JPH07292132A - Low-temperature shrinkable film - Google Patents

Abstract

PURPOSE:To obtain the subject film, excellent in low shrinkability, strength after shrinking, etc., and useful for packaging materials, etc., by at least uniaxially stretching a resin comprising a specific rubber-modified styrenic resin composition and a block copolymer. CONSTITUTION:This film is obtained by at least uniaxially stretching a resin comprising (A) 99-91wt.% rubber-modified styrenic resin composition containing (i) a continuous phase comprising 100 pts.wt. rubber-modified styrenic resin containing 20-70wt.% constituent unit expressed by formula I (R1 is H or methyl; R2 is H or a 1-5C alkyl), 0.5-20wt.% constituent unit expressed by formula II (R3 is H or methyl; R4 is a 1-8C alkyl, with the proviso that R4 is a 2-8C alkyl when R3 is methyl) and 29.5-79.5wt.% constituent unit expressed by formula III and a dispersed phase containing 1-20wt.% rubber-like elastomer having 0.1-1.2mum dispersed particle diameter and (ii) 1-15 pts.wt. terpenic resin and (B) 1-9wt.% block copolymer containing a vinyl aromatic hydrocarbon and a conjugated diene at (20:80) to (80:20) weight ratio of the vinyl aromatic hydrocarbon to the conjugated diene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a rubber-modified styrene resin composition excellent in low-temperature shrinkability, waist hardness and the like, which is used for packaging materials, and is stretched at least uniaxially using a resin composed of a block copolymer. And a low temperature shrinkable film.

[0002]

2. Description of the Related Art A rigid PVC film is often used as a shrink wrapping material. However, in addition to the problems of hygiene and quality (whitening in water, etc.) due to the plasticizer contained in PVC, it also contains a large amount of chlorine, which causes pollution during disposal and incineration. Due to the above problems, alternative materials are required. As an alternative material, polystyrene and a styrene-butadiene block copolymer mixture are used, but low temperature shrinkability and poor strength after shrinkage are used as a packaging material only for very limited applications. The current situation.

A low-temperature shrinkable film using a special styrene resin and a styrene-butadiene block copolymer mixture has been proposed (Japanese Patent Laid-Open No. 61-25819), but the low-temperature shrinkability is improved, but the shrinkage is reduced. The strength afterwards is poor,
In addition, the gel-like substance caused by using a large amount of styrene-butadiene block copolymer has a bad influence on the appearance and printability of the film. I haven't arrived.

[0004]

Means for Solving the Problems The present inventor has made diligent studies in view of the present situation, and as a result, as a second and a third monomer copolymerizable with a styrene-based monomer, an acrylic ester (methacrylic ester) is used. ) System monomer, methyl methacrylate was introduced, the polymer composed of these monomers was used as the continuous phase, the rubber-like elastic body was used as the dispersed phase, and the particle size of the rubber-like elastic body of the dispersed phase was optimized. A rubber-modified styrene-based resin composition (I) comprising a rubber-modified styrene-based resin and a terpene-based resin, a polymer block mainly composed of at least one vinyl aromatic hydrocarbon polymer block and at least one conjugated diene A resin comprising a block copolymer (II) having a weight ratio of vinyl aromatic hydrocarbon and conjugated diene of 20:80 to 80:20, the rubber-modified styrene resin composition (I The ratio of the block copolymer (II) and the block copolymer (II) is (I) 99 to 91% by weight (II) 1 to 9% by weight, and a film stretched at least uniaxially has low-temperature shrinkability, strength after shrinkage, They have found that they have excellent appearance characteristics, printing characteristics, etc., and have completed the present invention.

