface layer, wherein the first surface layer and the second surface layer each comprise a copolymerized polyester resin, And has a specific gravity of 1 g / cm 3 or less and exhibits a heat shrinkage ratio of 35 to 90% in a longitudinal direction or a width direction when heat-treated at a temperature of 90 캜 for 10 seconds.
The heat shrinkable film according to the present invention can be produced by the following process.
(1) providing a copolymerized polyester resin constituting each of the first surface layer and the second surface layer, and a copolymerized olefin resin constituting the base layer; (2) co-extruding the resins to produce an unoriented sheet; And (3) stretching the unstretched sheet.
First, the copolymer polyester resin can be produced by an esterification reaction between a diol repeating unit and a dicarboxylic acid repeating unit and a solid phase polymerization process according to a conventional method.
The copolymerized olefin resin can be produced by a polymerization process of a C 2 -5 alkylene repeating unit and a repeating unit represented by the formula (1).
Next, the copolymer polyester resin and the copolymerized olefin resin were co-extruded (melt-extruded) into different layers according to a conventional method, and then cooled to obtain a three-layered laminate of the first surface layer / base layer / To produce an unstretched sheet of the structure.
Specifically, the melt extrusion is carried out by mixing the copolymerized polyester resin at a temperature of Tm 1 + 30 ° C to Tm 1 + 80 ° C, and the copolymerized olefin resin at a temperature of Tm 2 + 120 ° C to Tm 2 + It can be extruded. Tm 1 is the melting point of the copolymer polyester resin, and Tm 2 is the melting point of the copolymerized olefin resin.
Further, it is preferable that the cooling is performed at a temperature of 30 DEG C or less, for example, 15 to 30 DEG C.
Thereafter, the unstretched sheet is stretched in one or both directions in the first direction, for example, the longitudinal direction (machine direction) and the second direction, for example, the width direction (tenter direction) have.
Specifically, the unstretched sheet may be uniaxially or biaxially stretched.
The unstretched sheet may be stretched 1.0 to 4.5 times in the first direction, for example, in the longitudinal direction, and 1.0 to 5.0 times in the second direction perpendicular to the first direction, for example, in the width direction. More specifically, the unstretched sheet may be stretched 1.0 to 3.5 times in the first direction, for example, in the longitudinal direction, and 3.0 to 4.5 times in the second direction perpendicular to the first direction, for example, in the width direction.
The stretching temperature may be Tg + 5 ° C to Tg + 80 ° C. In order to further improve the brittleness of the film, the stretching temperature range may be Tg + 10 ° C to Tg + 50 ° C. Tg is the glass transition temperature of the copolymer polyester.
After initiating the heat setting, the film relaxes in the longitudinal and / or width direction and the stretched sheet can be heat set at a temperature of 60 to 240 캜, more specifically 65 to 120 캜.
The heat-shrinkable film of the present invention thus produced has a high heat shrinkage ratio and a low specific gravity of 1 g / cm 3 or less, so that it can be easily recycled by easy separation in a container such as a PET bottle and water. Furthermore, it has excellent solvent adhesive strength and can be usefully used as a label for a container such as a PET bottle or a film for coating and a film for packing. The copolymerized olefin resin used for the base layer of the heat shrinkable film is excellent in compatibility with the polyester resin and does not cause delamination at the time of lamination and has an advantage that it is not pyrolyzed at a high temperature. And exhibits excellent lamination stability.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
[ Example ]
Manufacturing example 1: Production of copolymerized polyester resin- (1)
After the temperature of the esterification reaction tube was elevated to 200 ° C, 77 mol% of ethylene glycol, 18 mol% of neopentyl glycol, 5 mol% of diethylene glycol and 100 mol% of terephthalic acid were added and, as a catalyst, 0.017 parts by weight were added and stirred. Then, the mixture was subjected to pressure elevation under the conditions of gauge pressure 0.34 MPa and 240 deg. C, the esterification reaction tube was returned to normal pressure, and 0.014 part by weight of phosphoric acid was added. Thereafter, the temperature was raised to 260 DEG C over 15 minutes, and 0.012 part by weight of trimethyl phosphate was added as a stabilizer. Subsequently, after 15 minutes, dispersion treatment was carried out with a high-pressure disperser. After 15 minutes, the obtained esterification reaction product was transferred to a polycondensation reaction tube and polycondensation reaction was carried out at 280 ° C under reduced pressure.
