JP2002178473A - Heat resistant multilayer adhesive wrapping film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant adhesive wrapping film, in which various request characteristics (using facility or the like) of a packaging time are fulfilled as the film of a material conservation type of an unhalogenated system equipped with barrier properties and heat resistance and also disposal treatment is easy and the same is available as a film for household wrapping. SOLUTION: The heat resistant multilayer adhesive wrapping film is comprised of both at least one layer consisting of a resin composition (C) and at least one layer consisting of a resin composition (E). The resin composition (C) contains a liquid additive (B) at <=3 pts.wt. for 100 pts.wt. resin comprising an aliphatic/aromatic copolymerized polyester resin (A) as a main body, in which melting point of a crystal is 110-230 deg.C, containing 10-90 mol% component consisting of an aromatic monomer. The resin composition (E) contains the liquid additive (B) at 1-25 pts.wt. for 100 pts.wt. resin comprising an aliphatic polyester resin (D) as the main body. In this film, tensile modulus is 15-180 kg/mm2 and heat resistance is >=110 deg.C and adhesive work done is 5-50 g.cm/25 cm2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive heat-resistant wrap film which is suitably used for packaging, especially as a wrap film for home use. Hereinafter, the description will be limited to the home wrap film.

[0002]

2. Description of the Related Art A household wrap film is mainly used for preserving food in a refrigerator or a freezer, or for heating in a microwave oven, for overlapping food in a container. For this reason, household wrap film has not only transparency, but also appropriate elastic modulus during packaging, storage, and heating, melt perforation during heating, large deformation, fusion to containers, deterioration of the container itself, etc. There is a demand for non-stability and proper adhesion between wrap films or between containers at low to high temperatures. Currently, commercially available household wrap films include the most convenient stretched polyvinylidene chloride resin-based film, and the following lap suitability, which is significantly inferior in wrap suitability, extruded cast polyethylene resin, plastic And those made of a film mainly containing a modified polyvinyl chloride resin, a poly-4-methylpentene-1 resin or the like.

[0003] Moreover, there has never been a resin made of an aliphatic polyester resin which is considered to be more safe in all aspects, and it is easy to use, and is more environmentally and hygienic than the vinylidene chloride resin. The level beyond the wrap film has never been seen before. For example, a stretched film made of a polylactic acid-based aliphatic polyester resin is described in, for example, Japanese Patent Application Laid-Open No. Hei 6-23836, which is not used for household wrap film. The ratio is too high, exceeding 220 kg / square mm, and there is no adhesion between the wraps, nor the wrap suitability referred to in the present invention, in addition to the problems described below, and it is not suitable as a household wrap film at all. .

Japanese Patent Application Laid-Open No. 9-272794 discloses that
In order to impart flexibility like conventional polyethylene for general packaging, a large amount (25 to 80% by weight) of a polylactic acid-based resin is made of a flexible aliphatic polyester resin having a low softening point and a crystallization point of room temperature or lower. %) To control and suppress the crystal by the flexibility and the interaction between the molecules of both resins, and to impart transparency. This is also in a field different from the specific wrap application of the present invention. Also, JP-A-7-25
No. 7660 discloses vegetables using polylactic acid resin,
Water vapor permeability of 50 to 300 g / m ² · 24 hr, used for transporting and storing flowers and fruits, etc., and a thickness of 10 to 10 for conventional freshness retaining applications in the field of biaxially oriented polystyrene films (packaged with OPS films). There is a disclosure of a 500 μm film and the like. These are in fields different from the application of the present invention and are not easily used in the specific wrap of the present invention described below.

Japanese Patent Laid-Open Publication No. Hei 10-60136 discloses that
There is a description of a stretched film of a specific polyglycolic acid,
In the examples, there are descriptions of high barrier properties, high tensile elasticity, and the like. There is no property or the like, and the range of the elastic modulus of the wrap is different from the range of the present invention, and the application field is different. In order to solve these problems, the present inventors proposed a wrapping film using a polylactic acid-based resin in Japanese Patent Application Laid-Open No. 2000-26623,
JP-A-26624 proposes a wrap film made of a polyglycolic acid-based resin, and JP-A-2000-37837 proposes a multilayer wrap film composed of these aliphatic polyester-based resins. These are films having a layer structure mainly composed of an aliphatic polyester resin, and have a structure different from that of the present invention.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a resin composition comprising an aliphatic / aromatic copolymerized polyester resin (A) as a main component and / or a resin composition (C) containing a liquid additive (B) in the resin. , A wrap film for household use, which is processed into a film and is excellent in processability, and for wrapping an object to be packaged with various containers (including those made of porcelain and plastics).
Also suitable for wrapping packaging without containers, and preserved,
In particular, it is an object of the present invention to provide a heat-resistant multilayer adhesive wrap film having a barrier property, which is suitable for use in heating using a microwave oven.

[0007]

The crystal melting point is 110 to 23.
A liquid additive (B) is added to 100 parts by weight of a resin mainly composed of an aliphatic / aromatic copolymerized polyester resin (A) containing 10 to 90 mol% of a component composed of an aromatic monomer at 0 ° C. To at least one layer of the resin composition (C) containing 3 parts by weight or less (including 0 parts by weight) and 100 parts by weight of the resin mainly composed of the aliphatic polyester resin (D).
A film composed of at least one layer of the resin composition (E) containing 1 to 25 parts by weight of the liquid additive (B), and having a tensile modulus of 15 to 180 kg / mm.
² , the heat resistance is 110 ° C or higher, and the adhesiveness (the work of adhesion)
Is 5 to 50 g · cm / 25 cm ² .

In the present invention, the crystal melting point is 110 to 23.
Aliphatic / aromatic copolymerized polyester resin (A) containing 10 to 90 mol% of a component composed of an aromatic monomer at 0 ° C.
Specifically, the acid component is, as an aliphatic acid component, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, at least one dicarboxylic acid structure selected from 1,4-cyclohexanedicarboxylic acid Monomer having a unit, further terephthalic acid as an aromatic acid component,
It is at least one monomer selected from isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid.

Next, the alcohol component is ethylene glycol, propylene glycol, 1,4-butanediol,
It is at least one monomer selected from 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and polyethylene glycol (having 2 to 10 polymerization units). In addition, within a range not exceeding 50 mol% based on the total amount of each of the above monomers,
For example, other hydroxycarboxylic acids may be copolymerized, preferably in the range of 1 to 40 mol%. In this case,
As monomers to be copolymerized, D-lactic acid, L-lactic acid, DL (racemic) form of the lactic acid, meso form of the lactic acid, and glycolic acid, 3-hydroxyvaleric acid, ε-caprolactone, 2-
At least one is selected from hydroxy-2,2-dialkylacetic acid, 2-hydroxy-2,2-dialkylpropionic acid, 4-hydroxybutanoic acid, 3-hydroxyhexanoic acid, and cyclic dimers thereof.

These copolymerization methods are performed before, during, and after the reaction.
Later, at a free stage, by controlling the feed conditions and amount of the monomer, using a polyfunctional monomer or the like at appropriate times, or by controlling the terminal reaction during or after polymerization, etc. The method may be a method in which a copolymer having a shape, a branched shape, an ionomerization or the like existing alone or as a mixed structure is formed. Also, a method of polymerizing block chains having different properties as described above (melting point, compatibility, crystallinity, crystal properties, etc.) mainly composed of different types of monomers into a shape which is branched in a timely manner from a branch point. But good.

Preferred aliphatic acidic components constituting the aliphatic / aromatic copolymerized polyester resin (A) are oxalic acid,
Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 1,4-cyclohexanedicarboxylic acid, at least one selected from naphthalenedicarboxylic acids, more preferably succinic acid, glutaric acid, at least one selected from adipic acid, Preferably, at least one kind is selected from succinic acid and glutaric acid. The preferred aromatic acid component is at least one selected from terephthalic acid and naphthalenedicarboxylic acid. Next preferred alcohol components are ethylene glycol, diethylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, 1,4
-At least one monomer selected from cyclohexanedimethanol, and more preferably at least one monomer selected from ethylene glycol, diethylene glycol, 1,4-butanediol and the like.

[0012] Among the acid components to be subsequently copolymerized, the amount range of the aliphatic acid component is usually 90 to 10 mol%, and the amount range of the aromatic acid component is usually 10 to 90 mol%, preferably The former is 90 to 15 mol% and the latter is 10 to 85 mol%, and more preferably the former is 60 to 30 mol% and the latter is 4
0 to 70 mol%, more preferably 70 to 70 mol%.
40 mol% and the latter are 30 to 60 mol%. If the range of the aromatic component is less than 10 mol%, the effect of improving extrusion processing stability, hydrolysis during kneading, transesterification reaction prevention, stretchability, barrier properties, heat resistance, etc. is limited, and 90 If the amount is more than mol%, the plasticity by the additive (to impart adhesion) or the biodegradability in the compost treatment at the time of waste treatment deteriorates, and a problem arises.

