JP5295068B2 - Heat shrinkable laminated film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-shrinkable laminated film which is excellent in low temperature shrinkage characteristics, rigidity, transparency and peeling strength. <P>SOLUTION: Disclosed is the heat-shrinkable laminated film which comprises at least three layers including an intermediate layer, a surface layer and a back layer and is oriented at least in one axial direction and has a heat shrinkage rate of 30% or more in the main shrinking direction in hot water of 80&deg;C for 10 seconds, wherein the surface layer and back layer comprises at least one kind of polyester resin, and in the intermediate layer, a copolymer (2) of a monomer having an acid anhydride and/or a carboxylic group having reactivity with the primary modified block copolymer or a functional group of the hydrogenated matter (1) thereof, and the vinyl aromatic hydrocarbon is coupled to a primary modified block copolymer or a hydrogenated matter (1) thereof, formed by an addition reaction of a block copolymer comprising at least one polymer block A having vinyl aromatic hydrocarbon as a principal component and at least one polymer block B having conjugated diene as a principal component, with a functional group-containing modifier. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a heat-shrinkable laminated film.

A block copolymer consisting of a vinyl aromatic hydrocarbon and a conjugated diene, which has a relatively high vinyl aromatic hydrocarbon content, uses properties such as transparency and impact resistance, It is used for extrusion molding applications such as films.
In particular, heat-shrinkable films using block copolymer resins composed of vinyl aromatic hydrocarbons and conjugated dienes have problems with residual monomers in vinyl chloride resins used in the past, residual plasticizers, and chlorination during incineration. Since there is no problem of hydrogen generation, it is used for food packaging, cap seals, labels, and the like.

As heat-shrinkable films for shrinkable labels, polyester-based heat-shrinkable films are mainly used.
Polyester-based heat-shrinkable films are excellent in low-temperature shrinkability, have a low natural shrinkage rate, and have a good rigidity. However, they have drawbacks in shrinkage finishing properties such as shrinkage unevenness.

  Conventionally, various studies have been made to obtain a heat-shrinkable film satisfying properties such as natural shrinkage, low-temperature shrinkage, transparency, mechanical strength, and packaging machine suitability.

Patent Document 1 proposes a laminated film of three types and five layers in which an outermost layer made of a polyester resin is laminated on an intermediate layer made of a polystyrene resin.
Patent Documents 2 and 3 propose laminated films using a polystyrene resin as an intermediate layer and a polyester resin containing 1,4-cyclohexanedimethanol as an outer layer.

Patent Document 4 discloses a specific conjugated diene monomer and vinyl as a film made of a hydrogenated copolymer that is rich in flexibility, excellent in resilience and scratch resistance, and easy to handle (blocking resistance). Disclosed is a film comprising a hydrogenated copolymer having a weight ratio to an aromatic hydrocarbon monomer, an amount of a vinyl aromatic hydrocarbon monomer polymer block, and no crystallization of a DSC chart in a specific temperature range Has been.
In Patent Document 5, as a heat-shrinkable laminated film excellent in breakability, transparency and recyclability, the front and back layers are made of a polyester resin, and the intermediate layer is made of a block copolymer of a styrene hydrocarbon and a conjugated diene hydrocarbon. A film is disclosed.

JP 61-41543 A JP-A-7-137212 JP 2002-351332 A International Publication No. 03/035705 JP-A-2005-131824

  However, the conventional heat-shrinkable films as described above still have room for improvement in low-temperature shrinkage, rigidity, transparency, and peel strength. It does not have sufficient characteristics as a heat-shrinkable laminated film used in the above.

  Therefore, an object of the present invention is to provide a heat-shrinkable laminated film that is excellent in low-temperature shrinkage, rigidity, transparency, and peel strength, and is suitable for shrink wrapping, shrink-bound wrapping, shrinkable labels, and the like.

As a result of intensive studies in order to solve the problems of the prior art related to the heat-shrinkable film as described above, the present inventors use a specific modified block copolymer as an intermediate layer of a film composed of at least three layers. In addition, the present inventors have found that a heat-shrinkable laminated film using a polyester resin as layers on both sides of the intermediate layer can achieve the above object, and has completed the present invention.
That is, the present invention is as follows.

[1]
The middle layer,
Consists of at least three layers including a surface layer and a back layer respectively laminated on both sides of the intermediate layer,
Stretched in at least uniaxial direction,
A heat-shrinkable laminated film having a heat shrinkage rate of 30% or more in 10 seconds in 80 ° C. warm water in the main shrinkage direction,
The front layer and the back layer include at least one polyester resin,
The intermediate layer is
Addition reaction of functional group-containing modifier to block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene An acid anhydride having reactivity with a functional group of the primary modified block copolymer or the hydrogenated product (1) and / or a hydrogenated product (1) thereof, and / or a hydrogenated product (1) thereof. A copolymer (2) of a monomer having a carboxyl group and a vinyl aromatic hydrocarbon,
Bound seen contains the modified block copolymer has,
The functional group-containing modifier is
By the addition reaction with the block copolymer, the primary modified block copolymer or the hydrogenated product (1) thereof,
Having a function of generating an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group;
Heat shrinkable laminated film.

[2]
The heat-shrinkable laminated film according to [1] , wherein the copolymer (2) is a styrene-maleic anhydride copolymer or a copolymer in which a part thereof is a carboxyl group.

[3]
The intermediate layer is
The heat according to [1] or [2] , further containing 0.1 to 80% by mass of at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c): Shrinkable laminated film.
(A) Styrene polymer (b) At least one aliphatic selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with unsaturated carboxylic acid or derivative thereof (c) Rubber-modified styrene polymer

[4]
The polyester resin is composed of a dicarboxylic acid component and a diol component,
The dicarboxylic acid component and the diol component each include a main component in an amount of 60 to 100 mol% with respect to the total amount (100 mol% of each),
The total amount of other components is 10 to 40 mol% with respect to the total (200 mol%) of the total amount (100 mol%) of the dicarboxylic acid component and the total amount (100 mol%) of the diol component [ [ 1] The heat-shrinkable laminated film according to any one of [3] .

[5]
The main component of the dicarboxylic acid is terephthalic acid,
The main component of the diol component is ethylene glycol,
The heat-shrinkable laminated film according to [4] , wherein the other component is 1,4-cyclohexanedimethanol.

[6]
The amount of 1,4-cyclohexanedimethanol is
Total amount of dicarboxylic acid component (100 mol%) and total amount of diol component (100 mol%)
The heat-shrinkable laminated film according to [4] or [5] , which is in the range of 10 to 40 mol% with respect to the total (200 mol%).

[7]
The heat-shrinkable laminated film according to any one of [1] to [6] , wherein the intermediate layer contains 3 to 30% by mass of the polyester resin based on the total weight of the resin constituting the intermediate layer.

[8]
The heat-shrinkable laminated film according to any one of [1] to [7] , wherein a haze value measured in accordance with ASTM D1003 is 10% or less.

[9]
[1] to [1], wherein the heat shrinkage rate in the main shrinkage direction in 10 seconds in 70 ° C. warm water is 5% or more.
[8] The heat-shrinkable laminated film according to any one of [8] .

[10]
The production of the heat-shrinkable laminated film according to any one of [1] to [9] , comprising at least three layers, comprising an intermediate layer and a front layer and a back layer, which are respectively laminated on both sides of the intermediate layer. A method,
At least one polymer block A mainly composed of vinyl aromatic hydrocarbons;
A primary modified block copolymer obtained by addition-reacting a functional group-containing modifier to a block copolymer comprising at least one polymer block B mainly comprising a conjugated diene, or a hydrogenated product (1) thereof. A manufacturing process;
An acid anhydride and / or a carboxyl group having reactivity with the functional group of the primary modified block copolymer or hydrogenated product (1) is added to the primary modified block copolymer or hydrogenated product (1) thereof. A step of producing a modified block copolymer by bonding a copolymer (2) of a monomer having a vinyl aromatic hydrocarbon,
Forming the intermediate layer using the modified block copolymer, and forming the surface layer and the back layer using at least one polyester resin;
I have a,
The functional group-containing modifier is
By the addition reaction with the block copolymer, the primary modified block copolymer or the hydrogenated product (1) thereof,
Having a function of generating an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group;
A method for producing a heat-shrinkable laminated film.

  According to the present invention, it is possible to obtain a heat-shrinkable laminated film that is excellent in low-temperature shrinkage, rigidity, and transparency and hardly peels off due to external stress.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described.
The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

[Heat-shrinkable laminated film]
The heat-shrinkable laminated film of this embodiment is
It consists of at least three layers including an intermediate layer and a front layer and a back layer, which are respectively laminated on both sides of the intermediate layer.
The heat-shrinkable laminated film of the present embodiment is stretched at least in the uniaxial direction, and the heat shrinkage rate in 10 seconds in 80 ° C. warm water in the main shrinkage direction is 30% or more.
The surface layer and the back layer contain at least one polyester resin.
The intermediate layer contains a predetermined modified block copolymer.
The “main shrinkage direction” refers to the larger direction of the shrinkage ratio among the transverse direction and the longitudinal direction of the heat-shrinkable laminated film. Here, the horizontal direction generally refers to the film flow direction (extrusion direction), and the vertical direction refers to a direction orthogonal to the horizontal direction.
The heat-shrinkable laminated film of the present embodiment is excellent in low-temperature shrinkage, rigidity, and transparency, and particularly has a characteristic that peeling due to external stress hardly occurs because the peeling strength between the intermediate layer and the front and back layers of the film is large.