That is, according to the present invention, in a rubber-modified styrene resin containing rubber-like elasticity as dispersed particles, (a) the continuous phase is represented by the following formula (A):

[0006]

[Chemical 4] (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms.) The following formula (B), and

[0007]

[Chemical 5] (In the formula, R ₃ is hydrogen or a methyl group, and R ₄ is an alkyl group having 1 to 8 carbon atoms. However, when R ₃ is a methyl group, R ₄ is an alkyl group having 2 to 8 carbon atoms. The following formula (C)

[0008]

[Chemical 6] The structural unit (A),
The ratio of (B) and (C) is (A): 20 to 70% by weight (B): 0.5 to 20% by weight (C): 29.5 to 79.5% by weight (however, (A) + (B) + (C) = 100% by weight),

(A) The dispersed particle diameter of the dispersed phase is 0.1 to 1.
2 μm, the content of the rubber-like elastic body is 1 to 20% by weight
The rubber-modified styrenic resin composition (I) consisting of 1 to 15 parts by weight of the terpene-based resin per 100 parts by weight of the rubber-modified styrenic resin, and at least one vinyl aromatic hydrocarbon polymer block and at least one conjugate. A resin comprising a block copolymer (II) having a diene-based polymer block and a vinyl aromatic hydrocarbon / conjugated diene weight ratio of 20:80 to 80:20, wherein the rubber is modified. At least uniaxially stretched low temperature shrinkability formed from a resin in which the proportion of the styrene resin composition (I) and the block copolymer (II) is (I) 99 to 91% by weight (II) 1 to 9% by weight It provides a film.

The present invention will be described in detail below. The amount of the structural unit (B) forming the continuous phase is in the range of 0.5 to 20% by weight. It is more preferably in the range of 2 to 17% by weight. When it exceeds 20% by weight, the heat resistance is lowered, and as a result, the film before shrinking causes natural shrinkage and cannot be used as a packaging material. On the other hand, if it is less than 0.5% by weight, the low temperature shrinkability is deteriorated. The amount of the structural unit (C) is 29.5.
It is in the range of 79.5% by weight. More preferably 30 to 7
It is 0% by weight. Outside of this range, the transparency of the rubber-modified styrenic resin decreases, which is not preferable. In the present invention,
The refractive index of the continuous phase is not particularly limited, but it is preferable from the viewpoint of transparency to control the difference between the refractive index of the rubber-like elastic body forming the dispersed phase and the refractive index within 0.01.

Since the amount of the structural unit (B) is determined by the resin physical property design value of the rubber-modified styrene resin, it is necessary to control the refractive index of the continuous phase with the structural units (A) and (C). . The degree of polymerization of the continuous phase of the rubber-modified styrene resin of the present invention is not particularly limited, but may be 25 ° C.
The viscosity of the 10 wt% toluene solution in 15 is in the range of 15 to 80 centipoise, more preferably 20.
It can be set in the range of centipoise to 70 centipoise. In the present invention, as the structural unit (A),
For example, the following structure can be mentioned.

[0012]

[Chemical 7] In the present invention, examples of the structural unit (B) include those having the following structures.

[0013]

[Chemical 8]

The dispersed phase of the present invention may be any as long as it exhibits rubbery properties at room temperature, and examples thereof include polybutadienes, styrene-butadiene copolymers, styrene-butadiene block copolymers and isoprene polymers. Etc. are used. More preferred are styrene-butadiene copolymers and styrene-butadiene block copolymers. Particularly, those having a styrene content of 10 to 50% by weight are preferable. Further, the molecular weight and branching of the rubber-like elastic body are not limited.

The particle size of the dispersed phase of the present invention is 0.1 to 1.2.
It must be in the μm range. More preferably,
It is 0.2 to 0.9 μm. When the dispersed particle size is less than 0.1 μm, the strength reinforcing effect is not exhibited or the strength reinforcing effect is very small. On the other hand, when the dispersed particle size exceeds 0.9 μm, the strength-reinforcing effect is great, but the transparency is poor. In particular, the haze after shrinkage becomes large, which is not preferable. Particle size referred to in the present invention means the number average particle size unless otherwise specified.

The particle size distribution state is not particularly limited, but the following two types are preferable. One is a distribution state in which the particle size distribution (weight average particle size / number average particle size) is 3.0 or less, and the other is a distribution state having a bimodal distribution. At this time, the distribution of each of the large and small particle diameters is preferably 3 or less, and the total average particle diameter is required to be in the range of 0.1 to 1.2 μm which is a constituent requirement of the present invention.

The amount of the rubber-like elastic material in the rubber-modified styrenic resin of the present invention is 1 to 20% by weight. Preferably 3 to
It is 15% by weight. When the amount of the rubber-like elastic body is less than 1% by weight, the strength reinforcing effect is not exhibited. On the other hand, if it exceeds 20% by weight, the transparency is lowered, and especially the cloudiness after shrinkage is increased, which is not preferable.