Next, it is needless to say that the amount ratio of the acid component to the alcohol component is essentially the same, ignoring the molecular terminal portion. Or use a small amount of a third reactant (monomer) to modify intramolecularly. More specifically, the copolymerization of the aliphatic / aromatic copolymerized polyester resin (A) means that each monomer or polymerization unit has a random shape, a compositionally tapered shape, a block shape, or a polyfunctionality. The polymer is polymerized in a star shape around a point, or a polymer having a required length and a required number of branches from a polyfunctional point, or a material containing the above-mentioned free mixed structure, but is not particularly limited. For indirectly increasing the molecular weight of various oligomers, medium molecules and high molecular weight molecules, polyfunctional glycols, polyfunctional carboxylic acids, those having both polyfunctional glycols and carboxylic acids, isocyanate compounds, carbonate compounds For example, the molecular weight may be increased or the branches may be formed. In this case, the reaction may be carried out at the time of polymerization, each segment may have an appropriate molecular weight, or the reaction may be carried out after the polymerization.

More specifically, for example, even in the above-mentioned aliphatic / aromatic copolymer polyester (A), a portion where terephthalic acid and ethylene glycol are polymerized, a portion where terephthalic acid, succinic acid and ethylene glycol are copolymerized, and the like. And succinic acid and ethylene glycol polymerized parts, lactic acid, a part where glycolic acid and the like are polymerized, glycolic acid and lactic acid are copolymerized in a free structure and a block unit having a free structure, and a star from a multifunctional point. It may have a structure having polymerization or free branches. Further, in order to improve the tension and the tear strength at the time of extrusion melting, it may include those obtained by ionizing the above-mentioned branched structure and / or the above terminal portion with an alkali metal ion, an alkaline earth metal ion or the like.

Further, in order to improve the heat resistance, extrusion stability, hydrolysis prevention, transesterification reaction, and gelation by cross-linking reaction inside and outside the molecule, the terminal of the molecule is used for further processing the above resin. (Especially esterification, etherification of terminal carboxylic acid groups, esterification of terminal alcohol groups,
It is better to measure the inactivation by other capping processes for stabilization. The stabilizer can be freely added to these. Furthermore, as a measure to prevent the resin from easily absorbing water and hydrolyzing during heating and kneading (during extrusion processing), the molecular weight is significantly reduced, and the processability becomes too poor, a structure (hydrocarbon cyclo ring, Relatively long carbon bond: For example, when it is preferable to introduce a monomer having the same or higher position in C2 or higher, such as a tertiary carbon or a quaternary carbon, or the same block in a predetermined amount at a predetermined position in the molecule. There is.

Further, the resin mainly composed of the aliphatic / aromatic copolymerized polyester resin (A) of the present invention contains 50 to 99% by weight of the above aliphatic / aromatic copolymerized polyester resin,
In order to improve processability, water resistance, etc., a resin composition containing 1 to 50% by weight of a thermoplastic resin other than the resin (A) may be used. The mixing amount in this case is preferably 5 to 4
0% by weight, more preferably in the range of 7 to 30% by weight. Next, one group of these thermoplastic resin resins other than the resin (A) is an aliphatic polyester resin (D), which is as follows.

Aliphatic polyester resins composed of an aliphatic dicarboxylic acid and an aliphatic dialcohol, or D-lactic acid, L-lactic acid as a monomer, DL (racemic) form of the lactic acid, meso form of the lactic acid, and glycol At least one selected from an acid, 3-hydroxyvaleric acid, ε-caprolactone, 2-hydroxy-2,2-dialkylacetic acid, 2-hydroxy-2,2-dialkylpropionic acid, 4-hydroxybutanoic acid, and 3-hydroxyhexanoic acid And at least one selected from aliphatic polyester-based resins comprising a cyclic dimer and a monomer comprising a hydroxycarboxylic acid. The lactone is selected from resins composed of monomers such as β-butyrolactone, β-propiolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

For the same reason, in the case of a monomer having a structural isomer such as a lactic acid-based resin, the D-form and the L-form within the above-mentioned range are mixed at a mixing ratio of 7/3 to 3/7. A special mixture having a eutectic (stereo complex) forming ability and exhibiting a higher crystal melting point than a polymer of both alone can also be included in the above. The molecular structure is modified and optimized in order to satisfy various manufacturing and practical requirements, and the method of optimizing the molecular structure is the same as that of the resin (A). Next, the resin constituting each layer described above as a thermoplastic resin tree other than these other resins (A) and (D):
Further, another thermoplastic resin (hereinafter referred to as F) may be mixed. These are:

Polyolefin resin, ordinary polyester resin containing aromatic monomer, polyamide resin, ethylene-aliphatic unsaturated fatty acid copolymer resin, ethylene-aliphatic unsaturated fatty acid ester partially saponified resin, and Ionomer resins composed of these, ethylene-vinyl alcohol copolymer resins, α-olefins (ethylene, etc.)
Styrene copolymer resin (or condensed ring hydrogenated resin), α-olefin-carbon monoxide copolymer resin (or condensed hydrogenated resin),
Ethylene-alicyclic hydrocarbon copolymer resin (or hydrogenated resin), styrene and butadiene or isoprene copolymer resin (or hydrogenated resin), petroleum resin (or hydrogenated resin), terpene resin (or Hydrogenated resin).

The weight average molecular weight of the resins (A) and (D) used in the present invention is 10,000 to 15,000,000, preferably 20,000 to 11,000,000, more preferably 30,000 to 1,000,000, and further preferably,
400,000 to 900,000. The reason for this is that if it is less than the lower limit, it is not preferable in terms of maintaining an appropriate viscosity during processing and film strength. Exceeding the upper limit is not preferable in terms of extrusion processability (thermal decomposition, increase in resin pressure in the system, straightening of uneven thickness, etc.). The resin (A) has a crystal melting point (here, 10 ° C. in accordance with the DSC method of a resin annealed at an appropriate temperature).
/ Peak value measured at a scan speed of / min) of 110
The main component is one in the range of ° C to 230 ° C. If the melting point of the main crystal of the resin as a raw material is less than 110 ° C., the practical heat resistance potential of the wrap film described later is insufficient, and the shrinkage is excessive, which is not preferable.

On the other hand, if the crystal melting point exceeds 230 ° C., the decomposition temperature at the time of processing becomes close, and the processability (decomposition, viscosity decrease, etc.) such as extrudability and stretchability, and the recovery and recyclability become poor. Not preferred. For the same reason, the lower limit of the crystal melting point is preferably 120 ° C. and the upper limit is 230 ° C., and more preferably the lower limit is 130 ° C. and the upper limit is 225 ° C.
It is. Further, the crystal melting point may have a plurality of peak values, and it is sufficient that a component within the above-mentioned range is contained in a crystallinity of 10% or more. In addition, as long as the crystal melting point satisfies the above range, other components at 110 ° C. or lower may be included. Further, the range of the saturated crystallinity of the aliphatic / aromatic polyester resin (A) as a raw material is generally about 5 to 80%, preferably 7 to 70%.
The range of crystallinity of the film is usually about 5 to 70%, preferably 7 to 60%.

Below these lower limits, poor heat resistance of the film and excessive stickiness of the amorphous portion are predominantly exhibited due to plasticization, and there are adverse effects such as the elastic modulus being excessively lowered during plasticization. If the upper limit is exceeded, there is an adverse effect on the molding processability of the raw material, the bleeding effect of the additive, the lack of flexibility, the transparency of the film, and the like. However, after processing into a film under the influence of processing conditions (quenching etc.) and additives (crystal control) due to the characteristics of the raw material (although the degree of crystallinity is lower than that described above), this is used under heating (for example, cooking) ), When the crystallization rate is high, the crystal is immediately crystallized, and as a result, the heat resistance is effectively obtained (even if the film is localized, but does not melt or perforate). In addition, the film properties after practical use may satisfy the above.

Next, the film of the present invention contains, if necessary, 3 parts by weight or less of a liquid additive (B) in 100 parts by weight of the resin (A). 1-2 for 100 parts by weight of the above-mentioned other resin (D)
It is characterized by including at least one layer comprising the resin composition (C) or (E) containing 5 parts by weight. The liquid additive (B) used in the present invention is used for the primary purpose of imparting adhesion to the wrap film. In addition, it is useful for suppressing the generation of static electricity, preventing blocking of wound rolls, and providing flexibility during handling by adjusting the tensile elasticity. Volume) etc. are always required to be controlled within a suitable range without excessive stickiness. Even if the adhesiveness is high, the adhesiveness (adhesion) such as an adhesive tape is not preferable because the processability, the packaging property, the preservability and the like are remarkably deteriorated.

As the additive (B), the viscosity of the main component at 50 ° C. (hereinafter, measured by a B-type viscometer) is 5 centipoise to 500 centipoise at 100 ° C., preferably Is 300 centipoise or less at 100 ° C., and the boiling point of the main component is 170 ° C.
The above liquids are preferably used. A liquid refers to a state at least at 100 ° C, preferably at 50 ° C. But 50
Including pastes at ° C. In the case of a mixed multi-component, even if one component is a solid oligomer at 50 ° C., it also includes a case where it is dissolved in another component at the time of heating.