(Modified block copolymer)
The intermediate layer constituting the heat-shrinkable laminated film of this embodiment contains a predetermined modified block copolymer.
The modified block copolymer is
At least one polymer block A mainly composed of vinyl aromatic hydrocarbons;
A primary modified block copolymer obtained by addition-reacting a functional group-containing modifier to a block copolymer comprising at least one polymer block B mainly comprising a conjugated diene, or a hydrogenated product thereof (1) But,
A copolymer of an acid anhydride and / or a carboxyl group-reactive monomer having a reactivity with the functional group of the primary modified block copolymer or hydrogenated product (1) thereof and a vinyl aromatic hydrocarbon (2 ) Modified block copolymer.

<Primary modified block copolymer or hydrogenated product thereof (1)>
First, a functional group-containing modifier is added to a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene. The primary modified block copolymer obtained by addition reaction or the hydrogenated product (1) thereof will be described.
The polymer block A mainly composed of vinyl aromatic hydrocarbon is a copolymer block of vinyl aromatic hydrocarbon and conjugated diene containing vinyl aromatic hydrocarbon at 50% by mass or more, or vinyl aromatic hydrocarbon alone It shall indicate a polymer block.
The polymer block B mainly composed of conjugated diene is a copolymer block of conjugated diene and vinyl aromatic hydrocarbon or conjugated diene homopolymer block containing conjugated diene in an amount of more than 50% by mass. Shall.

When a random copolymer portion of vinyl aromatic hydrocarbon and conjugated diene is present in polymer block A mainly composed of vinyl aromatic hydrocarbon or polymer block B mainly composed of conjugated diene, copolymerization The vinyl aromatic hydrocarbons may be distributed uniformly in the polymer block A or B, or may be distributed in a taper (gradual decrease).
In addition, the random copolymer portion of the vinyl aromatic hydrocarbon and the conjugated diene includes a portion where the vinyl aromatic hydrocarbon is uniformly distributed and / or a portion where the portion is distributed in a tapered shape. Also good.

  Further, when the above-mentioned primary modified block copolymer or hydrogenated product (1) thereof has a plurality of polymer blocks A (and / or B), they are molecular weight, composition, type. Etc. may be different from each other.

A block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene is basically known in the art. It can be synthesized by the method.
For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17879, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 57-49567, Japanese Patent Publication No. 58-11446, etc. Can be synthesized by a block copolymerization method of a conjugated diene and a vinyl aromatic hydrocarbon using an anionic initiator such as an organolithium compound in a hydrocarbon solvent.
In the present embodiment, the production conditions for each constituent polymer are set as described later.

Examples of the polymer structure of a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene include the following: Examples thereof include linear block copolymers such as (a) to (c).
A- (BA) _n (a)
A- (BA) _n -B (b)
B- (A-B) _{n + 1} (c)
Here, A is a polymer block mainly composed of vinyl aromatic hydrocarbons, and B is a polymer block mainly composed of conjugated dienes.
The boundary between the A block and the B block does not necessarily have to be clearly distinguished.
n is an integer greater than or equal to 1, and is generally 1-5.

The polymer structure of the block copolymer comprising at least one polymer block A mainly composed of the vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of the conjugated diene has the above-mentioned line structure. In addition to the block copolymer, the following structures (d) to (g) are also exemplified.
[(A−B) _k ] _m −X (d)
[(A−B) _k −A] _m −X (e)
[(BA) _k ] _m -X (f)
[(B−A) _k −B] _m −X (g)
Here, A and B are the same as the above formulas (a) to (c), and k and m are integers of 1 or more, generally 1 to 5.
X represents, for example, a residue of a coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound. As the block copolymer, a radial block copolymer, Alternatively, a mixture of any polymer structure of these block copolymers can be used.

Examples of the vinyl aromatic hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene etc. are mentioned, Styrene is especially preferable. These may use only 1 type and may mix and use 2 or more types.
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- Examples thereof include butadiene, 1,3-pentadiene, 1,3-hexadiene, and 1,3-butadiene and isoprene are particularly preferable. These may use only 1 type and may mix and use 2 or more types.

When 1,3-butadiene and isoprene are used in combination, isoprene is preferably 10% by mass or more, more preferably 25% by mass or more based on the total mass of 1,3-butadiene and isoprene. More preferably, it is 40 mass% or more.
When the isoprene content is 10% by mass or more, the modified block constituting the intermediate layer has a good balance between appearance characteristics and mechanical strength because thermal decomposition does not occur during molding at high temperature and the molecular weight does not decrease. A polymer and its composition are obtained.

In the step of synthesizing a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene, Use solvent.
Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; benzene, Aromatic hydrocarbons such as toluene, ethylbenzene and xylene can be used.
These may use only 1 type and may mix and use 2 or more types.

In the step of synthesizing a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene, anion initiation Use the agent.
As the anion initiator, for example, an organic lithium compound can be used, and an organic monolithium compound, an organic dilithium compound, an organic polylithium compound, or the like in which one or more lithium atoms are bonded in the molecule can be applied.
Specific examples include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl dilithium, and isoprenyl dilithium. .
These may use only 1 type and may mix and use 2 or more types.

In the step of synthesizing a block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene, a polymerization rate is obtained. Polar compounds and randomizing agents are used for the purpose of adjusting the microstructure of the polymerized conjugated diene moiety (cis, trans, vinyl ratio), adjusting the reaction ratio of conjugated diene and vinyl aromatic hydrocarbon, etc. can do.
Examples of polar compounds and randomizing agents include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol dibutyl ether; amines such as triethylamine and tetramethylethylenediamine; thioethers; phosphines; phosphoramides; alkylbenzene sulfonates; Examples thereof include sodium alkoxide.

  The polymerization temperature condition of the block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene is generally as follows: Is in the range of -10 ° C to 150 ° C, preferably in the range of 40 ° C to 120 ° C.

The time required for polymerization varies depending on the conditions, but in general, it can be carried out within 48 hours, and can be carried out in 1 to 10 hours by selecting particularly good conditions.
Moreover, it is preferable that the atmosphere of the system at the time of polymerization is in a state where it is substituted with an inert gas such as nitrogen gas.
The pressure at the time of carrying out the polymerization is not particularly limited as long as it is in a range sufficient to maintain the monomer and solvent in the liquid layer within the above polymerization temperature range.
Furthermore, it is necessary to take care not to mix impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, into the polymerization system.

Content of vinyl aromatic hydrocarbon in block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of conjugated diene Is preferably in the range of 30 to 95% by mass, more preferably in the range of 40 to 95% by mass, and still more preferably in the range of 50 to 95% by mass.
When the vinyl aromatic hydrocarbon content in the block copolymer is in the range of 30 to 95% by mass, the composition constituting the intermediate layer is excellent in balance between elongation and rigidity and excellent in transparency. Is obtained.

A vinyl aromatic incorporated in a block copolymer comprising at least one polymer block A mainly composed of the vinyl aromatic hydrocarbon and at least one polymer block B mainly composed of a conjugated diene. The block ratio of the hydrocarbon polymer block is preferably 10 to 98% by mass, more preferably 15 to 95% by mass, and still more preferably 20 to 90% by mass.
When the block ratio is in the range of 10 to 98% by mass, the balance between rigidity and elongation of the heat-shrinkable laminated film of this embodiment is excellent.
The block ratio of the vinyl aromatic hydrocarbon block is such that at least a part of the vinyl aromatic hydrocarbon and the conjugated diene are copolymerized at the time of production of the block copolymer. It can be controlled by adjusting the weight, the weight ratio thereof, the polymerization reactivity ratio, and the like.
Specifically, (a) a mixture of vinyl aromatic hydrocarbon and conjugated diene is continuously supplied to the polymerization system for polymerization, and / or (b) a polar compound or a randomizing agent is used. And a method of copolymerizing a vinyl aromatic hydrocarbon and a conjugated diene.

  Examples of the polar compound or randomizing agent include ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; amines such as triethylamine and tetramethylethylenediamine; thioethers; phosphines; phosphoramides; alkylbenzene sulfonates; And sodium alkoxide.

  The block ratio of the aromatic hydrocarbon polymer block is determined by a method of oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)], and the vinyl aromatic hydrocarbon polymer block component (excluding vinyl aromatic hydrocarbon polymer components having an average degree of polymerization of about 30 or less) was determined. Furthermore, it is computable using the following formula.

The number average molecular weight (Mn) of the vinyl aromatic hydrocarbon polymer block in the block copolymer is preferably in the range of from 50,000 to 150,000, and more preferably in the range of from 7,000 to 120,000.
When the (Mn) is from 50,000 to 150,000, excellent rigidity and elongation can be obtained, and molding processability and transparency can be improved.
The above (Mn) of the vinyl aromatic hydrocarbon polymer block is a method of oxidizing and decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1, 429 (1946)] can be obtained by analyzing the vinyl aromatic hydrocarbon polymer block component by gel permeation chromatography (GPC).
That is, GPC measurement of monodisperse polystyrene for GPC is performed, a calibration curve between the peak count number and the molecular weight of the monodisperse polystyrene is prepared, and can be calculated according to a conventional method (for example, “Gel Chromatography <Basics> Issued by Kodansha”). .

  Next, a hydrogenated product of the block copolymer comprising at least one polymer block A mainly composed of vinyl aromatic hydrocarbons and at least one polymer block B mainly composed of conjugated diene ( Hereinafter, this is simply referred to as a hydrogenated product of a block copolymer.

The hydrogenated block copolymer is obtained by hydrogenating the block copolymer obtained above.
The hydrogenation catalyst for hydrogenation is not particularly limited, and conventionally known catalysts such as (1) metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like. Supported so-called heterogeneous hydrogenation catalyst, (2) so-called Ziegler-type hydrogenation using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum Catalysts and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh and Zr can be applied.

  Specifically, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041 Can be applied.