The terpene resin used in the present invention is a Friedel-Crafts type catalyst (d-limonene obtained from citrus cortex or dipentene obtained by isomerization of α-pinene obtained from raw pine resin and aromatic hydrocarbons). For example, it can be obtained by performing cationic polymerization using aluminum chloride, boron trifluoride, etc.). The resin obtained by hydrogenating this polymer is also the terpene resin in the present invention. There is no particular restriction on the hydrogenation rate. Styrene, α-methylstyrene, vinyltoluene and the like are preferably used as the aromatic hydrocarbon.

The degree of polymerization of the terpene resin is not particularly limited, but the degree of polymerization is 1000 or less, preferably 500 or less, more preferably 200 or less. When the degree of polymerization is high, the compatibility with the styrene resin is lowered and the plasticizing effect is lowered.
Further, the effect of preventing fogging after shrinking the film is reduced. Examples of the terpene resin include YS resin TO-125, TO-115, and TO-1 manufactured by Yasuhara Chemical Co., Ltd.
05, TO-85 and CLEARON M-115, M-10
5, P-85 and the like can be used.

The content of the terpene resin is 1 to 15 parts by weight per 100 parts by weight of the rubber-modified styrene resin. The terpene-based resin has a plasticizing effect, and has an effect as a viscosity modifier of the rubber-modified styrene-based resin at the time of film formation,
In addition, when the film is shrunk, it has an effect of suppressing fogging. When the amount of the rubber-like elastic material in the rubber-modified styrenic resin is small, the content of the terpene-based resin may be small because the film after shrinkage is less cloudy. It is desirable to determine the addition amount of the terpene-based resin according to the amount of the rubber-like elastic body. Addition amount of terpene resin is 1
If it exceeds 5% by weight, the effect of suppressing fogging is saturated, and
It reduces the rigidity of the film.

The rubber-modified styrenic resin composition of the present invention contains an organic polysiloxane such as polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, and an epoxy group or a hydroxyl group at the terminal or molecular chain of these polymers. What introduced the carboxyl group, the vinyl group, the amino group, the alkoxy group, etc. can be added. Content is rubber-modified styrene resin composition 10
0.002-0.3 parts by weight per 0 parts by weight is a preferred amount used.

To obtain the styrenic resin of the present invention, a method frequently used in the production of rubber-reinforced polystyrene (HIPS resin) can be used. That is, the rubber-like elastic material is prepared from a styrene monomer and / or an acrylic acid ester (methacrylic acid ester) monomer and / or methyl methacrylate and / or a polymerization solvent and / or a polymerization initiator and / or a polymerization degree adjusting agent. The raw material solution in which the rubber-like elastic material is dissolved is supplied to a reactor equipped with a stirrer for polymerization. The particle size of the dispersed particles is controlled by a generally used method, by changing the stirring number of stirring blades. In addition, as a method for maintaining transparency, a general method, for example, a method of adding a monomer as needed during the polymerization or a method of continuously additional addition is used.

The content of the rubber-like elastic material can be achieved by adjusting the raw materials and the polymerization rate so that the target content is obtained. In addition, a rubber-modified styrene resin containing a high concentration of a rubber-like elastic material is produced by the above method, and the separately prepared rubber-like elastic material is not contained or mixed with a styrene-based polymer having a low rubber-like elastic material content. It can also be achieved by doing. However, it is a matter of course that all the constituent requirements of the invention are satisfied.

At this time, a polymerization solvent such as ethylbenzene, toluene or xylene can be used.
In addition, an organic peroxide that is commonly used in the polymerization of polystyrene may be used or may be added during the process. As the polymerization method, a bulk polymerization method or a solution polymerization, which is commonly used in the polystyrene production method, is used. Either a batch polymerization method or a continuous polymerization method can be used.

The styrenic monomer of the present invention includes styrene, α-methylstyrene, pt-butylstyrene,
p-Methylstyrene or the like can be used. These styrene-based monomers may be used alone or in combination. As an acrylic acid ester (methacrylic acid ester) monomer,
Butyl acrylate, butyl methacrylate, ethyl acrylate and the like can be used. These acrylic acid ester (methacrylic acid ester) monomers can be used alone or in combination.