Next, the addition amount is in the range of 1 to 25 parts by weight based on 100 parts by weight of the resin (D), and the preferred range thereof is 3 to 25 parts by weight, more preferably 5 to 25 parts by weight. -20 parts by weight. The reasons are as described below. The resin composition (E) obtained by adding the liquid additive (B) to the resin (D) preferably has at least one layer disposed on the surface. In addition, when the liquid additive (B) is added to the resin (A), the addition of 3 parts by weight or less (including the case where it is not added) to 100 parts by weight of the resin is effective for the following effects and processing during extrusion. Used for imparting stability and moderate flexibility to the layer made of the resin, but is not essential. Hereinafter, mainly the case where the additive (B) is used for the resin (D) disposed on the surface layer is mainly described.
Adjustment of the tensile modulus of the wrap film of the additive (B), ease of use (slipperiness, drawability from roll winding,
Static electricity generation control, self-adhesion area, sharpness, etc.)
The properties and the adhesion (work of adhesion) cannot be controlled in a suitable range, which is not preferable, and the stretching stability is often poor.

If the amount of the additive (B) is larger than the above upper limit, the resin (D) may be excessively plasticized, possibly resulting in insufficient heat resistance, and may have a film tensile modulus (film stiffness, handling). ), The extension (extension) after cutting in the box blade part becomes poor, the overlapping part which hinders the packaging property increases, and the wrinkle part accompanying these becomes difficult to peel off and to stretch easily. , Making it difficult to pack in a stretched condition. In addition, the film may be excessively shrunk by heating, and the film may be easily detached from the container, resulting in uneven heating and contaminating the inside of the refrigerator. In addition, an excess of the additive (B) may be added over time to the surface of the wrap film,
Bleed out to the end of the roll, dirty the box,
It is not preferable because the wrap film is sticky, shifts to food, or the work of adhesion is out of a preferable range.

The additives (B) include, among others, aliphatic alcohols or alicyclic alcohols, polyhydric alcohols thereof, polycondensates and modified products thereof (adducts such as alkylene oxides). At least one selected alcohol component, and an ester of the above-mentioned alcohol component with an aliphatic or aromatic (poly) carboxylic acid, or an aliphatic hydroxycarboxylic acid with an alcohol and / or
Or esters with aliphatic fatty acids, and modified products of these esters, polyoxyethylene alkyl ethers and / or
Or at least one selected from the group consisting of esters thereof, oligomers of the resins (A) and (D), cyclic dimers, monomers, and mineral oils, liquid paraffins, and low-polymers of saturated hydrocarbon compounds. Certain plasticizers can be used more preferably. Although not limited to the examples, these include, for example, polyglycerols such as diglycerin, triglycerin, tetraglycerin..., And these as a raw material of an alcohol component, and a fatty acid,
For example, acetic acid, propionic acid, lacnic acid, caproic acid, caprylic acid, capreic acid, lauric acid, palmitic acid,
With stearic acid, oleic acid, linoleic acid, etc., at least one ester selected from mono, di, triester, polyester, etc., or a free ester of sorbitan with the above fatty acids, or ethylene glycol, propylene glycol, As a free ester of tetramethylene glycol, a condensation polymer thereof and the above fatty acid, or an aliphatic hydroxycarboxylic acid, a free alcohol such as citric acid, malic acid, tartaric acid, etc., and a lower alcohol having 10 or less carbon atoms can be used. Free esters of malonic acid, succinic acid, glutaric acid, adipic acid, etc. with aliphatic alcohols as esters or polycarboxylic acids, or ethylene oxide adducts or epoxidized There are soybean oil, epoxidized linseed oil, ... and others.

Preferably, among these, a saturated ester type or the like in which an active functional group is blocked, and a single chain aliphatic ester fatty acid having a small number of carbon atoms, for example, having 1 carbon atom
At least one, preferably at least one,
Or an ester containing at least one long-chain fatty acid having a relatively large number of carbon atoms, for example, about 5 to 18 (1).
May be included. These esters have plasticizing ability,
It is often preferred from the viewpoint that a complicated exchange reaction or the like is difficult to perform.

Further, preferably, another type or at least two types of additives selected from these are used, and the viscosity difference (hereinafter, the viscosity measurement difference at 50 ° C. is at least 3 centipoise)
It is advisable to select ones with a mixture and use them mixed. More preferably, in addition to the above, the weight mixing ratio of “high-viscosity material / low-viscosity material” is preferably used in a range of “0.5 / 10 to 9/1”. More preferably, the viscosity difference is at least 1
It is preferable to mix and use the products of No. 0 in a weight mixing ratio of “high-viscosity product / low-viscosity product” in the range of “1/9 to 5/5”. 3
When mixing more than one kind, at least 5
It is only necessary that any two components of the substances added by weight% or more satisfy the above relationship. The reason is believed to be that the speed and amount of bleed-out on the film surface are made uniform, averaged over time, and act synergistically. More preferably, among these, it is more preferable to combine the additives having different compatibilization coefficients in an appropriate amount so as to obtain the above-mentioned effects.

In addition, according to the properties of the base resin, known solubility parameters (SP value: Polymer Handbook, 3rd edition, pages VII-517): WILY INTER
Published by SCIENCE, or Polymer Engine
eering and Science, Februr
y, 1974, vol. 14． No2 Page 15
Additives that are not too far from the resin (for example, in the vicinity of 1 to 154) (for example, the difference between the two is less than 2.5; however, when the additives have a mixed composition, the synthetic value obtained by proportionally distributing the respective additives) ), And these additives may be mainly (50% by volume or more, preferably 60% by volume or more). The reason for the above is that if the SP value is too far away, the plasticizing effect will generally be lost, and not only will it not be possible to separate and knead, but if it can be mixed, it will be whitened and separated, making it not only brittle, but also difficult to finish into a transparent film. is there.

Therefore, within the above range, the difference between the SP values is small when a small amount of an additive which is separated to some extent is used.
For example, bleed out quickly to the surface to exert the initial effect, or slowly bleed out later, and these are phase-separated and dispersed in a finely effective shape on the surface in the form of layers, micelles, islands, dots, etc. However, it is preferable because it can exhibit performance such as suppressing excessive stickiness, not causing whitening contamination, and satisfying contradictory properties such as adhesion and slippage. In detail, the composite component bleeds stably (with time, thermally, and stably when the roll film is peeled off), and while having good adhesion, has moderate lubricity. This is because, if the workability is improved, a synergistic effect may be exhibited, which may be preferable (there may be an effect for preventing excessive adhesion such as excessive adhesiveness).

Further, in order to prevent the reaction with the resin during processing (transesterification reaction, hydrolysis of the resin and additives, etc.),
When the reactivity with the resin (including the oligomer) is high, it is better to inactivate the additive with respect to the resin used. For example, to reduce the number of active residues capable of reacting, attach a group having a strong reaction bonding force (the above-mentioned reaction is difficult) without losing plasticizing performance, capping, or putting it in the molecule,
It is preferable to prevent ester decomposition and the same exchange reaction, or to inactivate the catalyst residue, and to add other additives for preventing the above-mentioned undesirable reaction. For example, an additive that absorbs water (has a higher affinity) than the resin is added and removed. When the effect of the catalyst residue is large, an additive for preventing the adverse effect is effectively used. In addition, additives such as an antioxidant, an anti-coloring agent, a crystal nucleating agent, a deodorant, a coloring agent, and an antibacterial agent are also effectively used.

In order to further positively enhance the adhesion, an appropriate resin is selected from the above-mentioned other thermoplastic resins (F) and mixed with the base resin in the range of 3 to 30% by weight. May be used. In this case, when used in combination with the liquid additive (B), a synergistic effect such as sustained release of the additive and flexibility due to plasticization of both additives is exhibited, which may be preferable in some cases. In further optimizing the film of the present invention, it is convenient to synergistically and effectively exert the properties of the respective resins and additives in a multilayer form, in which case many complicated For the first time, it is possible to satisfy the characteristics required for practical use and to allocate optimal functions.

A preferred example of a multilayer structure, that is, a function sharing example, is that a resin having a relatively low elastic modulus, a resin having a low melting point and a low degree of crystallinity is used in the surface layer, and a relatively large amount of additive is used. , Mainly contributing to the surface properties, adhesion, transparency, anti-fogging properties, flexibility, in some cases, slightly shrinkage when microwave oven heating, handling properties, etc. A resin having a high melting point, a high elastic modulus, and a high degree of crystallinity, with or without a small amount of additives (plasticizer, tackifier, etc.) , Moisture), heat resistance and the like are often preferred.

Specifically, in the present invention, the resin mainly composed of the above-mentioned aliphatic / aromatic copolymerized polyester resin (A) is optionally added with a small amount of the additive (B), and is preferably used as an inner layer. . However, this is not always the case when the surface layer is used without adding more additives. or,
Next, the aliphatic polyester-based resin (D) is preferably used as a surface layer, uses a large amount of additives as described above, and mainly aims at the effect of expressing surface characteristics. However,
It may be used by itself or additionally for the inner layer.

It is more preferred that the surface layer be made of a resin having a lower crystal melting point than the inner layer and / or be composed of a composition containing a large amount of the liquid additive (B). In these, it is sufficient that the inner layer mainly contributes to the improvement of the heat resistance, which contributes to the improvement of the heat resistance and the elastic modulus of the whole film. (Approximately 100 ° C.), and it is better to exhibit appropriate heat resistance for preventing fusion of the surface layers. In the present invention, the surface layer may be more heat-resistant than the inner layer. However, the inner layer is preferably more heat-resistant than the surface layer (the crystal melting point of the film, and / or the crystallinity thereof, or The lower the additive is, the higher the processability,
It is more preferable from the viewpoints of imparting adhesion and optical characteristics.