Preferable examples of the hydrogenation catalyst include a mixture of a titanocene compound and a reducing organometallic compound.
As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The temperature condition for carrying out the hydrogenation reaction on the block copolymer is preferably in the range of 0 to 200 ° C, more preferably in the range of 30 to 150 ° C.
The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and further preferably 0.3 to 5 MPa.
The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
The hydrogenation reaction can be performed by a batch process or a continuous process, and these may be performed alone or in combination.

In the hydrogenated block copolymer, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound is not particularly limited.
In the hydrogenated block copolymer, 70% or more, preferably 80% or more, more preferably 90% or more of the unsaturated double bond based on the conjugated diene compound may be hydrogenated, or only a part thereof. May be hydrogenated.
When only a part is hydrogenated, the hydrogenation rate is preferably 10% or more and less than 70%, more preferably 15% or more and less than 65%, and more preferably 20% or more and less than 60%. Further preferred.

Furthermore, in the hydrogenated block copolymer, the hydrogenation rate of the vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and 95%. More preferably, the above is used. This improves the thermal stability of the hydrogenated product of the block copolymer.
In addition, the hydrogenation rate of the said vinyl bond means the ratio of the vinyl bond hydrogenated among the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the block copolymer.
Further, the hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less. More preferably, it is 20% or less.
The hydrogenation rate and the vinyl bond amount based on the conjugated diene compound can be measured by a nuclear magnetic resonance apparatus (NMR).

The primary modified block copolymer or hydrogenated product (1) thereof can be obtained by subjecting the above-mentioned block copolymer or hydrogenated product to an addition reaction with a functional group-containing modifier.
The primary modified block copolymer or hydrogenated product (1) is obtained by adding a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride to the block copolymer or the hydrogenated product thereof. Group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile Group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silanol group, alkoxysilane, halogenated silicon group, halogenated tin group, alkoxytin group, phenyltin group, etc. A functional group is attached.

As a method for obtaining such a block copolymer to which a functional group is bonded or a hydrogenated product thereof, at least one functional group selected from the living terminal of the block copolymer or the hydrogenated product and the functional group is used. A method of performing an addition reaction with a functional group-containing modifier that generates the primary modified block copolymer to which the atomic group is bonded, or a function to which an atomic group in which the functional group is protected by a known method is bonded An example is a method in which a group-containing modifier is subjected to an addition reaction.
Further, an organic alkali metal compound such as an organic lithium compound is reacted (metalation reaction) with the block copolymer or a hydrogenated product thereof, and the organic alkali metal is added to the block copolymer or the hydrogenated product thereof. A method of adding the functional group-containing modifier to the polymer may be mentioned.

  Depending on the type of functional group-containing modifier, the hydroxyl group or amino group may be an organometallic salt at the stage of reaction. In such a case, treatment with a compound having active hydrogen such as water or alcohol By doing so, a hydroxyl group, an amino group, or the like can be obtained.

When the functional group-containing modifier is reacted with the living end of the block copolymer or its hydrogenated product, the partially unmodified block copolymer or its hydrogenated product is converted into the primary modified block copolymer. You may come to mix in a polymer or its hydrogenated material (1).
The proportion of the unmodified block copolymer is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less in the primary modified block copolymer or its hydrogenated product (1). .

Preferable examples of the primary modified block copolymer or the hydrogenated product (1) thereof include, for example, a primary bonded with a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. Examples thereof include a modified block copolymer or a hydrogenated product thereof.
Examples of the structure in the vicinity of the functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group include the following formulas (I) to (XIII).

Here, R < ¹ > -R < ⁴ > is C1-C24 which has a functional group chosen from hydrogen or a C1-C24 hydrocarbon group, or a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. A hydrocarbon group is shown.
R ⁵ represents a hydrocarbon chain having 1 to 48 carbon atoms or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group.
Further, in the hydrocarbon group of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, nitrogen, silicon, etc., in a bonding mode other than a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group Elements may be bonded.
R ⁶ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.

  An atom having at least one functional group selected from the above-mentioned hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilane group, which is suitable as the primary modified block copolymer or its hydrogenated product (1). The functional group-containing modifier used for obtaining the primary modified block copolymer or hydrogenated product (1) to which the group is bonded is shown below.

  Examples of such functional group-containing modifiers include tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, and diglycidyl. Orthotoluidine, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltri Propoxysilane and γ-glycidoxypropyl tributoxysilane can be used.

  Also, 1- [3- (triethoxysilyl) -propyl] -4-methylpiperazine, 1- [3- (diethoxyethylsilyl) -propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) ) -Propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) -propyl] -3-ethylimidazolidine, 1- [3- (triethoxysilyl) -propyl] -3-methylhexa Hydropyrimidine, 1- [3- (dimethoxymethylsilyl) -propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxysilyl) -propyl] -1-methyl-1,2,3,4 Tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) -propyl] -1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3 -[3- (Trimethoxysilyl) -propyl] -imidazolidine, (2- {3- [3- (trimethoxysilyl) -propyl] -tetrahydropyrimidin-1-yl} -ethyl) dimethylamine can be used.

  Also, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycyl Sidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, and γ-glycidoxypropyldimethylphenoxysilane can be used.

In addition, γ-glycidoxypropyl diethylmethoxysilane, γ-glycidoxypropylmethyl diisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, Bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxy Silane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) Methylphenoxysilane can be used.

  Further, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, Bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl- Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxy Silane You can use.

  Β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane , Β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane , Β- (3,4-epoxycyclohexyl) ) Ethyl - diethyl ethoxysilane can be used.

Β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea and N-methylpyrrolidone can be used.

When the functional group-containing modifier is added to the living end of the block copolymer or its hydrogenated product, the living end of the block copolymer or its hydrogenated product is polymer block A, Any of the combined blocks B may be used, but it is preferably a living terminal of the polymer block A from the viewpoint of obtaining a composition for the heat-shrinkable laminated film of the present embodiment having good mechanical strength and the like.
The use amount of the functional group-containing modifier is preferably more than 0.5 equivalent and 10 equivalents or less, and more than 0.7 equivalent, with respect to 1 equivalent of the living terminal of the block copolymer or hydrogenated product thereof. It is more preferably 5 equivalents or less, more preferably more than 1 equivalent and 4 equivalents or less.
The amount of the living end of the block copolymer or hydrogenated product thereof may be calculated from the amount of the organic lithium compound used for the polymerization and the number of lithium atoms bonded to the organic lithium compound. It may be calculated from the number average molecular weight of the obtained block copolymer or its hydrogenated product.

  In addition, the hydrogenated primary modified block copolymer is obtained by subjecting the primary modified block copolymer obtained by addition reaction of the functional group-containing modifier to the above-described block copolymer to a hydrogenation treatment. In addition, the hydrogenated block copolymer was reacted with an organic alkali metal compound such as an organolithium compound (metalation reaction) and the block copolymer water obtained thereby. It can also be produced by subjecting a polymer in which an organic alkali metal is added to an additive to the above-mentioned functional group-containing modifier.

The above-mentioned primary modified block copolymer or its hydrogenated product (1) has a weight average molecular weight of the primary modified block copolymer or its hydrogenated product (1) or the heat-shrinkable laminated film of this embodiment. From the viewpoint of improving the mechanical strength of the composition constituting the intermediate layer, it is preferably 30,000 or more.
On the other hand, it is preferably 1 million or less from the viewpoint of ensuring good processability and compatibility with the thermoplastic resin.
The weight average molecular weight is more preferably in the range of 40,000 to 800,000, and further preferably in the range of 50,000 to 600,000.
The weight average molecular weight was measured by gel permeation chromatography (GPC), and the molecular weight of the chromatogram peak was determined from a calibration curve obtained from the measurement of commercially available standard polystyrene (the peak molecular weight of standard polystyrene was used. Can be determined using).

The above-mentioned primary modified block copolymer or hydrogenated product (1) thereof is obtained as a solution in the synthesis step, but if necessary, the catalyst residue is removed and separated from the solution.
As a method for separating the solvent, for example, a polar solvent that becomes a poor solvent for the primary modified block copolymer such as acetone or alcohol or the hydrogenated product thereof after the polymerization or the hydrogenated solution is used. The primary modified block copolymer or its hydrogenated product is precipitated and recovered, or the solution of the primary modified block copolymer or its hydrogenated product (1) is poured into hot water with stirring. In addition, a method of removing the solvent by steam stripping and collecting it, and a method of directly heating the solution and distilling off the solvent can be mentioned.

  The primary modified block copolymer or the hydrogenated product (1) described above may be provided with stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers as necessary. It may be added.

<Copolymer (2)>
The modified block copolymer contained in the intermediate layer includes the above-described primary modified block copolymer or its hydrogenated product (1), an acid anhydride having reactivity with the functional group bonded thereto, and It can be obtained by reacting a copolymer (2) of a monomer having a carboxyl group and a vinyl aromatic hydrocarbon.
Hereinafter, the copolymer (2) will be described.

The copolymer (2) is a copolymer of a monomer having an acid anhydride and / or a carboxyl group and a vinyl aromatic hydrocarbon.
Examples of the monomer having an acid anhydride include acid anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is particularly preferable.
Examples of the monomer having a carboxyl group include acrylic acid and methacrylic acid.
Examples of the aromatic vinyl hydrocarbon include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1. -Diphenylethylene etc. are mentioned, Styrene is especially preferable.

  1000-50000 is preferable and, as for the weight average molecular weight of a copolymer (2), the range of 1000-30000 is more preferable.

The copolymer (2) can be produced by a known method.
For example, it can be produced by an anionic polymerization method, a cationic polymerization method, a radical polymerization method, a condensation polymerization method, a polyaddition reaction, or the like.
Further, the acid anhydride of the obtained copolymer (2) may be esterified or partially esterified with alcohol or the like.