After completion of the polycondensation reaction, the mixture was filtered through a nylon filter having a cut-off size of 95% at a size of 5 탆, extruded from the nozzle into a strand shape, and cooled and solidified using cooling water previously subjected to filtration treatment (pore size: And cut into pellets to produce a copolymer polyester resin chip.
Manufacturing example 2: Production of copolymerized polyester resin - (2)
S2008 product of SK Chemical Co. was used.
Manufacturing example 3: Production of copolymerized polyester resin - (3)
Except that ethylene glycol 100 mole% was used instead of ethylene glycol 77 mole%, neopentyl glycol 18 mole%, and diethylene glycol 5 mole%, and terephthalic acid 82 mole% and isophthalic acid 18 mole% were used instead of terephthalic acid 100 mole% , And a copolymerized polyester resin chip was produced in the same manner as in Production Example 1.
Manufacturing example 4: Preparation of copolymerized olefin resin - (1)
According to the production method described in the Korean Patent No. 10-1338836, the polymerization was carried out using ethylene and n-butyl acrylate monomer under the same process conditions, whereby the number average molecular weight was 90,500 and the butyl acrylate content was 17% by weight of poly (ethylene-co-butyl acrylate) (copolymer).
Specifically, a reactor at 145 캜, a pressure of 2180 kg / cm 2 (214 MPa), a supply temperature of 50 캜, an ethylene feed rate of 6.8 kg / h, a feed rate of butyl acrylate of 1.3 kg / Methanol solvent feed rate, and a propane telogen feed rate of 1.14 kg / h in a high pressure test-scale autoclave reactor. In addition, di (secondary-butyl) peroxydicarbonate diluted to 5 vol% in an odorless mineral spirits (Ruperox 225 from Arcema) initiator was used.
Manufacturing example 5: Preparation of copolymerized olefin resin - (2)
According to the production method described in the Korean Patent No. 10-1338836, the polymerization was carried out using the ethylene and methyl acrylate monomers, and the number average molecular weight was 100,500 and the methyl acrylate content was 18 weight % Of poly (ethylene-co-methyl acrylate) (copolymer).
A supply pressure of 2180 kg / cm 2 (214 MPa), a supply temperature of 50 ° C, an ethylene feed rate of 6.8 kg / h, a methyl acrylate feed rate of 0.8 kg / h, and a methanol solvent supply of 0.45 kg / Speed, and a propane telogen feed rate of 1.14 kg / h in a high pressure test-scale autoclave reactor. In addition, di (secondary-butyl) peroxydicarbonate diluted to 5 vol% in an odorless mineral spirits (Ruperox 225 from Arcema) initiator was used.
Example One.
The resin chips were melted and co-extruded through an extruder at 275 DEG C so that the copolymerized polyester resin produced in Production Example 1 constituted both surface layers and the copolymerized olefin resin produced in Production Example 4 constituted the base layer , And was then closely contacted with a casting roll at 25 DEG C to prepare an unoriented sheet. The unstretched sheet was stretched 3.5 times in the width direction at 75 캜, heat treated (heat set) at 70 캜 for 10 seconds and cooled to obtain a three-layer heat shrinkable film having a thickness of 25 탆 (first surface layer: base layer: Thickness ratio = 7.5: 85: 7.5).
Example 2 to 5 and Comparative Example 1 to 6.
A heat-shrinkable film was produced in the same manner as in Example 1, except that the thickness ratio of the first surface layer, the base layer and the second surface layer, and the kind of the surface layer resin and / .
(Samsung Total, DR530G)
(Samsung Total, DR530G)
(Samsung Total, DR530G)
(Exxon Mobil, 35-05H)
(Samsung Total, HY110)
(SK Corporation, 8700)
Experimental Example 1. Specific gravity
ASTM D1505, and the measurement results are shown in Table 2 below.
Experimental Example 2. Heat shrinkage
Each of the films prepared in Examples 1 to 5 and Comparative Examples 1 to 6 was heat-treated for 10 seconds in a water bath at 90 DEG C and then the heat shrinkage ratio in the transverse direction (TD, tenter direction) was measured according to the following formula. The results are shown in Table 2 below.