In another embodiment, the resin (A) and / or
Alternatively, in addition to the layer made of the resin (D), a layer made of another thermoplastic resin may be freely added. Other thermoplastic resins (F) are selected from the following. Polyolefin resin, ordinary polyester resin containing aromatic monomer, polyamide resin, ethylene and aliphatic unsaturated fatty acid copolymer resin, or ethylene and aliphatic unsaturated fatty acid ester partially saponified resin, and composed of these Ionomer resin, ethylene-vinyl alcohol copolymer resin, α-
Olefin (ethylene, etc.)-Styrene copolymer resin (or condensed hydrogenated resin), α-olefin-carbon monoxide copolymer resin (or condensed hydrogenated resin), ethylene-alicyclic hydrocarbon copolymer resin (Or hydrogenated resin), styrene and butadiene or isoprene copolymer resin (or hydrogenated resin)
And the like, and the addition of additives is freely performed according to the situation. In addition, known free substances (nucleating agent, stabilizer, antioxidant, coloring agent, etc.) may be freely added as other additives.

More specifically, the inner layer retains heat resistance, strength, film elastic modulus (film elasticity), barrier properties, etc., improves handling properties (including packaging properties), etc., and improves film processing properties, etc. If functions such as reducing the cost by reducing the thickness and reducing the amount of waste are mainly shared, a further synergistic effect may be exhibited. In contrast, in the case of a single-layer film, there is a limit in fully utilizing each property. For example, increase the copolymerization ratio in order to satisfy workability, adhesion, transparency, and fit characteristics due to flexibility, and add a large amount of additive to effectively exert the effect of the additive. As a result, the heat resistance of the film tends to decrease significantly, for example, by about 20 to 60 ° C. On the other hand, in the case of a multilayer, the bleed (amount, type, time) of the additive on the surface can be controlled by using the same or different additive in each layer, or using a different amount of additive. The fact that the surface characteristics can be controlled as described below has an unexpected effect that a synergistic effect can be exhibited.

Next, the crystal melting point (peak value at a scan speed of 10 ° C./min by the DSC method) of the surface resin of the multilayer film in the present invention is usually 100 ° C. or higher, preferably 105 ° C. or higher. More preferably, it is 110 ° C. or higher. The lower limit is that the surface layer is heated to steam of at least 100 ° C. during heating in a microwave oven or the like, so that if the surface layer melts, it adheres to the container or film and becomes difficult to peel off after heating. Also, the melting point should be as high as possible because it will fuse with the contents of the package.However, in order to easily exert the effects of a plasticizer, adhesive, etc. It is not necessary to be higher than the melting point.

Similarly, the crystallinity of the surface resin film is preferably about 3 to 80%, more preferably about 5 to 70%, in order to mainly maintain the heat resistance as the surface layer.
More preferably, it is about 7 to 60%. The ratio of each layer of the film of the present invention is such that the layer composed of the resin (A) has a total thickness ratio of usually 80 to 5%, preferably 70 to 10%, more preferably 60 to 15%, to all layers. More preferably, it is 50 to 20%. Similarly, the ratio of the layer made of the resin (D) is usually 20 to 95%, preferably 30 to 9%.
0%, more preferably 40-85%, even more preferably 5%
0 to 80%.

Preferably, a collecting layer (R) made of a collected resin, in which the above-mentioned multilayer film made of the resin (A) and / or the resin (D) is collected, may be arbitrarily added. . In this case, more specifically, at least one recovery layer (R) may be added at a thickness ratio within the range of preferably 5 to 50% of the whole layer. However, as long as the transparency, gloss and the like are not impaired, it may be used for the surface layer in some cases. In addition, when at least one layer made of another thermoplastic resin (F) is further added, it is preferable that the total thickness ratio to the total layer be 1%.
It should be 0 to 50%, more preferably 10 to 40%, and still more preferably 10 to 30%. Other thermoplastic resins (F) include aromatic polyester resins,
Selected from polyolefin-based resins, ethylene-vinyl alcohol-based resins, polyamide-based resins, ethylene (or at least one other α-olefin-based resin) -carbon monoxide-based (hydrogenated) resin, and the like. At least one other resin can be used.

More specifically, polyolefin resins (PO) such as polyethylene resins, polypropylene resins, polybutene-1 resins, poly-4-methylpentene-1 resins, and polyethylene terephthalate (including modified resins) ) Resins, polyester resins (PEST) partially containing aromatic components such as polybutylene terephthalate (modified) resins, ethylene-vinyl alcohol copolymer resins (EVOH), α-olefin- Carbon oxide copolymer resin (containing hydrogenated resin), α-olefin (ethylene) -styrene copolymer resin (containing cyclic hydrogenated resin), ethylene-cyclic hydrocarbon-based compound copolymer resin (containing hydrogenated resin) , A polyamide-based resin, at least one layer of a resin selected from at least one selected from caprolactone-based resin, It may have a structure. Further, an arbitrary layer may be irradiated with a known method such as a high energy beam such as an electron beam and crosslinked to have heat resistance.

In a preferred form of the layer structure, the layers composed of the above-mentioned resins are respectively composed of a resin (A) composition C, a resin (D) composition E, and other thermoplastic resins. When the composition is abbreviated as F and the recovery layer is abbreviated as R, the layer configuration is represented as follows. However, the suffixes 1 and 2 mean different resins of the same type, or compositions having the same resin even if the additives are different. Specifically, Group 1
C / E, E / C / E, C / E / C / E, E / C / E / C
/ E, C / E / C / E / C,... Group 2 is E1 / E2 / C / E2 / E1,
E / C1 / C2 / E, E / C1 / C2 / C1 / E, E1
/ C / E2 / C / E1, C1 / C2 / E / C2 / C1,
..., etc. Group 3 is C / R / E,
C / E / R, E / R / C, E / R / C / R / E, E / C
/ R / C / E, etc.

Next, a typical production method of these films will be described. The resin (A), the composition (C), the resin (D), the composition (E), and / or other heat if necessary. Plastic resin (F), selected from the composition comprising the resin (F), each plasticized separately by an extruder, and if necessary, kneaded with a predetermined additive, and extruded with a multilayer die,
Preferably, it is stretched at least uniaxially, more preferably biaxially, formed into a film, suitably heat-set, imparts dimensional stability, and if necessary, temperature and time, degree of orientation, premixed crystal nucleating agent, etc. Thus, the degree of crystallinity can be freely controlled for each layer to impart heat resistance and dimensional stability, and the adhesive multilayer heat-resistant wrap film of the present invention can be obtained.

More specifically, for example, in the flat method,
Extrusion from a multilayer T-die, pull-down at a high draw ratio with cast rolls, quenching, heat treatment to impart heat resistance, or extrusion similarly, preferably quenching, and stretching with a roll stretching machine or tenter frame, Extrusion into a multilayer form from a circular annular die by a circular method, inflation at a high magnification, biaxial stretching, quenching, and then heat treatment, or more preferably, extrusion from a circular multilayer die, to a predetermined temperature by a water-cooled ring, etc. After quenching, there is a method of reheating to a predetermined temperature in the next step, blowing air, biaxially stretching by a tubular method, quenching, and then heat setting to promote dimensional stability and crystallization. Among these manufacturing methods, the manufacturing process is inexpensive, the productivity is good, and the multilayer (2
To 7 layers) is easy, the thickness accuracy in the width direction of the obtained film is good, the uneven thickness dispersion can be almost completely achieved, and the product yield is good.

The relationship between the heat shrinkage (X) and the heat shrinkage stress (Y) in a preferred range, expressed at 100 ° C., which is suitable for the heat-resistant multilayer adhesive wrap film of the present invention is as follows. In the following description, units to be described later are simply abbreviated as (%, g). In the XY coordinate system, within the range of the figure surrounded by the lines of the above formulas (1), (2), and (3), the reason is that the heat shrinkage (X) exceeds 45%. On the other hand, if the heat shrinkage stress (Y) exceeds 500 g, the wrap film placed on the dish during heating (for example, in a microwave oven) shrinks and comes off or breaks from the container, or the container or packaged object (foodstuff). ) Is undesirably deformed.

The following formulas (1) to (3) (the above units are omitted) Formula (1) Y ≦ (1500−20X) / 3 Formula (2) 0 ≦ X ≦ 50 Formula (3) 0 ≦ Y ≦ 500. A more preferable range is a range surrounded by the following formulas (4), (5), and (6) (units are omitted). Formula (4) Y ≦ (1400-20X) / 3 Formula (5) 2 ≦ X ≦ 45 Formula (6) 5 ≦ Y ≦ 400 The preferred range of the heat shrinkage ratio is in the range of 2 to 45%, and the more preferred range is 3 to 40%. It is. The preferred range of the heat shrinkage stress is 5 to 4
00 g.

The reason why the temperature is represented by the above-mentioned temperature is that when an object to be heated containing water is placed in a heat-resistant container mainly by a microwave oven or the like and cooked or simply heated, most of the water is initially steamed at about 100 ° C. Is exposed, swells, and is heated. Although various preferable packaging suitability in the present invention are mainly represented by the above-mentioned properties and their ranges, other sensory packaging properties are also practically important, and are described as preferred ranges in the above and below examples, respectively. . The thickness of the adhesive heat-resistant wrap film of the present invention is easy to handle as a household wrap film, raw material cost, as thin as possible in terms of environmental measures, preferably 5 to 15 μm, more preferably The value is 6 to 13 μm, more preferably 7 to 11 μm.