As a copolymer (2), a styrene-maleic anhydride copolymer is mentioned as a suitable example, for example.
A suitable example is a copolymer obtained by esterifying maleic anhydride of a styrene-maleic anhydride copolymer with an alcohol or the like, or a copolymer obtained by partially esterifying.

(Method for producing modified block copolymer)
The modified block copolymer constituting the intermediate layer is obtained by reacting the above-described primary modified block copolymer or its hydrogenated product (1) with the above-described copolymer (2).
In carrying out this reaction, the primary modified block copolymer or its hydrogenated product (1) and the copolymer (2) have a mass ratio of 99.9 / 0.1 to 50/50. It is preferably 99/1 to 70/30, more preferably 99/1 to 80/20.
The reaction method of the primary modified block copolymer or its hydrogenated product (1) and the copolymer (2) is not particularly limited, and a known method can be used.
For example, a melt kneading method in which reaction is performed using a general mixer such as a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, or a multi-screw extruder, and each component is dissolved or dispersed in a solvent or the like Then, after the reaction, a method of removing the solvent by heating can be applied.
When the melt kneading method is carried out, the kneading temperature is preferably 50 to 250 ° C, more preferably 100 to 230 ° C. The kneading time is preferably within 3 hours, more preferably several seconds to 1 hour.
When the reaction is performed by dissolving or dispersing and mixing each component in a solvent or the like, the solvent to be applied is not particularly limited as long as each component can be dissolved or dispersed. For example, in addition to hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons, halogen-containing solvents, ester solvents, ether solvents, and the like can be used.
-10-150 degreeC is preferable and, as for the temperature conditions in the said reaction process, 30-120 degreeC is more preferable. The time required for the reaction varies depending on the conditions, but is generally within 3 hours, and preferably several seconds to 1 hour.

The weight average molecular weight of the modified block copolymer is 30,000 or more from the viewpoint of mechanical strength of the modified block copolymer and its composition, and 1,000,000 or less from the viewpoint of workability and compatibility with the thermoplastic resin. It is preferable that there is, more preferably 40,000 to 800,000, still more preferably 5 to 600,000.
The weight average molecular weight of the modified block copolymer was measured by gel permeation chromatography (GPC), and the molecular weight of the chromatogram peak was determined from a calibration curve obtained from the measurement of commercially available standard polystyrene (peak molecular weight of standard polystyrene). Can be determined using).

(Composition constituting the intermediate layer)
The intermediate layer constituting the heat-shrinkable laminated film of this embodiment is formed of a composition containing the above-described modified block copolymer.
The above-mentioned modified block copolymer (hereinafter sometimes referred to as component (A)) is combined with a vinyl aromatic hydrocarbon polymer (hereinafter also referred to as component (B)) to form an intermediate layer. It can be used as a composition constituting
The mass ratio of the modified block copolymer (component (A)) to the component (B) is preferably 99.9 / 0.1 to 20/80, more preferably 99.7 / 0.3 to 25. / 75, more preferably 99/1 to 30/70.
By combining the modified block copolymer (component (A)) and component (B) at such a mass ratio, a composition having excellent rigidity and blocking resistance can be obtained.
As the vinyl aromatic hydrocarbon polymer (component (B)) constituting the composition, it is preferable to use at least one selected from the following (a) to (c).
The vinyl aromatic hydrocarbon polymer is preferably contained in the intermediate layer in an amount of 0.1 to 80% by mass.
(A) Styrenic polymer (b) At least one aliphatic selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides, and aliphatic unsaturated carboxylic acid esters Copolymer with unsaturated carboxylic acid or derivative thereof (c) Rubber-modified styrene polymer

Of the vinyl aromatic hydrocarbon polymer (component (B)), (a) a styrene polymer will be described.
(A) The styrenic polymer is one obtained by polymerizing styrene or a monomer copolymerizable therewith (excluding (b)).
Examples of the monomer copolymerizable with styrene include α-methylstyrene, acrylonitrile, maleic anhydride and the like.
Examples of the styrene polymer include polystyrene, styrene-α-methylstyrene copolymer, acrylonitrile-styrene copolymer, and styrene-maleic anhydride copolymer. And polystyrene.
The weight average molecular weight of the styrenic polymer is generally 50,000 to 500,000.
Moreover, these styrenic polymers can be used alone or as a mixture of two or more, and can be used as a rigidity improving agent.

In addition, as the (a) styrene polymer, a block copolymer composed of a vinyl aromatic hydrocarbon having a vinyl aromatic hydrocarbon content of 85 to 98% by mass and a conjugated diene, and a hydrogenated product thereof are preferable. As mentioned.
Such a styrenic polymer preferably has a number average molecular weight of 30,000 to 300,000, more preferably 50,000 to 250,000, still more preferably 70,000 to 200,000, and a tan δ peak temperature of 80 to 110 ° C. Preferably, it is 83-105 degreeC, More preferably, it is 85-100 degreeC, Vicat softening temperature is preferable 60-85 degreeC, More preferably, it is 65-83 degreeC, More preferably, it is 68-80 degreeC It can be used as a stiffness and shrinkage improver.

Next, vinyl aromatic hydrocarbon, aliphatic unsaturated carboxylic acid, aliphatic unsaturated carboxylic acid anhydride, fat of (b) of the vinyl aromatic hydrocarbon polymer (component (B)) A copolymer with at least one aliphatic unsaturated carboxylic acid selected from aliphatic unsaturated carboxylic acid esters or derivatives thereof will be described.
Examples of the aliphatic unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid and the like.
Examples of the aliphatic unsaturated carboxylic acid anhydride include fumaric anhydride, itaconic anhydride, maleic anhydride and the like.
Examples of the aliphatic unsaturated carboxylic acid ester include mono- or diesters of the above aliphatic unsaturated carboxylic acid and an alcohol having C1 to C12, preferably C2 to C12.

  In the component (B), the content of the aliphatic unsaturated carboxylic acid and / or aliphatic unsaturated carboxylic acid derivative as the above (b) is generally 5 to 50% by mass, preferably 8 to 30% by mass. %, More preferably 10 to 25% by mass.

As the production method (b), a known method for producing a styrene resin, for example, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or the like can be used.
The weight average molecular weight of the above (b) is generally 50,000 to 500,000.

Examples of the aliphatic unsaturated carboxylic acid ester include alcohols having C1-C12, preferably C2-C12, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, and the like. Esters with acrylic acid, esters of methacrylic acid with C1-C12, preferably C2-C12 alcohols, and α, β-unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid, etc. And at least one selected from mono- or diesters of C1 to C12, preferably C2 to C12 alcohols.
The content of the aliphatic unsaturated carboxylic acid ester is generally 5 to 50% by mass in the copolymer of (b) vinyl aromatic hydrocarbon and aliphatic unsaturated carboxylic acid ester, preferably 8 to It is 30 mass%, More preferably, it is 10-25 mass%.

Particularly, as (b), among the copolymers of vinyl aromatic hydrocarbon and aliphatic unsaturated carboxylic acid ester, the aliphatic unsaturated carboxylic acid ester-styrene copolymer can improve the low temperature shrinkage. preferable.
The Vicat softening point in the aliphatic unsaturated carboxylic acid ester-styrene copolymer is preferably 50 to 95 ° C, more preferably 60 to 90 ° C, and further preferably 65 to 85 ° C.
The Vicat softening temperature is a value measured according to ASTM D-1525 (load: 1 kg, heating rate: 2 ° C./min) using a test piece compression-molded to a thickness of 3 mm.
Among the aliphatic unsaturated carboxylic acid ester-styrene copolymers, particularly preferable are copolymers mainly composed of n-butyl acrylate and styrene, and the total amount of n-butyl acrylate and styrene. Is preferably 50% by mass or more, and more preferably an aliphatic unsaturated carboxylic acid ester-styrene copolymer in which the total amount of n-butyl acrylate and styrene is 60% by mass or more.
A heat-shrinkable laminated film using an aliphatic unsaturated carboxylic acid ester-styrene copolymer mainly composed of n-butyl acrylate and styrene has good shrinkage.

Next, of the vinyl aromatic hydrocarbon polymer (component (B)), the above (c) rubber-modified styrene polymer will be described.
Examples of the (c) rubber-modified styrenic polymer include those obtained by polymerizing a mixture of a monomer copolymerizable with a vinyl aromatic hydrocarbon and an elastomer.
As the polymerization method, suspension polymerization, emulsion polymerization, bulk polymerization, bulk-suspension polymerization and the like are generally performed.
Examples of the monomer copolymerizable with the vinyl aromatic hydrocarbon include α-methylstyrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, maleic anhydride and the like.
Examples of copolymerizable elastomers include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, and high styrene rubber.
These elastomers are generally 3 to 50 parts by mass with respect to 100 parts by mass of vinyl aromatic hydrocarbon or a monomer copolymerizable therewith, and are dissolved in this monomer or become latex to form emulsion polymerization or bulk polymerization. , Used for bulk-suspension polymerization and the like.
Particularly preferable (c) rubber-modified styrenic polymer includes impact-resistant rubber-modified styrene polymer (HIPS).
(C) The rubber-modified styrenic polymer can be used as an agent for improving rigidity and impact resistance.
These (c) rubber-modified styrenic polymers generally have a weight average molecular weight of 50,000 to 500,000. The content of the rubber-modified styrenic polymer is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A) in consideration of maintaining transparency.

  The vinyl aromatic hydrocarbon polymer (component (B)), which is a composition constituting the intermediate layer together with the component (A), has an MFR (temperature of 200 ° C. under G condition, load of 5 kg). From the point, it is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and still more preferably 1 to 30 g / 10 min.