The particle size of the dispersed particles is controlled by a generally used method, by changing the number of stirring of the stirring blades. In addition, as a method for maintaining transparency, a general method, for example, a method of adding a monomer as needed during the polymerization or a method of continuously additional addition is used. The polymerization solution discharged from the reactor is introduced into a recovery system, where unreacted monomers, polymerization solvent, etc. are removed and pelletized.

The terpene resin used in the present invention is dissolved in a raw material solution in which a rubbery polymer is dissolved, or
During the polymerization, it is added in the molten state under heating or dissolved in a solvent, or after leaving the recovery system, it is added in the molten state under heating, or a rubber-modified styrene resin and a terpene resin are blended and extruded. It can be added by a method of melt-kneading with a machine. Alternatively, the rubber-modified styrene resin and the terpene resin may be mixed and mixed at the time of film formation.

Additives that are commonly used in styrenic resins, such as antistatic agents, antioxidants, lubricants, plasticizers, coloring agents, at any stage before or after recovering the unreacted monomer and / or the polymerization solvent. Agents and the like can be added.

The block copolymer (II) of the present invention is a block copolymer having at least one vinyl aromatic hydrocarbon polymer block and at least one polymer block mainly containing a conjugated diene. is there. here,
The polymer block mainly containing a conjugated diene is a polymer block having a conjugated diene content of 50% by weight or more, preferably 70% by weight or more, and more preferably 90% by weight or more. The vinyl aromatic hydrocarbon copolymerized in the polymer block mainly composed of the conjugated diene may be uniformly distributed in the polymer or may be distributed in a taper shape.

The weight ratio of vinyl aromatic hydrocarbon to conjugated diene in the block copolymer is 30:70 to 55:45,
It is preferably 35:65 to 50:50. When the content of the vinyl aromatic hydrocarbon is less than 30% by weight, the transparency is significantly lowered when mixed with the rubber-modified styrene resin composition. On the other hand, if it exceeds 55% by weight, the strength of the sheet mixed with the rubber-modified styrene-based resin composition, especially the folding endurance strength is low, and the transparency is lowered, which is not preferable.

The block copolymer used in the present invention is a linear block copolymer (AB) _n A (BA) _n B (AB) _n (A is vinyl) represented by the following general structural formula. Aromatic hydrocarbon polymer block, B
Is a polymer block mainly composed of a conjugated diene. The boundary between the A block and the B block does not necessarily have to be clearly distinguished. ) Alternatively, it is a radial block copolymer represented by the following general formula. {(BA) _n } _{m + 2} X {(AB) _n } _{m + 2} X {(BA) _n } _{m + 2} X (A and B are the same as above, and X is, for example, It represents a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride or an initiator residue such as a polyfunctional organolithium compound.) In the general formulas, n is 1 to 4 and m is 1 to 3. .

In the block copolymer used in the present invention, the vinyl aromatic hydrocarbon polymer block has a number average molecular weight of 10,000 to 70,000, preferably 15,000.
It is 60,000. The number average molecular weight of the polymer block containing a conjugated diene as a main component is not particularly limited, but is 500 to 200.
000, preferably 1,000 to 100,000.

The block copolymer used in the present invention can basically be produced by a conventionally known method.
-19286, Japanese Patent Publication No. 43-14979,
The methods described in JP-B-48-2423, JP-B-48-4106, JP-B-49-36957 and the like can be mentioned.

In the present invention, styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, α-methylstyrene and the like can be used as the vinyl aromatic hydrocarbon. You may use these individually or in mixture of 2 or more types. Particularly popular is styrene.

The conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene; 2-methyl-1,3-butadiene (isoprene); 2,3-dimethyl. -1,3-butadiene; 1,3
-Pentadiene; 1,3-hexadiene and the like can be used. You may use these individually or in mixture of 2 or more types. Particularly common are 1,3-butadiene,
Examples include isoprene.

The base resin of the film of the present invention is obtained by mixing the rubber-modified styrene resin composition (I) and the block copolymer (II). The amount of the block copolymer in the base resin is 1 to 9% by weight, preferably 1 to 8% by weight, more preferably 1 to 7% by weight. When the amount of the block copolymer is less than 1% by weight, the effect of strengthening the strength, particularly the strength after shrinkage is not exhibited, which is not preferable. If it exceeds 9% by weight, the rigidity of the film decreases. In addition, gel-like substances caused by the block copolymer are frequently generated to deteriorate the film appearance.