The range of the tensile modulus of this film is 1
Within the range of 5 to 180 kg / mm ^2, the lower limit is the cut property of the film (having good cutting ability), the stiffness of the film, and the extensibility of the film (after being pulled, cut, and stretched until wrapping, The upper limit is for keeping the fit and the cut (good cutting edge) at the time of packaging, in relation to the effect of controlling the breaking elongation of the film to an appropriate value. For the same reason, a preferred range is 20 to 170 kg / mm ² , more preferably 25 to 150 kg / mm ² .

The preferred range of shrinkage in the present invention is 10
It is usually 0 to 50% at 0 ° C, more preferably 2 to 45%.
%, More preferably 2-40%, most preferably 3-3%
The lower limit is 5%, and the lower limit is the fit at the time of heating (even if it is loosely packaged, it shrinks slightly and fits perfectly to the contents of the container. It is limited by such factors as disappearance and enlargement of the adhesion area, or less adhesion of the film to the surface of the film due to wrinkles, and adhesion.) The upper limit is limited by film detachment, tearing, containers (in the case of plastics), deformation of the contents, and the like.

The preferred range of the shrinkage stress value in the present invention is 0.
~500 (g / mm ^2), more preferably 5 to 400
(G / mm ² ), more preferably 5-350 (g / mm ² )
² ), most preferably from 10 to 300 (g / mm ² ). The lower limit is limited by the shrinkage rate at the time of heating, the fit to the container and the article to be packaged (same as the above-described case of the heat shrinkage rate), the strength exhibited by stretching, the cut property, and the like.
It is limited by detachment or tearing of the film from the container at the time of heating, deformation of the container or contents, and the like. The range of adhesion in the present film is in the range of 5 to 50 g · cm / 25 cm ² ,
The reason for this is that if it is less than the lower limit, film peeling occurs due to insufficient adhesion between the container or the film surface during packaging, storage (including refrigeration), and heating. Exceeding the upper limit will result in poor drawability from boxes and rolls, and the films will adhere too closely to each other during packaging, resulting in film extensibility after cutting (overlapping parts are unlikely to peel off and overlap naturally increases, etc.)
Poor packaging. The preferred range is 7 to 40 g.
cm / 25 cm ² , more preferably 8-35 g · cm /
25 cm ² .

The range of heat resistance of this film is usually 105
° C or higher, preferably 110 ° C or higher, more preferably 13 ° C or higher.
It is at least 0 ° C, more preferably at least 140 ° C, most preferably at least 160 ° C. Below the lower limit, the content shatters due to shrinkage of the package due to breakage of the package during heating in a microwave oven or the like, and the content is dried too much, and insufficient heating causes local heating. Although the upper limit is not particularly limited, it is about 230 ° C., and preferably about 200 ° C., because it is interlocked with other characteristics (for example, the workability is deteriorated, the tensile modulus is too high, etc.). In addition, the reason for the above heat resistance range is good for the time being if the film is not damaged by water vapor at about 100 ° C. in the initial stage of heating in a microwave oven or the like, but the portion in contact with the contents is,
(End of heating, especially when the amount of water vapor is reduced) If the mixture contains an oil component and salts, the temperature may become particularly high, and if the heat resistance is poor, holes may open and spread, or the film components may melt. Not only is it unfavorable for hygiene, but if it is packaged and heated without a container, the film will weld,
Furthermore, while taking out the package, it adheres and deforms in a vacuum state,
This is because if the contents are not separated, it may be impossible to take out the contents as they are.

The range of the crystallinity of the resin used in the present invention is as described above, and the crystallinity of a practical film is determined by the conditions of the composition constituting the film, the conditions of production of the raw material, and the stretching conditions. It can be freely controlled by heat treatment conditions and the like, and can be changed over a wider range than when only the composition conditions are changed. The upper limit can be higher than the raw material (pellet) if properly oriented and crystallized.
In some cases, it can be made amorphous by controlling the crystallization speed to some extent. In the present invention, these conditions can be freely controlled according to the purpose. The preferred barrier property in the present invention is mainly the barrier property of various odors. Here, the barrier property is represented by the oxygen barrier property (unit: cc / day · atm · m ² (23 ° C.-65%
RH), 1000 cc or less, preferably 5 to 700 c
c, more preferably about 10 to 500 cc, still more preferably about 15 to 400 cc, and most preferably about 20 to 300 cc. A part of the unit is omitted and represented. It is known that it is almost proportional to the smell bayer property of foods used in foods (correlated with grilled fish, vinegar, and other foods that are difficult to transfer if a special smell is transferred), the upper limit of the above range If it exceeds, the odor barrier property is deteriorated.

The methods for measuring various characteristics shown in the present invention are as follows. (1) The tensile modulus is defined as 100% of the stress value at 2% elongation in the vertical and horizontal directions with respect to the flow direction at the time of extrusion of the film, measured according to ASTM-D882.
And the average value of the thickness-converted values, and the elastic modulus (% unit) of the average value for each sample number n = 5 (units are partially omitted in the following items). (2) The heat shrinkage ratio is a 100 mm square (5
A 0 mm square film sample is dusted with powder of talc or the like so as not to adhere, placed horizontally in an air oven type constant temperature bath set at a predetermined temperature, and treated for 10 minutes while freely shrinking. Is calculated, expressed as a percentage of a value obtained by dividing the original dimension, similarly expressed as an average value (% unit) in the vertical and horizontal directions, and expressed as an average value for n = 5 samples.

(3) The heat shrinkage stress value is obtained by sampling a film into a strip having a width of 10 mm, setting the same to a predetermined length at a chuck interval of 50 mm at a chuck interval of 50 mm without loosening the film, and setting the same. It is immersed in silicone oil heated to a predetermined temperature and is detected by detecting the generated stress. It is expressed as the maximum value developed within 20 seconds after immersion. Similarly, the average value of the same value in vertical and horizontal directions is converted to thickness Of the sample (g / mm ² unit), and furthermore, the average number of samples at n = 5. (4) The contact work amount is a constant temperature chamber at 23 ° C. and a relative humidity of 65%. The film is tensioned and fixed to one end of each of two cylinders having a circular cross-sectional area of 25 square centimeters without wrinkling. Then, the two cylinders are aligned so that the film surfaces overlap with each other, and the film surfaces are pressed under a load of 500 g for 1 minute, and then peeled off at a speed of 100 mm / min in a direction perpendicular to each other by a tensile tester. Of work (g · cm / 25 square centimeters, hereinafter a part of the unit is abbreviated), and the number of samples is represented by an average value at n = 5.

(5) The heat resistance is defined as 30 mm width and 70 mm width.
Reinforce the 10mm each end of the long film with heat-resistant tape, clamp it, apply a load of 10gr to one end to the center of the film, and suspend it for about 10 minutes in a temperature-controlled air oven. It is determined whether or not the wire breaks at a predetermined temperature. If the wire does not break, it is determined that there is heat resistance. Also, when extending without breaking, mark 50
When 20% or more of the mm part has been extended, it is determined that there is no heat resistance. In the measurement, the temperature was measured at a pitch of 5 ° C., and expressed as the temperature one step before the fracture, and the number of sample repetitions n = 5
Expressed as the average of

(6) The crystallinity is defined as a standard sample in which the raw material resin is sufficiently annealed at an optimum temperature for crystallization and is in an equilibrium state, and the crystallinity determined by a wide-angle X-ray diffraction method is fixed. The correlation with the melting energy of the sample is determined and, for simplicity, a calibration curve is determined by the DSC method (according to JIS K7122), and the target sample is measured. However, when the film of the product is measured, the film is used as it is, or when it is not clear, it is converted to an experiment with a single layer equivalent, or the crystal melting point of the resin (A) component contained therein is 110.
The crystalline component at a temperature of at least ℃ is measured in terms of the crystalline component derived from the raw material component (mixed with other resins, also in the form of a multilayer), and expressed as the sum. However, preferably, the heat-resistant layer composed of the resin (A) is used. It shall be expressed only by. The degree of crystallinity of the film is freely controlled by the composition conditions, raw material production conditions, stretching conditions, heat treatment conditions, etc., and can be varied over a wide range from the values measured by the raw materials themselves. It is known to those skilled in the art that it can be made higher than the raw material if properly oriented and crystallized.

(7) The barrier property is represented by oxygen barrier property, which is measured according to the method of ASTM-D-3985, and the unit is; cc / m ² · day · 0.1 MPa.
(Atm) (measurement environment is 23 ° C.-65% RH).
(Hereinafter, the unit is partially omitted and is represented by cc.) (8) The viscosity of the liquid additive (B) is a B-type viscometer, for example, manufactured by Toki Sangyo Co., Ltd., in a low viscosity region (1000 centipoise). The following values are measured with a BL No. 2 rotor at a rotation speed of 30 rpm, and the values in the high viscosity region (1000 centipoise or more) are represented by values measured in the same manner using the same No. 4 rotor.

[0059]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. The aliphatic / aromatic copolymerized polyester resin (A) used herein is as follows. A-1 is an alcohol component of ethylene glycol 92 mol%, diethylene glycol 8 mol%, and an acid component of succinic acid 20. A copolymerized polyester resin consisting of 80% by mole of terephthalic acid and 80% by mole of terephthalic acid (crystal melting point: 190 ° C., crystallinity: 38%).