Heat shrinkage percentage (%) = (initial length - length after heat treatment) / initial length x 100
Experimental Example 3. Adhesion
10 [mu] l of 1,3-dioxolane was dropped on the surfaces of the films prepared in Examples 1 to 5 and Comparative Examples 1 to 6, another one of the same film was covered, and a uniform pressure was applied with a roller. The glued film was aged for 30 minutes and then peeled off from the seaming position with a width of 30 mm and a length of 90 mm. Each end of each film was gripped with a clip, and one end was pulled at a rate of 300 mm / min using an adhesion tester (available from CK Corporation) to measure a maximum force (gf) at the time of separation of the heat shrinkable film. The results are shown in Table 2 below.
As shown in Table 2, all of the heat shrinkable films of Examples 1 to 5 had a low specific gravity (1 g / cm 3 or less), a high heat shrinkage rate (70% or more), and a high adhesive force (800 gf or more) Films 1 to 6 exhibited more than one falling property. As a result, it was confirmed that the heat-shrinkable film of the present invention can be easily recycled because it is used as a label for containers such as PET bottles due to the low specific gravity and high heat shrinkage ratio as described above.
Claims (13)
Wherein the first surface layer and the second surface layer each comprise a copolymerized polyester resin containing a dicarboxylic acid repeating unit and a diol repeating unit,
Wherein the substrate layer comprises a copolymerized olefin resin comprising a C 2-5 alkylene repeating unit and a repeating unit represented by the following formula (1)
Wherein the base layer has a thickness at least four times the sum of the thicknesses of the first and second surface layers,
Wherein the first surface layer and the second surface layer each comprise 1 to 30 mol% of neopentyl glycol repeating units based on the total diol repeating units, 60 to 98 mol% of ethylene glycol repeating units and 0.5 to 10 mol% of diethylene glycol repeating units Wherein the heat shrinkable film comprises:
[Chemical Formula 1]
In Formula 1,
n is an integer of 1 to 4,
R is C 1-4 alkoxycarbonyl, carboxyl or C 2-10 alkenyl.
Wherein the copolymerized olefin resin has a weight average molecular weight of 80,000 to 120,000.
Wherein the C 2 -5 alkylene repeating unit is an ethylene repeating unit.
Wherein R is C 1 -4 alkoxycarbonyl is, heat-shrinkable film.
The base layer, heat-shrinkable film comprising a repeating unit and C 2 -5 alkylene repeating units of 60 to 95 mol% represented by general formula (I) of from 5 to 40 mol%, based on the total repeating units in the copolymer the olefin resin.
Wherein the repeating unit represented by the formula (1) is a repeating unit of methyl acrylate, ethyl acrylate or butyl acrylate.
Wherein the copolymerized olefin resin comprises a repeating unit represented by the following formula (2):
(2)
In Formula 2,
m is an integer from 2,500 to 3,300,
l is an integer from 120 to 280,
R 1 is C 1 -4 alkoxy-carbonyl.
Wherein the heat-shrinkable film has a specific gravity of 1 g / cm 3 or less.
Wherein the heat shrinkable film exhibits a heat shrinkage ratio of 35 to 90% in a longitudinal direction or a width direction when the heat shrinkable film is heat-treated at a temperature of 90 DEG C for 10 seconds.
Wherein the heat shrink film has a first surface layer, a substrate layer, and a second surface layer in a thickness ratio of 1: 8 to 100: 1.
Wherein the heat shrink film is co-extruded with a first surface layer, a base layer and a second surface layer.
Wherein the first surface layer and the second surface layer each comprise a copolymerized polyester resin,
Said base layer comprising a copolymerized olefin resin,
Has a specific gravity of 1 g / cm < 3 &
Exhibits a heat shrinkage of 35 to 90% in the longitudinal direction or the width direction when heat-treated at a temperature of 90 DEG C for 10 seconds,
Wherein the first surface layer and the second surface layer each comprise 1 to 30 mol% of neopentyl glycol repeating units based on the total diol repeating units, 60 to 98 mol% of ethylene glycol repeating units and 0.5 to 10 mol% of diethylene glycol repeating units And a heat shrinkable film.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000148020A (en) * | 1998-11-05 | 2000-05-26 | Dainippon Printing Co Ltd | Heat shrinkable label |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000148020A (en) * | 1998-11-05 | 2000-05-26 | Dainippon Printing Co Ltd | Heat shrinkable label |
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