The base resin of the film of the present invention is obtained by mixing the rubber-modified styrene resin composition (I) and the block copolymer (II). The mixing method is a known method, for example, an extruder, It is possible to use a method such as mixing with a calender roll, a Banbury mixer or the like, or a method of melt kneading at the stage of forming a film.

In order to prepare the uniaxially stretched film according to the present invention, the above-mentioned base resin may be melt-extruded and then T-die, circular die or the like, or in the case of a batch method, a compression molding method or the like may be used, preferably. It is extruded continuously with a circular die or the like to prepare a rapidly cooled raw material, which is reheated and continuously stretched by the bubble method or the tenter method. The stretching ratio at this time is 3 to 15 times, preferably 3 to 7 times. The stretching temperature is 110 to 50 ° C, preferably 100 to 6
It is 0 ° C. In the case of stretching such as a tenter, this temperature represents an average temperature at a place where the deformation between the starting point and the ending point of stretching is largely performed.

[0039]

EXAMPLES Examples will be described in detail below, but the invention is not limited thereto.

(Rubber-modified styrene-based resin composition 1) A rubber-modified styrene-based resin was prepared by using a polymerization apparatus in which two reactors equipped with a stirrer were connected in series and then an extruder with a two-stage vent was arranged. To manufacture. Styrene 47.5 parts by weight, butyl acrylate 10.0 parts by weight, methyl methacrylate 33.2 parts by weight, rubber type elastic body of B-S type (B: butadiene block, S: styrene block) and styrene content of 38 parts by weight. % Rubber-like elastic body 6.5
Parts by weight, 2.8 parts by weight of ethylbenzene, 1,1 bis (t
A raw material solution consisting of 0.01 part by weight of -butylperoxy) cyclohexane is supplied to the reactor to carry out polymerization. 100 parts by weight of the obtained rubber-modified styrene resin and 5 parts by weight of a terpene resin (Clearon M115) are blended and granulated with a single-screw extruder. Table 1 shows the physical properties of the obtained rubber-modified styrene resin composition.

(Rubber-modified styrene-based resin composition 2) A rubber-modified styrene-based resin composition 2 is obtained in the same manner as the rubber-modified styrene-based resin composition 1 except that the terpene-based resin is not added. The physical properties are shown in Table 1. (Rubber-modified styrene-based resin composition 3) A rubber-modified styrene-based resin composition 3 is obtained in the same manner as the rubber-modified styrene-based resin composition 1 except that the amount of the terpene-based resin added is 10 parts by weight. The physical properties are shown in Table 1.

(Rubber-modified styrene resin composition 4, 5,
6, 7) The rubber-modified styrene resin composition 4, 5, 6, 7 is obtained in the same manner as the rubber-modified styrene resin composition 1 except that the number of agitators in the reactor is changed. However, the amount of the terpene-based resin added to the rubber-modified styrene-based resin composition 7 is 10
Parts by weight. The physical properties are shown in Table 1.

(Rubber-modified styrene resin composition 8) 50.8 parts by weight of styrene, 10.7 parts by weight of butyl acrylate, 35.5 parts by weight of methyl methacrylate, 3.0 parts by weight of ethylbenzene, 1,1 bis (t- (Butylperoxy) cyclohexane 0.01 parts by weight of the raw material solution is supplied, and the rubber-modified styrene-based resin composition 8 is obtained in the same manner as the rubber-modified styrene-based resin composition 1 except that the terpene-based resin is not added. . The physical properties are shown in Table 1.

(Rubber-modified styrene resin composition 9) 75.3 parts by weight of styrene, 12.6 parts by weight of butyl acrylate, 6.5 parts by weight of rubber-like elastic material used in the rubber-modified styrene resin composition 1, ethylbenzene 5.6 parts by weight, 1,
1 bis (t-butylperoxy) cyclohexane 0.0
Rubber-modified styrene resin composition 3 other than 1 part by weight
A rubber-modified styrene resin composition 9 is obtained in the same manner as in. The physical properties are shown in Table 1.