The composition which is a forming material of the intermediate layer constituting the heat-shrinkable laminated film of the present embodiment includes the above-described modified block copolymer (component (A)) and the above-described vinyl aromatic hydrocarbon polymer (component ( It may be a mixture of at least one component selected from predetermined thermoplastic resins other than the component (B)).
The amount of the thermoplastic resin used is preferably a ratio of the modified block copolymer (component (A)) / thermoplastic resin, preferably 1/99 to 99/1, more preferably 3/97 to 97/3. 5/95 to 95/5 are more preferable.

  Although it does not restrict | limit especially as a thermoplastic resin, The thermoplastic resin shown below is mentioned.

For example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride and / or polyvinyl chloride containing 50% by mass or more of vinyl chloride and / or polyvinylidene chloride and a copolymer of other monomers copolymerizable therewith Vinyl resin is mentioned.
Further, a polyvinyl acetate resin which is a copolymer of vinyl acetate having a vinyl acetate content of 50% by mass or more and another monomer copolymerizable therewith, and its hydrolyzate, acrylic acid and its ester, Polymers of amides, polymers of methacrylic acid and esters thereof and amides, polyacrylate resins which are copolymers with other copolymerizable monomers containing 50% by mass or more of these acrylic acid monomers, acrylonitrile and Examples thereof include methacrylonitrile polymers and nitrile resins which are copolymers with other copolymerizable monomers containing 50% by mass or more of these acrylonitrile monomers.

  Also, linear polymers in which structural units of the polymer are bonded by repeating amide group bonds, for example, ring-opening polymers and copolymers such as ε-aminocaprolactam and ω-aminolaurolactam, ε-aminoundecanoic acid Condensation polymer of hexamethylenediamine and dibasic acid such as adipic acid or sebacic acid, specifically nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon Polyamide resins such as -12 and nylon-6-nylon-12 copolymers.

  Also, linear polymers in which the structural units of the polymer are bonded by repeating ester bonds, such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, P, P′-dicarboxydiphenyl, 2,6-naphthalene dicarboxylic acid A dibasic acid or a derivative thereof such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, P-xylene glycol, bisphenol A and the like ( Or a diol).

  In addition, polyester-based resins of ring-opening polymers such as pivalolactone, β-propiolactone, and ε-caprolactone, polyester diols such as poly (1,4-butylene adipate), poly (1,6-hexaneadipate), and polycaprolactone Glycol components such as polyethylene glycol, polypropylene glycol, polyether diol such as polyoxytetramethylene glycol, glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and aromatic and alicyclic Alternatively, thermoplastic polyurethane polymerization obtained by polyaddition reaction with diisocyanate components such as aliphatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate And the like.

  In addition, a linear polymer in which the structural units of the polymer are bonded by repeating carbonate bonds, such as 4,4′-dihydroxydiphenylalkane, 4,4′-dihydroxydiphenyl sulfide, and the like obtained by reaction of phosgene with a dihydroxy compound. Or a polymer obtained by transesterification of the dihydroxy compound and diphenyl carbonate, specifically, a polycarbonate-based polymer such as poly-4,4'-dioxydiphenyl-2,2'-propane carbonate Is mentioned.

  Also, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, specifically polysulfone resins such as poly (ether sulfone), poly (4,4′-bisphenol ether sulfone), poly (thioether sulfone), formaldehyde or Examples include trioxane polymers, polyoxymethylene resins such as copolymers of formaldehyde or trioxane with other aldehydes, cyclic ethers, epoxides, isocyanates, vinyl compounds, and the like.

  Also, polyphenylene ether resins such as poly (2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide resins such as polyphenylene sulfide and poly 4,4′-diphenylene sulfide, bisphenol A and phthalic acid components Polyarylate resins, polyetherketone polymers or copolymers, which are polycondensation polymers, specifically, polyketone resins such as polyetheretherketone.

  In addition, polymers having a structure in which part or all of the hydrogen of the chain hydrocarbon polymer compound is substituted with fluorine, specifically, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoro Fluorine resins such as ethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer, polyvinylidene fluoride, polyvinyl fluoride, etc. .

  In addition, polyoxybenzoyl heavy polymers such as polymers or copolymers produced by solution polycondensation or melt polycondensation using paraoxybenzoic acid, terephthalic acid, isophthalic acid, 4,4′-dihydroxydiphenyl or derivatives thereof. Polymers having imide bonds in the main chain, such as polyimide, polyaminobismaleimide (polybismaleimide), bismaleimide / triazine resin, polyamideimide, polyetherimide and other polyimide resins, 1,2-polybutadiene, transpolybutadiene And the like.

1000 or more are preferable, as for the number average molecular weight of various thermoplastic resins mentioned above, 5000-5 million are more preferable, and 10,000-1 million are further more preferable.
In addition, a thermoplastic resin may be used independently and may use 2 or more types together.

<Additives for the composition constituting the intermediate layer>
In the composition in which the above-mentioned modified block copolymer (component (A)), vinyl aromatic hydrocarbon polymer (component (B)), and further a thermoplastic resin are combined, a predetermined composition is required as necessary. You may mix | blend an additive.
As the additive, any one commonly used in the thermoplastic resin composition can be applied.
For example, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium sulfate, barium sulfate, silica, clay, talc, mica, wollastonite, montmorillonite, zeolite, alumina, titanium oxide, magnesium oxide, zinc oxide, slug wool, glass fiber Inorganic fillers such as carbon black, pigments such as iron oxide, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, ethylene bisstearamide, mold release agents, paraffinic process oil, Examples include naphthenic process oils, aromatic process oils, and paraffins.
Also, softeners / plasticizers such as organic polysiloxane and mineral oil, hindered phenol antioxidants, antioxidants such as phosphorus heat stabilizers, hindered amine light stabilizers, benzotriazole ultraviolet absorbers, flame retardants Further, reinforcing agents such as antistatic agents, organic fibers, glass fibers, carbon fibers, and metal whiskers, coloring agents, and the like are also used.
As other additives, those disclosed in “Rubber / Plastic Compounding Chemicals” (edited by Rubber Digest Co., Ltd.) can be used.

(Manufacturing method of the composition constituting the intermediate layer)
The method for producing the composition constituting the intermediate layer described above is not particularly limited, and a known method can be used.
For example, a melt kneading method using a general mixer such as an open roll, a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, a multi-screw extruder, etc., after dissolving or dispersing and mixing each component, A method of removing the solvent by heating can be applied.
In particular, a melt kneading method using an extruder is preferable from the viewpoints of productivity and good kneading properties.
The melt kneading temperature is preferably from 100 to 350 ° C., more preferably from 150 to 350 ° C., and from 180 to 330 ° C. in consideration of the melting point, melt viscosity, thermal degradation of the modified block copolymer, etc. Further preferred.
The melt kneading time (or the average residence time in the melt kneading process) is 0.2 to 60 in consideration of the degree of kneading (dispersibility), productivity, deterioration of the modified block copolymer, thermoplastic resin, and the like. Minutes are preferred, 0.5 to 30 minutes are more preferred, and 1 to 20 minutes are even more preferred.

(Physical properties of the intermediate layer)
In the heat-shrinkable laminated film of the present embodiment, the front and back layers contain at least one polyester resin described later, and the intermediate layer contains the above-described modified block copolymer.
The storage modulus (E ′) at 30 ° C. of the resin composition constituting the intermediate layer is preferably 1 × 10 ⁹ Pa or more and the peak temperature of the loss modulus (E ″) is 60 ° C. or more and 110 ° C. or less. Thus, a film having a good balance between low-temperature shrinkage and rigidity can be obtained.
The storage elastic modulus and loss elastic modulus were measured using a viscoelasticity measuring / analyzing apparatus DVE-V4 manufactured by UBM Co., Ltd., using a test piece compression-molded by a hot press, with a vibration frequency of 35 Hz and a heating rate of 3 It is determined by measuring a temperature range of -100 ° C to 150 ° C under the condition of ° C / min.
The refractive index (n1) of the modified block copolymer in the intermediate layer measured in accordance with JIS K7142 is the refractive index (n2) ± 0.02 of the polyester resin in the front and back layers, particularly (n2) ± 0. Preferably it is within the range of .015.
In this way, by setting the difference between the refractive index of the intermediate layer and the refractive index of the front and back layers within a predetermined range, the cut pieces generated in the heat shrinkable laminated film manufacturing process are kneaded with the resin constituting the intermediate layer. Thus, a film with good transparency can be obtained.
The modified block copolymer includes a composition ratio of the vinyl aromatic hydrocarbon and the conjugated diene of the primary modified block copolymer or its hydrogenated product (1), the primary modified block copolymer or its hydrogenated product ( By adjusting the weight ratio of 1) to the copolymer (2), the refractive index (n1) can be adjusted to a substantially desired value.
Therefore, n1 within the range of n2 ± 0.02 can be obtained by adjusting the composition ratio according to the refractive index (n2) of the polyester resin in the front and back layers to be used.
Such a predetermined refractive index may be achieved by a single block copolymer hydrogenated vinyl aromatic hydrocarbon and conjugated diene or by a mixed resin of two or more kinds.

Further, as described above, the preferred storage elastic modulus (E ′) at 30 ° C. of the resin constituting the intermediate layer is 1.00 × 10 ⁹ Pa or more, and the peak temperature of the loss elastic modulus (E ″) is 60 ° C. More than at least 110 ° C. or more, more preferably, storage elastic modulus (E ′) at 30 ° C. is 1.50 × 10 ⁹ Pa or more, and peak temperature of loss elastic modulus (E ″). Is at least one in the range of 65 to 100 ° C.
The elastic modulus (E ′) at 30 ° C. affects the rigidity of the heat-shrinkable laminated film and represents the stiffness of the film. The peak temperature of the loss elastic modulus (E ″) greatly affects the low-temperature shrinkability. .
By having the storage elastic modulus (E ′) and the peak temperature of the loss elastic modulus (E ″), a film having an excellent balance between rigidity and low temperature shrinkability can be obtained.