A-2 is composed of 95 mol% of ethylene glycol, 5 mol% of 1,4-butanediol, 85 mol% of terephthalic acid and 1 mol of glutaric acid.
Copolymer consisting of 3 mol% and succinic acid 2 mol% (crystal melting point: 180 ° C., crystallinity: 35%). In A-3, the alcohol component is 1,4-butadiol, and the acid component is adipic acid 41.
Glycerin triacetyl as a small amount of a polyhydric alcohol component is allowed to react with the copolymerized polyester consisting of 59% by mole of terephthalic acid and before branching.
Chain-extended resin (crystal melting point 129 ° C, crystallinity 28
%).

A-4 has an alcohol component of ethylene glycol, an acid component of succinic acid 60 mol% and terephthalic acid 4
A urethane-based compound is used as a polyfunctional monomer material in a copolymerized polyester-based resin consisting of 0 mol%, and a branched structure having a polymer structure in which an alcohol component is ethylene glycol and an acid component is succinic acid has a former structure of 4 and a latter structure. Are graft-polymerized at a ratio of 1 (a main peak having a crystal melting point of 188 ° C., a sub-peak at 104 ° C., and a former having a crystallinity of 24
%). A-5 is a copolymerized polyester composed of 1,4-butanediol as an alcohol component, 65 mol% of succinic acid and 35 mol% of terephthalic acid as an acid component,
A resin having 7 to 10 branches in the molecule with a polyhydric alcohol as a branch point, and a terminal carboxylic acid moiety ionized with Mg ions (crystal melting point: 125 ° C., crystallinity: 32%).

The aliphatic polyester resin (D) used herein is as follows. D-1 is obtained by adding 90 mol% of lactide (cyclic dimer) composed of L-lactic acid to D-lactic acid,
An aliphatic polyester resin obtained by copolymerizing 10 mol% of DL lactide composed of L-lactic acid (crystal melting point: 160 ° C., crystallinity: 34%). D-2 is an aliphatic polyester resin in which the alcohol component is ethylene glycol and the acid component is succinic acid (crystal melting point: 102 ° C., crystallinity: 33%). D-3
Is 85 mol% of glycolide and 15 mol% of L-lactide
Polyester resin (having a crystal melting point of 20)
0 ° C., crystallinity 31%). D-4 is an aliphatic polyester-based resin obtained by copolymerizing 90% by mole of 3-hydroxylacnic acid and 10% by mole of 3-hydroxyvaleric acid (crystal melting point: 125
° C, crystallinity 24%). D-5 is a polyester in which the alcohol component is 1,4-butanediol and the acid component is succinic acid.
A resin obtained by subjecting a terminal carboxylic acid portion to an ionomerization treatment with Mg ions (crystal melting point: 115 ° C., crystallinity: 35%).

The resins (F) other than the resins (A) and (D) used herein are as follows. F-1
Is a polybutylene terephthalate-based copolymer resin obtained by copolymerizing 84 mol% of 1,4-butanediol as an alcohol component, 15 mol% of triethylene glycol, and 1 mol% of polytetramethylene glycol.
7 ° C, crystallinity 38%). F-2 is an ethylene-vinyl alcohol copolymer resin (39 mol% ethylene copolymerized, crystal melting point 170 ° C., crystallinity 43%). F-3
Is ethylene-methacrylic acid-methyl methacrylate
Copolymer ionomer resin (having a methacrylic acid group content of 18% by weight, an ester group content of 60 mol%, and a degree of neutralization of Mg ions of 25%, temperature 190 ° C./load 2160
g having a melt index of 2.5).

The liquid additive (B) used herein has the above-mentioned preferred viscosity range described below, and the viscosity is hereinafter referred to in parentheses by centipoise, and the viscosity is measured at a temperature of 50 ° C./100° C. It is described in order. B-1 is diglycerin triacetyl monolaurate (200/30),
B-2 is a diglycerin triacetyl monocaprate (3
00/50), B-3 is glycerin triacetate (1
00/20), B-4 is epoxidized soybean oil (110/1
6), B-5 is diglycerin triacetyl monolaurate (250/10), B-6 is polyoxyethylene sorbitan laurate (210/34), B-7 is tetraglycerin pentaacetyl monolaurate (110/8) ),
B-8 is acetyl tributyl citrate (11/2).

The resin composition (C) used here is as follows. C-1 is 80% by weight of A-1,
A composition obtained by mixing 20% by weight of D-2 and mixing 1 part by weight of B-2 and 1 part by weight of B-3 as a liquid additive (B) with 100 parts by weight of these resins. C-2 is A-
2 to 60% by weight and D-1 to 40% by weight, and 100 parts by weight of these resins, as a liquid additive (B),
A composition in which 1 part by weight of B-7 and 1 part by weight of B-8 are mixed. C-3 is obtained by mixing A-3 to 60% by weight, D-3 to 30% by weight, and F-2 to 10% by weight.
A composition obtained by mixing 1 part by weight of B-1 and 1 part by weight of B-6 as a liquid additive (B) with respect to parts by weight. C-4 is
A-5 was mixed with 60% by weight and D-4 with 40% by weight, and as a liquid additive (B), 1 part by weight of B-8 and 1% by weight of B-4 were added to 100 parts by weight of these resins. The composition which mixed parts. C-5 is composed of 70% by weight of A-1 and 30% of F-1.
% By weight, and 1 part by weight of B-3 and 1 part by weight of B-6 as a liquid additive (B) are mixed with 100 parts by weight of these resins.

Also, the product itself, its packaging properties, its properties at the time of use, and other preferable reference checkpoints relating to the present invention are the following items which are difficult to quantify and include sensual performances. It is desirable to satisfy. Aging preservation of small rolls (50 m at 30 cm width)
When stored in a rolled box at 30 ° C. and 65% relative humidity for 30 days), the additive oozes out from the end of the roll, and the film has an appropriate peeling property and a sticky film surface. There is no roll, pulling out of the roll box, the film edge is stretched, static electricity is not badly generated, sticking is not done on the hand, box, etc., the film is easy to spread and easy to grasp by hand, pullout resistance That the film can be cut accurately, without cutting, wrinkling while the film is stretched, with moderate resistance, comfortable (with a light sound), without stretching and permanent deformation ,

The extensibility of the film means that the cut film can be wrapped well without being wrinkled or overlapped. Without or without a container, between the film-container, between the film-packaged material, between the films, the overlapped portion without swelling, and that it is in close contact, and that it does not come off during low-temperature storage or heating, It is heat-resistant and does not tear or melt during heating to form holes, and the film loses internal pressure and does not expand abnormally.It does not change its taste and hygiene during storage and heating. Odors and additives are not transferred to the film, and film fragments are not mixed in.The film can be easily removed after heating. To prevent fouling by welding to the contents or containers (especially made of synthetic resin), and that there is little problem in disposal after use.

(Example 1), (Comparative Examples 1 and 2) A-1 was mixed with 80% by weight and D-3 was mixed with 20% by weight, and 100 parts by weight of these resins were used as a liquid additive (B). ,
A composition obtained by mixing 1 part by weight of B-8 and 1 part by weight of B-1 was used as an inner layer (second layer), and then a D-layer was formed on the surface layer (first and third layers).
B-3 as a liquid additive (B) was added to 100 parts by weight of
Part B, 8 parts by weight of B-8, and 2 parts by weight of B-5 were used, and the same additive (B) was added to the surface layer as Comparative Example 1.
28 parts by weight in the same ratio, and 0.5 parts by weight of the same additive (B) as in Comparative Example 2 in the surface layer as in Comparative Example 2. Melt kneading with 100mm diameter and 1mm slit
Extruded from the annular die of two kinds and three layers structure with the layer ratio of 1/1/1 (the order of the first layer / second layer / third layer), and liquid paraffin was injected inside the tube. Then, the outside is quenched and solidified by a coolant (water), taken up by a rotary nip roll for uneven thickness distribution, and the position in the extrusion width (circumferential) direction is sequentially dispersed (twisted) in the flow direction, and the fold width is 140 mm. A uniform tubular raw material was created. Then, these raw materials are passed in a uniform state between two pairs of differential nip rolls in a stretching step, and then heated under a 55 ° C. atmosphere in a heating zone and heated. In a stretching zone under a 50 ° C. hot air atmosphere,
The expansion bubble is continuously formed by injecting air into the inside with the nip roll for air enclosing installed at the outlet in the flow direction, and at the end of the stretching of the cooling zone, the cold air of 16 ° C. is blown by the air ring to finish the stretching. I let it.

Next, the outlet nip roll on the downstream side in the flow direction is closed and the internal air is confined, and the film is simultaneously biaxially stretched so that the stretching ratio becomes approximately 5.0 times vertically and 4.6 times horizontally. Next, the nip roll and the deflator located upstream of the nip roll in the flow direction are uniformly folded, and in the next step, they are continuously passed through a heat set zone consisting of three zones each controlled to a predetermined temperature, and then the ear is cut off by a winder. And wound on two films each having a thickness of about 9.0 μm.
The stretching stability of the film was good, and the wound roll-shaped film was heated to about 30 ° C. and aged for about 12 hours. The film of Example 1 did not show any problems at this point. In the film of Comparative Example 1, turbulence between layers was easily generated during extrusion, and a uniform raw material could not be obtained, and bubbles were easily punctured during stretching. In addition, in the finished film, the additives tended to bleed out to the surface excessively after aging, and the roll-shaped winding had a tendency to collapse. In addition, the film surface was also soft and soft.