(Rubber-modified styrenic resin composition 10) Other than styrene 53.3 parts by weight, butyl acrylate 0.0 parts by weight and methyl methacrylate 37.4 parts by weight,
A rubber-modified styrene-based resin composition 10 is obtained in the same manner as the rubber-modified styrene-based resin composition 9. The physical properties are shown in Table 1.

(Block Copolymers 1 to 4) Styrene-butadiene block copolymers having polymer structures and styrene contents shown in Table 2 are polymerized using n-butyllithium as a catalyst.

Examples 1 to 7 and Comparative Examples 1 to 9 The rubber-modified styrenic resin composition and the block copolymer were pellet-blended in the proportions shown in Table 3, and then T
A 250 μm original fabric is prepared from the die. Other than Comparative Example 9, the temperature was 80 ° C. in Comparative Example 9, and the comparative example 9 was stretched at a temperature of 100 ° C. by a tenter at a low temperature in a uniaxial transverse direction to obtain a stretched film of about 40 μm.

The physical properties are shown in Tables 4-1 and 4-2. Here, the tensile rupture strength and elongation are measured according to ASTM D 882-67, and the values in the stretching direction are shown. The tensile modulus is measured according to ASTM D 882-67. Two
Measured by converting the value in% elongation to 100%. HA
The ZE value is measured according to ASTM D 1003-52. The 80 ° C. shrinkage percentage is the percentage (%) of the value obtained by dividing the length shrunk by the linear shrinkage percentage after heating in hot air for 5 minutes by the original dimension;
In this case, the stretching direction. The shrinkage stress is represented by the peak value of the curve obtained by plotting the stress value after 10 seconds measured in a silicon bath at each temperature on a graph.

The cracking property after packaging is the presence or absence of cracking in the neck and body of the sample (n = 5) after packaging which was left outdoors in direct sunlight. In this case, ⊚: 2 weeks Even after that, no occurrence was observed in any part. Δ: One spot was observed on the neck or body of n = 1 to 3 within 2 weeks. ×: Two or three spots were observed in the neck or body of n = 1 to 4 within 2 weeks.

Regarding the tear strength, whether or not to use can be determined by observing the state of tearing when a shrink film is attached to a glass bottle and rubbed together. ◎: Level that can withstand actual use △: Level that is difficult to withstand actual use Judgment of the film appearance is based on the amount of gel-like substances present, and whether there is a problem with aesthetics or printing characteristics. ◎: Level that can withstand actual use ×: Level that cannot withstand actual use

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

The uniaxially stretched low temperature shrinkable film obtained from the rubber-modified styrenic resin composition and the block copolymer of the present invention can be molded at a low temperature and has excellent strength, transparency and appearance characteristics. It can be understood.

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Claims (1)

[Claims] 1. A rubber-modified styrenic resin containing a rubber-like elastic material as dispersed particles, wherein (a) the continuous phase is represented by the following formula (A): (In the formula, R ₁ is hydrogen or a methyl group, and R ₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms.) The following formula (B), and (In the formula, R ₃ is hydrogen or a methyl group, and R ₄ is an alkyl group having 1 to 8 carbon atoms. However, when R ₃ is a methyl group, R ₄ is an alkyl group having 2 to 8 carbon atoms. The following formula (C): The structural unit (A),
The ratio of (B) and (C) is (A): 20 to 70% by weight (B): 0.5 to 20% by weight (C): 29.5 to 79.5% by weight (however, (A) + (B) + (C) = 100% by weight), (a) the dispersed particle diameter of the dispersed phase is 0.1 to 1.2 μm, and the content of the rubber-like elastic body is 1 to 20% by weight. A rubber-modified styrene resin composition (I) comprising 1 to 15 parts by weight of a terpene resin per 100 parts by weight of a rubber-modified styrene resin, at least one vinyl aromatic hydrocarbon polymer block and at least one conjugated diene. A resin comprising a block copolymer (II) having a main polymer block and a weight ratio of vinyl aromatic hydrocarbon and conjugated diene of 20:80 to 80:20, wherein the resin is a rubber-modified styrene-based resin. The ratio of the resin composition (I) and the block copolymer (II) is (I) 99 to 91% by weight (II) At least uniaxially stretched low temperature shrinkable film made of 1 to 9% by weight resin.