Moreover, the peak temperature of storage elastic modulus (E ') and loss elastic modulus (E ") uses two or more types of primary modified block copolymers or hydrogenated products (1) as constituent resins of the intermediate layer. Alternatively, it can be achieved by using a mixed resin containing a vinyl aromatic hydrocarbon polymer together with a modified block copolymer.
In particular, the mixed resin of the modified block copolymer and the vinyl aromatic hydrocarbon polymer is preferable for achieving the peak temperatures of the storage elastic modulus (E ′) and the loss elastic modulus (E ″), and the preferable mass thereof. The ratio is 99.9 / 0.1 to 20/80, more preferably 99.7 / 0.3 to 25/75, and still more preferably 99/1 to 30/70.
In addition, the peak temperatures of the storage elastic modulus (E ′) and the loss elastic modulus (E ″) may be achieved by blending with other resins as long as the transparency is not impaired.

(Surface layer, back layer)
The surface layer and the back layer constituting the heat-shrinkable laminated film of this embodiment contain at least one polyester resin.
The polyester resin imparts rigidity and elongation to the film and suppresses natural shrinkage while imparting low temperature shrinkage.

As the polyester resin contained in the surface layer and the back layer, those derived from a dicarboxylic acid component and a diol component are preferable.
Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacic acid. It is done.
Examples of the diol component include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and polyethylene glycol. , Polytetramethylene glycol, 1,4-cyclohexanedimethanol and the like, preferably terephthalic acid and ethylene glycol.
The polyester resin is not limited to a simple substance, and may be a blend of two or more kinds.

The dicarboxylic acid component and the diol component each include a main component in an amount of 60 to 100 mol% with respect to each total amount (100 mol% of each), and the total amount of other components other than the main component is the dicarboxylic acid. It is preferable that it is 10-40 mol% with respect to the sum total (200 mol%) of the total amount (100 mol%) of an acid component, and the total amount (100 mol%) of the said diol component.
In addition, a main component means having a content of 60-100 mol% with respect to each total amount (100 mol% of each) of a dicarboxylic acid component and a diol component.
By making the dicarboxylic acid component and / or the diol component into a mixture system, the crystallinity of the obtained polyester resin is lowered, and even when it is blended in the resin of the intermediate layer from the surface layer and the back layer, the crystallization is possible. It is possible to make it difficult to proceed, which is preferable.
The polyester resin is blended in the intermediate layer resin, in addition to the case where it is mixed from the front layer and the back layer in the film production process, as well as the case where a predetermined amount of the polyester resin is contained in the intermediate layer.

As a preferred diol component mixture, the above-mentioned ethylene glycol is used as a main component, and the other components are 1,4-butanediol, neopentyl glycol, diethylene glycol, polytetramethylene glycol, and 1,4-cyclohexanedimethanol. It is preferable to use at least one selected from the group, and 1,4-cyclohexanedimethanol is particularly preferable.
As a preferred dicarboxylic acid component mixture, terephthalic acid is used as the main component, and at least one selected from the group consisting of isophthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, and adipic acid is used as the other component. It is preferable to use terephthalic acid.
That is, it is preferable that the dicarboxylic acid component is terephthalic acid, the main component of the diol component is ethylene glycol, and the other components are 1,4-cyclohexanedimethanol.

The total amount of the other components, that is, the total amount of the other components in the dicarboxylic acid component and / or the diol component is the total amount of the dicarboxylic acid component (100 mol%) and the total amount of the diol component (100 mol%) It is preferable that it is 10-40 mol% with respect to the sum total (200 mol%), More preferably, it is 20-35 mol%.
If it is less than the lower limit, the degree of crystallinity of the resulting polyester resin will be high. On the other hand, if the upper limit is exceeded, the advantages of the main component may not be utilized.
When a mixture of ethylene glycol and 1,4-cyclohexanedimethanol is used as the diol component, the amount of 1,4-cyclohexanedimethanol is based on a total of 200 mol% of ethylene glycol and 1,4-cyclohexanedimethanol. Preferably it is 10-40 mol%, More preferably, it is the range of 25-35 mol%.
By using ethylene glycol and 1,4-cyclohexanedimethanol in such an amount range, the resulting polyester resin has almost no crystallinity and breakage resistance is improved.
As such a polyester resin, “PETG6763” (manufactured by Eastman Chemical Co., Ltd.), “SKYREEN PETG” (manufactured by SK Chemical Co., Ltd.) and the like are commercially available.

In the heat-shrinkable laminated film of this embodiment, the intermediate layer may contain 3 to 30% by mass of the front layer and / or the back layer polyester resin of the total mass of the resin constituting the intermediate layer.
Since the refractive indexes of the intermediate layer resin and the surface layer and / or the back layer resin are substantially the same within a predetermined range, the transparency is not impaired.
Further, by including the surface layer and / or the back layer resin, the familiarity with the surface layer and the back layer is improved, the peel strength between the surface layer, the back layer and the intermediate layer is improved, and the elongation of the film is also expected to be improved.
The blending amount of the polyester resin used for the surface layer and / or the back layer in the intermediate layer is preferably 3 to 30% by mass, more preferably 5 to 20% by mass of the total mass of the resin constituting the intermediate layer.
If it is less than the lower limit, the peel strength and / or elongation is not sufficiently improved. On the other hand, if it exceeds the upper limit, transparency may be impaired.

(Other materials)
The heat-shrinkable laminated film of the present embodiment is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass of a plasticizer and / or a tackifying resin based on the resin mass (100 parts by mass) as desired in each layer. Part may be added.
When the amount of the plasticizer and / or tackifying resin exceeds the above upper limit, the melt viscosity is lowered and the heat-resistant fusing property is lowered, so that the problem of spontaneous shrinkage tends to occur.
In addition to plasticizers or tackifying resins, various additives, such as ultraviolet absorbers, light stabilizers, antioxidants, stabilizers, colorants, antistatic agents, lubricants, inorganic fillers, etc., are used for various purposes. It can be added as appropriate.

(Configuration of heat-shrinkable laminated film)
The thickness ratio (surface layer / intermediate layer / back layer) of the intermediate layer, the surface layer, and the back layer constituting the heat-shrinkable laminated film of this embodiment is preferably in the range of 1/2/1 to 1/12/1. A range of 1/4/1 to 1/8/1 is more preferable.
Further, the laminated structure is not limited to two types and three layers as long as the intermediate layer and the surface layer / back layer are within the specified range.
For example, three types and five layers in which an adhesive layer and the like are arranged on the front and back layers and the intermediate layer may be used.
Although the heat-shrinkable laminated film of this embodiment can obtain sufficient adhesive strength even with two types and three layers, it is used for applications that require more peel strength, for example, applications that require more seal strength after bag making. For example, an adhesive layer may be provided as long as the transparency is not impaired.
As the adhesive layer, a carboxylic acid-modified vinyl aromatic hydrocarbon and conjugated diene elastomer or hydrogenated elastomer, or a maleic anhydride-modified vinyl aromatic hydrocarbon and conjugated diene elastomer or hydrogenated elastomer can be suitably used.

[Method for producing heat-shrinkable laminated film]
The heat-shrinkable laminated film of the present embodiment can be produced by co-extruding a resin constituting the intermediate layer and a resin constituting the front layer and the back layer using an extruder equipped with a T die.
In extruding, an existing method such as a T-die method or a tubular method may be employed.
Alternatively, the resin constituting the intermediate layer and the resin constituting the surface layer and the back layer may be separately formed into sheets, and then laminated using a press method, a roll nip method, or the like.

Specifically, the heat-shrinkable laminated film of the present embodiment can be produced as follows.
That is, the resin constituting the intermediate layer and the resin constituting the surface layer / back layer are melt-extruded, and the melt-extruded resin is cooled with a cooling roll, air, water, etc., and then hot air, hot water, infrared rays, etc. It is reheated by an appropriate method and stretched uniaxially or biaxially by a roll method, a tenter method, a tubular method or the like.
The stretching temperature needs to be changed depending on the softening temperature of the resin constituting the film and the use required for the heat-shrinkable laminated film, but is generally controlled in the range of 60 to 130 ° C, preferably 70 to 120 ° C.
The draw ratio in the main shrinkage direction is appropriately determined in the range of 2 to 7 times depending on the film composition, stretch means, stretch temperature, and target product form.
Whether to use uniaxial stretching or biaxial stretching is determined depending on the intended use of the product.
Even in applications that require shrinkage characteristics in almost one direction, such as labels for PET bottles, it is effective in terms of improving the finish to stretch in the vertical direction without impairing the shrinkage characteristics. It is.
The stretching temperature depends on components other than PET, but typically ranges from 60 to 90 ° C.
Furthermore, as the stretch ratio is increased, the fracture resistance is improved, but the shrinkage rate is increased accordingly, and it is difficult to obtain a good shrink finish. It is preferable that

In the heat-shrinkable laminated film of the present embodiment, the heat shrinkage rate for 10 seconds in 80 ° C. warm water in the main shrinkage direction is 30% or more, and preferably 40% or more.
Furthermore, it is preferable that the thermal shrinkage rate for 10 seconds in 70 ° C. warm water in the main shrinkage direction is 5% or more.
In particular, the shrinkage in the vertical direction for PET labels is preferably 10% or less, more preferably 5%, and even more preferably 3% or less in 80 ° C. hot water for 10 seconds.
When the shrinkage rate exceeds the upper limit, in the label application, shrinkage in the vertical direction becomes remarkable after shrinkage, resulting in dimensional deviation and appearance problems.
Moreover, after extending | stretching, shrinkage | contraction can be provided and hold | maintained by cooling a film rapidly within the time when the molecular orientation of a film does not ease.
The method described in the Example mentioned later is applicable about the measuring method of the shrinkage | contraction rate in the hot water of the main shrinkage | contraction direction of a heat-shrinkable laminated film.