Next, the film of Comparative Example 2 had a tendency that the surface of the finished film was easily stretched and deformed when the film was peeled off because the surface of the film was peeled off, and the adhesion was low and measurement was not possible. Next, these films are finished into a small roll wound about 50 m around a 30 cm wide paper tube, placed in a box of a commercial household wrap (for vinylidene chloride resin wrap of Asahi Chemical Industry Co., Ltd.), and heated at 30 ° C. Aged further for 3 days. In Example 1, the properties of the film were expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount” and “90/6/100/190/16 (each of the above-mentioned units was Abbreviated) and the barrier property is 11
It was 0c.

The film of Comparative Example 1 had “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount” of 14/52/490/165/7 (as described above). Was. This film was poor in roll drawability and wrapping property and was inconvenient to use, and the film was easily shrunk during heating and was broken.
The properties of the film of Comparative Example 2 are “250/5/220”.
/ 55/0 (same as above) ", and the tensile modulus was too high to be rugged, static electricity was easily generated, packaging was difficult, and there was almost no adhesion, and wrapping was impossible. The packaging test was carried out at a sample repetition number n = 5 by raising rice in a commercially available microwave heating porcelain (or plastics) container, placing curry thereon, and varying the heating time in the microwave oven in various ways. .

The film of Example 1 was made of a commercially available vinylidene chloride resin (hereinafter referred to as a commercially available PV).
As in the case of DC), a predetermined amount was accurately drawn out with an appropriate resistance. Next, with respect to the cutting property of the blade attached to the box, the film of Example 1 was cut comfortably and the cutting property was good as in the case of commercially available PVDC. Next, at the time of heating in a microwave oven, the contact portion with the contents (curry) is not broken even when the heating time is slightly long, and in the case of a plastics (PP; polypropylene) container, it is partially attached to the container. No fouling phenomena at all, good packaging and heating, easy peeling and removal of the film later, good taste of cooked products, good smell through storage during storage There was nothing. As a result, the film of Example 1 described above had characteristics within the preferable range of the reference check item.

(Example 2) D-2 was added to the surface layer (first and third layers).
Mixed resin 1 of 60 parts by weight of resin and 40 parts by weight of D-3 resin
The hydrogenated petroleum resin had a ring and ball softening point of 12
5 parts by weight of a resin at 5 ° C, B-2 as a liquid additive (B)
Was mixed with 5 parts by weight, 6 parts by weight of B-8, and 2 parts by weight of B-4, and A-1 resin 60 was used for the inner layer (second layer).
Using a resin obtained by mixing 40 parts by weight of A-3 resin in parts by weight,
Processed in the same manner as in Example 1 as a multilayer of a two-type three-layer structure in which the respective layer thickness ratios were (30/40/30: each%) in the order of (first layer / second layer / third layer). As a result, a film of about 8 μ was obtained. The characteristics of this film are expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount”, and are “130/5/70/180/29 (each of the above units is abbreviated)”. The barrier properties are
It was 180 cc. A packaging test was conducted in the same manner as in Example 1, but the packaging property was also within the above preferred range. No problems such as breakage were observed in the same heating test using a microwave oven. In the storage test, the smell did not leak much. As an additional embodiment, Embodiment 1
A total of 5 layers were inserted into the intermediate layer on both sides of the surface layer and the inner layer (the ratio was 10% with respect to the entire layer). A film was obtained in a similar manner. This film had substantially the same characteristics, and was in a preferable range including the packaging characteristics.

(Example 3) D-1 was added to the surface layer (first and third layers).
70% by weight of the resin and 30% by weight of the D-5 resin were mixed, and 100 parts by weight of the resin was mixed with 7 parts of B-3 as a liquid additive (B).
Using a composition obtained by mixing 10 parts by weight of B-7 and 10 parts by weight of B-7, mixing A-2 resin in the inner layer (second layer) and 2 parts by weight of B-1 as a liquid additive (B) in 100 parts by weight of the resin. The thickness ratio of each layer was (first layer / second layer / third layer)
Layer) in order (20/60/20:% each) 2
It was processed in the same manner as in Example 1 to obtain a film having a thickness of about 8.5 μ as a multilayer structure having three seed layers.
Expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount”, “120/3/130/17
5/18 (each of the above-mentioned units is abbreviated) ", the barrier property was 480 cc, and a packaging test was carried out in the same manner as in Example 1, but the packaging property was also within the preferred range. No problems such as breakage were observed in a similar heating test using a microwave oven, and almost no smell leaked out in a storage test.

(Example 4) D-4 was added to the surface layer (first and third layers).
3 parts by weight of a hydrogenated terpene resin, 10 parts by weight of B-3 as a liquid additive (B), and 100 parts by weight of the resin and 100 parts by weight of the resin
Using a composition obtained by mixing 5 parts by weight of -5, an inner layer (second layer)
A-2 resin is used for each layer thickness ratio (first layer /
A second layer / third layer (35/30/35:% each) was formed in the order (35/30/35:%), and processed in the same manner as in Example 1 to obtain a film of about 8.0 μm. The characteristics of this film are as follows: "tensile modulus / heat shrinkage / heat shrinkage stress /
Expressed in the order of “heat resistance / adhesion work amount”, “120/0/0”
/ 175/25 (each of the aforementioned units is abbreviated). " The barrier property was 400 cc. Example 1
A packaging test was carried out in the same manner as described above, but the packaging property was also within the above-mentioned preferred range, and no problems such as breakage were observed in a similar heating test using a microwave oven. In the preservation test, no odor leaked out as compared with that of the above-mentioned example, and the contents were not dried and deteriorated.

(Examples 5, 6, 7) and (Comparative Example 3) As shown in Table 1, resins used for the surface layers (first and third layers) were selected. However, in Example 5, a mixture of 55% by weight of D-2 and 45% by weight of D-3 was used.
A mixture of 40% by weight of -4 and 60% by weight of D-5 was used. Next, in each of 100 parts by weight of each resin, a liquid additive (B) of the type described above was added to the surface layer as shown in Table 1.
To the composition described in the above, and then the inner layer (second
The resin for the layer was selected as shown in Table 1. However, in the inner layer of Example 5, 2 parts by weight of a liquid additive (B) having a mixing ratio of 2/1 of B-5 / B-7 was used as the liquid additive (B) per 100 parts by weight of the resin. Similarly, as the liquid additive (B), a composition obtained by mixing 1 part by weight of a mixture having a mixing ratio of B-2 / B-1 of 2/1 was used.

These compositions were sufficiently kneaded with two extruders each having a screw diameter of 50 mm, and two kinds of the three types having a diameter of 100 mm and a slit of 0.8 mm were used.
Extruded from a multilayer (three-layer) annular die having a layer structure, and the thickness ratio of each layer was set to 35 /
Glycerin triacetate is injected into the inside of the tube, quenched and solidified with a coolant (water), taken up with a rotary nip roll for uneven thickness distribution, and extruded width. The positions in the (circumferential) direction were sequentially dispersed (twisted) in the flow direction, and a uniform tubular raw material having a folding width of 140 mm was created.

Next, these raw materials are uniformly dispersed.
In the stretching step, the nip roll is passed between two pairs of differential nip rolls, is heated in a heating zone under an atmosphere of 50 ° C., and is heated. The expansion bubble is continuously formed by injecting air into the inside at the end, the cold air of 15 ° C. is blown at the end of the extension of the cooling zone to terminate the extension, and then the outlet nip roll on the downstream side in the flow direction is closed and the inside is closed. The air is confined, and the film is continuously biaxially stretched so that the stretching ratio becomes approximately 5.0 times vertically and 4.7 times horizontally, and then uniformly folded by the nip roll and a deflator located upstream in the flow direction. In the next step, each was controlled to a predetermined temperature.
It was passed continuously through a heat-set zone consisting of two zones, then the ears were cut off by a winder and wound up into two films of about 9.2 μm thickness. Although the stretching stability of the films of Examples 5, 6, and 7 was good, in the case of Comparative Example 3, the bubbles were swayed and unstable, and these films were then placed in a 30 cm wide paper tube. Finish the roll into a small roll of 50 m and place it in a box for a commercial household wrap (vinylidene chloride resin wrap of Asahi Kasei Kogyo Co., Ltd.).
After aging for a week, a packaging test was performed.

Table 1 below shows the physical properties of the films of Examples 5, 6, 7 and Comparative Example 3.

[Table 1]

In the packaging test, rice was put on a porcelain (or plastics) container for heating a microwave oven,
A curry was placed thereon, and the heating time was variously changed in a microwave oven. At first,
The wrap was pulled out from each box containing the film and wrapped. As a result, it was found that the films of Examples 5, 6, and 7 were accurately drawn out from the box with appropriate resistance as in the case of the above-mentioned commercially available vinylidene chloride resin (hereinafter abbreviated as commercially available PVDC). Although the film could be pulled out quantitatively, the film of Comparative Example 3 (hereinafter, referred to as ratio 3) was not preferable because it came out of the box too much, or was stuck here and there due to generation of static electricity.