  The heat shrinkable laminated film of this embodiment preferably has a natural shrinkage of 1.5% or less, more preferably 1.0% or less after 30 days in a 30 ° C. environment.

  The heat-shrinkable laminated film of this embodiment preferably has a haze value measured in accordance with ASTM D1003 of 10% or less, more preferably 7% or less, and even more preferably 5% or less.

The breaking resistance of the film is evaluated by tensile elongation.
In a tensile test under an environment of 0 ° C., particularly in label applications, the elongation is 100% or more, preferably 200% or more, more preferably 300% or more in the film take-off (flow) direction (MD).
Moreover, rigidity measures the elasticity modulus about MD and orthogonal direction (TD) of a film, and evaluates the waist of a film with the average value of both.
The average value of tensile modulus in the MD and TD directions is preferably 0.7 GPa or more, and more preferably 1.0 GPa or more.

  Hereinafter, the present invention will be described in detail with reference to examples. This invention is not restrict | limited by the Example mentioned later.

<Production example of primary modified block copolymer>
[Primary modified block copolymer A-1]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 26 parts by mass of styrene, 0.086 parts by mass of n-butyllithium and tetramethylethylenediamine 0.3 times that of n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 30 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 7 parts by mass of styrene and 42 parts by mass of 1,3-butadiene at 65 ° C. for 65 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 25 parts by mass of styrene at 65 ° C. for 30 minutes.
Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-1).

[Primary modified block copolymer A-2]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 35 parts by mass of styrene, 0.088 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 40 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 3 parts by mass of styrene and 10 parts by mass of 1,3-butadiene at 65 ° C. for 20 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 6 parts by mass of styrene and 11 parts by mass of 1,3-butadiene at 65 ° C. for 25 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 29 parts by mass of styrene at 65 ° C. for 35 minutes.
Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-2).

[Primary modified block copolymer A-3]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 30 parts by mass of styrene, 0.083 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 35 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 12 parts by mass of styrene and 30 parts by mass of 1,3-butadiene at 65 ° C. for 55 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 28 parts by mass of styrene at 65 ° C. for 35 minutes.
Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-3).

[Primary modified block copolymer A-4]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 33 parts by mass of styrene, 0.085 parts by mass of n-butyllithium and 0.3 times that of tetramethylethylenediamine with respect to n-butyllithium Mole was added and polymerization was carried out by continuously feeding at 65 ° C. for 40 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 5 parts by mass of styrene and 37 parts by mass of 1,3-butadiene at 65 ° C. for 50 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 25 parts by mass of styrene at 65 ° C. for 30 minutes.
Thereafter, tetraglycidyl-1,3-bisaminomethylcyclohexane as a modifier was equimolarly reacted with n-butyllithium used in the polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-4).

[Primary modified block copolymer A-5]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 3 parts by mass of 1,3-butadiene, 0.040 parts by mass of n-butyllithium and tetramethylethylenediamine with respect to n-butyllithium Polymerization was carried out by adding 0.3 mol and continuously feeding at 65 ° C. for 10 minutes.
Next, a cyclohexane solution containing 14 parts by mass of styrene was continuously supplied at 65 ° C. for 20 minutes for polymerization.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 59 parts by mass of styrene and 10 parts by mass of 1,3-butadiene at 65 ° C. for 80 minutes.
Next, a cyclohexane solution containing 14 parts by mass of styrene was continuously supplied at 65 ° C. for 20 minutes for polymerization.
Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-5).

[Primary modified block copolymer A-6]
Using an autoclave equipped with a stirrer, 0.043 parts by mass of n-butyllithium in a cyclohexane solution containing 25 parts by mass of styrene and 0.3 times mol of tetramethylethylenediamine with respect to n-butyllithium in a nitrogen gas atmosphere Polymerization was carried out by continuously feeding at 65 ° C. for 30 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 44 parts by mass of styrene and 7 parts by mass of 1,3-butadiene at 65 ° C. for 60 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 24 parts by mass of styrene at 65 ° C. for 30 minutes.
Thereafter, 1,3-dimethyl-2-imidazolidinone as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-6).

[Primary modified block copolymer A-7]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, 0.041 parts by mass of n-butyllithium in a cyclohexane solution containing 16 parts by mass of styrene and 0.3 times mol of tetramethylethylenediamine with respect to n-butyllithium Polymerization was carried out by continuously feeding at 65 ° C. for 20 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 20 parts by mass of styrene and 6 parts by mass of 1,3-butadiene at 65 ° C. for 35 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 36 parts by mass of styrene and 6 parts by mass of 1,3-butadiene at 65 ° C. for 50 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 16 parts by mass of styrene at 65 ° C. for 20 minutes.
Thereafter, γ-glyoxypropyltrimethoxysilane as a modifier was equimolarly reacted with n-butyllithium used for polymerization.
After completion of the reaction, equimolar amount of methanol was added to the polymerization vessel with respect to n-butyllithium, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4, 0.5 part by mass of 6-di-t-pentylphenyl acrylate was added to 100 parts by mass of the primary modified block copolymer.
Thereafter, the solvent was removed to obtain a primary modified block copolymer (A-7).

[Block copolymer A-8]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, a cyclohexane solution containing 26 parts by mass of styrene was 0.86 parts by mass of n-butyllithium, and tetramethylethylenediamine was 0.3 times mol of n-butyllithium. Polymerization was carried out by continuously feeding at 65 ° C. for 30 minutes.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 7 parts by mass of styrene and 42 parts by mass of 1,3-butadiene at 65 ° C. for 65 minutes.
Next, polymerization was carried out by continuously supplying a cyclohexane solution containing 25 parts by mass of styrene at 65 ° C. for 30 minutes.
Then, without adding a modifier, methanol was added in an equimolar amount to n-butyllithium in the polymerization vessel, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) as a stabilizer was added. Ethyl] -4,6-di-t-pentylphenyl acrylate was added in an amount of 0.5 parts by mass based on 100 parts by mass of the unmodified block copolymer.
Thereafter, the solvent was removed to obtain a block copolymer (A-8).

[Block copolymer A-9]
Using an autoclave equipped with a stirrer, in a nitrogen gas atmosphere, in a cyclohexane solution containing 3 parts by mass of 1,3-butadiene, 0.040 parts by mass of n-butyllithium and tetramethylethylenediamine with respect to n-butyllithium Polymerization was carried out by adding 0.3 mol and continuously feeding at 65 ° C. for 10 minutes.
Next, a cyclohexane solution containing 14 parts by mass of styrene was continuously supplied at 65 ° C. for 20 minutes for polymerization.
Next, polymerization was performed by continuously supplying a cyclohexane solution containing 59 parts by mass of styrene and 10 parts by mass of 1,3-butadiene at 65 ° C. for 80 minutes.
Next, a cyclohexane solution containing 14 parts by mass of styrene was continuously supplied at 65 ° C. for 20 minutes for polymerization.
Then, without adding a modifier, methanol was added in an equimolar amount to n-butyllithium in the polymerization vessel, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) as a stabilizer was added. Ethyl] -4,6-di-t-pentylphenyl acrylate was added in an amount of 0.5 parts by mass based on 100 parts by mass of the unmodified block copolymer.
Thereafter, the solvent was removed to obtain a block copolymer (A-9).

The primary modified block copolymers (A-1) to (A-7) and the block copolymers (A-8) and (A-9) produced as described above are shown in Table 1 below.
In addition, the numerical value attached | subjected to the structures A and B showing the structure of a block copolymer distinguishes each, and may be the same structure and may differ.

<Production example of modified block copolymer>
Next, the primary modified block copolymers (A-1) to (A-7), block copolymers (A-8) and (A-9) produced as described above, acid anhydrides and Using a styrene-maleic anhydride copolymer shown in Table 2 below, which is a copolymer of a monomer having a carboxyl group and a vinyl aromatic hydrocarbon, a modified block copolymer B-1 B-9 was produced.

  First modified block copolymer / styrene-maleic anhydride copolymer = 90/10 parts blended, melt-kneaded using a 30 mmφ twin screw extruder at 220 ° C. and screw rotation speed 100 rpm, And a modified block copolymer was produced.

For the production of the modified block copolymer, any one of the following three types of styrene-maleic anhydride copolymers was used.
SMA1000 (registered trademark Gart made by SARTOMER, GPC has a weight average molecular weight of about 5500, styrene / maleic anhydride ratio is 1/1)
SMA2000 (registered trademark of SARTOMER, weight average molecular weight by GPC is about 7500, styrene / maleic anhydride ratio is 2/1)
SMA 1440 (registered trademark of SARTOMER, resin whose weight average molecular weight by GPC is about 7500, and styrene-maleic anhydride copolymer is esterified with alcohol)

  Using the gel permeation chromatography (GPC), the modified block copolymer was reacted with the primary modified block copolymer and the styrene-maleic anhydride copolymer (the primary modified block copolymer was converted to styrene). -As a result of examining the amount of the component obtained by the reaction and bonding of the maleic anhydride copolymer to increase the molecular weight), B-1 to B-7 show that the styrene-maleic anhydride copolymer disappears from the chart by the reaction. The reaction was observed, but no reaction was observed for B-8 and B-9.

<Example of production of aliphatic unsaturated carboxylic acid ester-styrene copolymer>
Styrene-n-butyl acrylate copolymers C-1 and C-2 were produced as follows.
To a 10 L autoclave with a stirrer, 5 kg of styrene and n-butyl acrylate were added in the ratio shown in Table 3 below, and at the same time, 0.3 kg of ethylbenzene and 1,1 bis (t-butylperoxy) were used to adjust MFR. ) A predetermined amount of cyclohexane was charged, polymerized at 110 to 150 ° C. for 2 to 10 hours, and then unreacted styrene, n-butyl acrylate and ethylbenzene were collected and produced by a vent extruder.
The MFR of the obtained C-1 was 3.0 g / 10 min.
The MFR of C-2 was 2.6 g / 10 min.

  Next, the primary modified block copolymer, the modified block copolymer, and the characteristic measurement method and evaluation method applied in Examples and Comparative Examples will be described.

(1) Styrene content It calculated from the absorption intensity of 262 nm using the ultraviolet spectrophotometer (Hitachi UV200).

(2) Block ratio A method of oxidatively decomposing a block copolymer with di-tertiary butyl hydroperoxide using osmium tetroxide as a catalyst [I. M.M. KOLTHOFF, et al. , J .; Polym. Sci. 1,429 (1946)] was determined by quantitative determination of the vinyl aromatic hydrocarbon polymer block component obtained from the following formula.

(3) Modification rate of primary modified block copolymers (A-1) to (A-7) 10 mg of primary modified block polymer and 10 mg of low molecular weight internal standard polystyrene having a weight average molecular weight of 8000 are added to 20 mL of tetrahydrofuran. The dissolved sample solution was measured by GPC (apparatus: LC10 manufactured by Shimadzu Corporation, column: Shimpac GPC805 + GPC804 + GPC804 + GPC803 manufactured by Tsu Manufacturing Co., Ltd.).
Tetrahydrofuran was used as the solvent, and the measurement was performed at a temperature of 35 ° C.
From the obtained chromatogram, the ratio of the primary modified block copolymer to the standard polystyrene was determined.
Moreover, about the said sample solution, it is 1 with respect to standard polystyrene from the chromatogram obtained by performing GPC measurement by the same method except having used the column of Zorbax (silica-type gel filler) which is a column made from US DuPont. The proportion of the next modified block polymer was determined.
Since the modified block copolymer in the primary modified block polymer is adsorbed to the GPC column using the silica gel as a filler, the ratio of the modified block copolymer in the primary modified block copolymer is It is the ratio of those adsorbed on the silica column.
By comparing these two ratios, the ratio of the primary modified block copolymer was determined.

(4) Melt flow rate Based on ASTM D1238, it was measured under the conditions of 200 ° C. and a load of 5 kg.

(5) Shrinkage The stretched film (TD direction) was immersed in warm water at 70 ° C. and 80 ° C. for 10 seconds, and calculated according to the following formula.
Thermal contraction rate (%) = (L−L1) / L × 100
Here, L indicates the length before contraction, and L1 indicates the length after contraction.
In general, it is preferable that the shrinkage rate is large (shrinks well).

(6) Tensile modulus (Rigidity standard)
As a test piece, what was cut out in the shape of a strip from a stretched film to a length of 10 mm in the MD and TD directions and 100 mm between the marked lines was used.
The measurement temperature was 23 ° C., the tensile speed was 10 mm / min, and the tensile modulus was obtained by a conventional method.
In addition, the average value of MD and TD direction was made into the value of the tensile elasticity modulus.

(7) Elongation at 0 ° C. As the test piece, a test piece cut into a strip shape having a width of 15 mm in the MD direction and a gap of 40 mm between the marked lines was used. The measurement temperature was 0 ° C. and the tensile speed was 100 mm / min.
The 0 ° C. elongation is preferably as large as possible.

(8) Haze (indication of transparency)
Liquid paraffin was applied to the stretched film surface and measured according to ASTM D1003.
Smaller values are more transparent and desirable.

(9) Peel strength The layer including the surface layer and the back layer was used as the peel layer, the layer containing the intermediate layer was used as the peeled layer, and the strength at which the layers were peeled in the 180 ° direction at a width of 10 mm was measured.
The larger the value, the stronger and more desirable the peel strength.

[Examples 1-8], [Comparative Examples 1-4]
As the intermediate layer, a modified block copolymer shown in Table 4 below or a modified block copolymer and a styrenic polymer are used, and as a front and back layer, a polyester resin (dicarboxylic acid component is 100 mol% terephthalic acid, glycol component is ethylene glycol 70). The copolymer polyester which consists of mol% and 1, 4- cyclohexane dimethanol 30 mol%, refractive index 1.568, brand name PETG6763, the Eastman Chemical company make) was used.
The amount of extrusion was melted in an extruder set in the range of 210 ° C. to 230 ° C. at a ratio of intermediate layer: front and back layers = 7: 3, and merged with a die, and two types and three layers (lamination ratio = 1) 5: 7: 1.5) and cooled with a cast roll to obtain an unstretched film having a thickness of 0.3 mm.
This unstretched film was stretched 1.3 times in the machine direction (MD) at 70 ° C., and then stretched 5 times in the perpendicular direction (TD) at 90 ° C. to a thickness of about 50 μm (lamination ratio = 1.5: 7). : 1.5) film was produced.

  As is apparent from the results shown in Table 4 above, the heat-shrinkable laminated films of the present embodiment (Examples 1 to 8) are excellent in low-temperature shrinkage, rigidity, transparency, and peel strength, and are in shrink packaging and shrink-bound packaging. And it was found to be suitable for shrinkage labels and the like.

  The heat-shrinkable laminated film of the present invention has industrial applicability as shrink wrap, shrink-bound wrap, shrink labels, and the like.

Claims (10)

The middle layer,
Consists of at least three layers including a surface layer and a back layer respectively laminated on both sides of the intermediate layer,
Stretched in at least uniaxial direction,
A heat-shrinkable laminated film having a heat shrinkage rate of 30% or more in 10 seconds in 80 ° C. warm water in the main shrinkage direction,
The front layer and the back layer include at least one polyester resin,
The intermediate layer is
At least one polymer block A mainly composed of vinyl aromatic hydrocarbons;
A primary modified block copolymer obtained by addition-reacting a functional group-containing modifier to a block copolymer comprising at least one polymer block B mainly comprising a conjugated diene, or a hydrogenated product thereof (1) ,
A copolymer of a monomer having an acid anhydride and / or a carboxyl group reactive with the functional group of the primary modified block copolymer or its hydrogenated product (1), and a vinyl aromatic hydrocarbon ( 2)
The modified block copolymer that is bonded,
Seen including,
The functional group-containing modifier is
By the addition reaction with the block copolymer, the primary modified block copolymer or the hydrogenated product (1) thereof,
Having a function of generating an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group;
Heat shrinkable laminated film. The heat-shrinkable laminated film according to claim 1 , wherein the copolymer (2) is a styrene-maleic anhydride copolymer or a copolymer in which a part thereof is a carboxyl group. The intermediate layer is
0.1 to 80% by mass of at least one vinyl aromatic hydrocarbon polymer selected from the group consisting of the following (a) to (c):
The heat-shrinkable laminated film according to claim 1 or 2 .
(A) Styrene polymer (b) At least one aliphatic selected from vinyl aromatic hydrocarbons and aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid anhydrides and aliphatic unsaturated carboxylic acid esters Copolymer with unsaturated carboxylic acid or derivative thereof (c) Rubber-modified styrene polymer The polyester resin is composed of a dicarboxylic acid component and a diol component,
The dicarboxylic acid component and the diol component each include a main component in an amount of 60 to 100 mol% with respect to the total amount (100 mol% of each),
The total amount of other components is 10 to 40 mol% with respect to the total (200 mol%) of the total amount (100 mol%) of the dicarboxylic acid component and the total amount (100 mol%) of the diol component. The heat-shrinkable laminated film according to any one of 1 to 3 . The main component of the dicarboxylic acid is terephthalic acid,
The main component of the diol component is ethylene glycol,
The heat-shrinkable laminated film according to claim 4 , wherein the other component is 1,4-cyclohexanedimethanol. The amount of 1,4-cyclohexanedimethanol is
Total amount of dicarboxylic acid component (100 mol%) and total amount of diol component (100 mol%)
The heat-shrinkable laminated film according to claim 4 or 5 , which is in a range of 10 to 40 mol% with respect to the total (200 mol%). The intermediate layer is
The heat-shrinkable laminated film according to any one of claims 1 to 6 , comprising 3 to 30% by mass of the polyester resin based on the total weight of the resin constituting the intermediate layer. The heat-shrinkable laminated film according to any one of claims 1 to 7 , wherein a haze value measured in accordance with ASTM D1003 is 10% or less. The heat-shrinkable laminated film according to any one of claims 1 to 8 , wherein a heat shrinkage rate in a main shrinkage direction in 10 seconds in 70 ° C warm water is 5% or more. The method for producing a heat-shrinkable laminated film according to any one of claims 1 to 9 , comprising at least three layers including an intermediate layer and a front layer and a back layer, which are respectively laminated on both sides of the intermediate layer. There,
At least one polymer block A mainly composed of vinyl aromatic hydrocarbons;
A primary modified block copolymer obtained by addition-reacting a functional group-containing modifier to a block copolymer comprising at least one polymer block B mainly comprising a conjugated diene, or a hydrogenated product (1) thereof. A manufacturing process;
An acid anhydride and / or a carboxyl group having reactivity with the functional group of the primary modified block copolymer or hydrogenated product (1) is added to the primary modified block copolymer or hydrogenated product (1) thereof. A step of producing a modified block copolymer by bonding a copolymer (2) of a monomer having a vinyl aromatic hydrocarbon,
Forming the intermediate layer using the modified block copolymer, and forming the surface layer and the back layer using at least one polyester resin;
I have a,
The functional group-containing modifier is
By the addition reaction with the block copolymer, the primary modified block copolymer or the hydrogenated product (1) thereof,
Having a function of generating an atomic group having at least one functional group selected from the group consisting of a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group;
A method for producing a heat-shrinkable laminated film.