Next, with respect to the cutting property with the knife attached to the box, the films of Examples 5, 6, and 7 were commercially available PVDC.
Like the product, it cut comfortably and had good cutting ability. Ratio 3
Is because the film has too high elasticity and little adhesion, so it is difficult to fix the film to the holding part of the box at the time of cutting, the core of the roll is blocked and it is difficult to pull out, The cutting surface was difficult to cut into the cutting edge, and the cut surface was disengaged from the cutting edge and was torn diagonally, resulting in markedly poor cutability. Poor packaging properties (Films stick together due to static electricity or stick to arbitrary places, but there is no adhesion to the container and film, so the film spreads, It couldn't be fixed).

Next, at the time of heating in a microwave oven, the ratio 3 is such that the film does not adhere as described above, so that water vapor easily leaks, the content is easily heated locally, the content is easily spilled out, and The taste has become worse. The films of Examples 5, 6, and 7 have none of these defective phenomena, can be satisfactorily packaged and heated, can easily peel off and remove the film later, and have good taste of cooked products. No odor leaked through the film, a property within the preferred range of the present invention. Examples 5 and 6
The barrier properties of No. 7 are 380cc / 480c, respectively.
c / 520 cc. Further, the roll films of the respective examples did not have the problem of odor during storage described above.

Next, as Comparative Example 4, a resin of D-2 (crystal melting point: 102 ° C., crystallinity: about 33%) was used for the surface layer, and A-3 (crystal melting point: 129 ° C., crystallinity: about 28%) was used for the inner layer. %), The liquid additive (B) was added in the same manner as in Example 5 (however, 10 parts by weight of the same liquid additive (B) was added to the inner layer), and processed in the same manner to form a film. Obtained. However, the heat treatment after the stretching was not performed. The characteristics of this film are
Expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount”, “10/70/530/90”
/ 15 (each of the above-mentioned units is abbreviated) ", and the tensile modulus was too low to easily elongate, and the handleability and packaging properties were poor. In addition, the package was too shrunk when heated, and the packaging was easily detached and easily broken. In addition, when the surfaces of the films are fused with each other, the object to be packaged, the container, and the like, and the surfaces are fused and peeled off, fragments tend to be cut off and remain.

(Examples 8, 9, 10, and 11) Resins for two types and three layers (surface layer / inner layer / surface layer) were selected as shown in Table 2 below. 35 /
30/35 (%), and the surface resin (D-1 / D
-2 / D-3 / D-5), 7 parts by weight of B-3 and 6 parts by weight of B-5, D-1 for the liquid additive (B), respectively.
2 is 5 parts by weight of B-2, 6 parts by weight of B-8, 2 parts by weight of B-4, and D-3 is 10 parts by weight of B-3 and 4 parts of B-2.
2 parts by weight of B-4, 2 parts by weight of B-4, 5 parts by weight of B-7 and 3 parts by weight of B-5 were added to D-5, and the resin shown in Table 2 was selected for the inner layer. These were processed in the same manner as in Example 1 by adjusting the stretching temperature, the stretching ratio, the heat treatment, and the like, respectively, and were processed in the same manner, each having an average thickness of about 9.3 μm and having the physical properties shown in Table 2 below. A stretched film was obtained. The stretchability was good and there was no major problem.

[0085]

[Table 2]

A packaging test was performed on these films in the same manner as in Example 1. As a result, the drawability, cut property, stretchability, overlap property, adhesion property, heating property, and other properties were sequentially tested, but no particular problem was observed. There was
The barrier properties are 460cc / 540cc, respectively.
/ 120cc / 650cc. (Example 12) 1 of A-4 for surface layer (1, 5 layers)
B-3 as a liquid additive (B) in 10 parts by weight
In the same manner, an ethylene-vinyl acetate copolymer resin (melt) containing 3 parts by weight of the additive B-2 was used as an inner layer (2 or 4 layers) using a composition in which 8 parts by weight of B-1 and 8 parts by weight of B-1 were mixed. (Index: 0.8, density: 0.930 g / cubic cm), A-4 resin is used as the intermediate (three-layer) layer, and the thickness ratio of each layer is “25/10/30/10 /
25 (each%) ", kneaded and plasticized by three extruders, and then extruded from a three-type five-layer die to form a raw material. Next, an electron beam (energy: 500K)
A stretched film having an average thickness of about 9.3 μm was obtained in the same manner as in Example 1 except that the treatment was carried out at 6 Mrad in V). The properties are expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / close contact work amount” and are expressed as “75
/ 30/270/180/24 (each of the aforementioned units is abbreviated). " Each packaging test was also within the preferred range as described above, and no major problems were observed. The packaging test was within the preferred range of the present invention.
c.

(Example 13) A-layer was applied to the surface layer (first and third layers).
(3) 100 parts by weight of resin, 8 parts by weight of liquid additive B-8 and B
A composition obtained by mixing 4 parts by weight of -2 and 3 parts by weight of B-4,
Using A-2 resin for the inner layer (third layer), a multilayer (three layers) T
Die (surface length: 500mm, opening slit: 0.5mm)
Using a commercially available casting equipment, a draw ratio (drawing ratio) of about 35 and a film of about 14 μm were obtained.
Next, heat treatment was performed to complete a small roll similar to the above. The properties are expressed in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / close work amount” and are expressed as “130/0/0 /
175/20 (each of the above units is abbreviated). "
It is easily clogged with gels and carbides, and the film being extruded is easily drawn down, making thickness control somewhat difficult.
The film could be obtained although it was easily carried into a cast roll and the roll releasability was somewhat poor. In the packaging test, the packaging workability such as cutability and adhesion was slightly inferior to Example 1, but was within the usable range. It is considered that the reason why the packaging workability is slightly inferior is that the film is not stretch-oriented due to the large thickness or the like. The barrier property was 380 cc.

(Example 14) As a surface layer (first and third layers), 100 parts by weight of D-1 resin, 8 parts by weight of B-1 and 6 parts by weight of B-8 as a liquid additive (B) were used. Are used, and A-2 resin is used as the inner layer (second layer), and the respective layer thickness ratios are (first layer / second layer / third layer).
2 types 3 in the order of (30/40/30:% each)
It was processed in the same manner as in Example 1 to obtain a multilayer
μ film was obtained. The properties of this film are expressed as “140/5/80/175/22” in the order of “tensile elastic modulus / heat shrinkage rate / heat shrinkage stress / heat resistance / adhesion work amount”.
(The above-mentioned units are omitted.) The barrier property was 340 cc. A packaging test was carried out in the same manner as in Example 1, but the packaging property was also within the above preferred range. No problems such as breakage were observed in the same heating test using a microwave oven. In the storage test, the smell did not leak much. Further, a resin layer formed by collecting and molding the above-mentioned film is inserted into the intermediate layer on both sides of the surface layer and the inner layer in a total of two layers, and each layer is added at a layer thickness ratio of 10% with respect to the entire layer, thereby adding a total of five layers. A film was obtained in a similar manner. This film had substantially the same characteristics as the above-mentioned film not containing the recovery layer, and was in a preferable range including the packaging characteristics.

[0089]

According to the present invention, a composition obtained by mixing a resin and a liquid additive excellent in environmental and sanitary properties and processability stability is processed into a thin film to give specific characteristics. In addition, as a non-halogen-based material-saving film with barrier properties and heat resistance, it fulfills various required characteristics (such as ease of use) at the time of packaging and is easy to dispose of, and is useful as a film for house hold wrap. A heat resistant adhesive wrap film could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/04 C08L 67/04 // (C08L 67/02 (C08L 67/02 101: 00) 101: 00 ) F-term (reference) 4F100 AH01A AH01B AH01C AH02A AJ11A AJ11B AJ11C AK41A AK41D AK42B AK42C AK42D AL01A AL01D BA02 BA03 BA06 BA07 BA10A BA10B BA10C BA15 CA04A CA04B CA04C CA30A CA30B CA30C GB15 JA04A JA06A JA06B JA06C JA11A JA20A JA20B JA20C JD02 JJ03 JK07 JL11 JL16D YY00A YY00B YY00C 4J002 CD162 CF031 CF061 CF071 CF081 EC056 EH046 GF00 GG02 4J029 AA03 AB07 AC02 AD01 AD06 AE03 BA02 BA03 BA05 BA08 BD03A BD07A CA02 CA03 CA04 CA05 CA06 CD03 EA02 EA05 EG02 EG03 EG09

Claims (11)

[Claims] An aliphatic / polyolefin having a crystalline melting point of 110 to 230 ° C. and containing 10 to 90 mol% of a component composed of an aromatic monomer.
At least one layer of a resin composition (C) containing 3 parts by weight or less of a liquid additive (B) with respect to 100 parts by weight of a resin mainly composed of an aromatic copolymerized polyester resin (A); 10 of resin mainly composed of resin (D)
A film composed of at least one layer of a resin composition (E) containing 1 to 25 parts by weight of a liquid additive (B) with respect to 0 parts by weight, and having a tensile modulus of 15 to 180 k.
g / mm ² , heat resistance of 110 ° C. or higher, and adhesion (working of adhesion) of 5 to 50 g · cm / 25 cm ² . 2. The heat shrinkage X% at 100 ° C. of the film, the heat shrinkage stress Yg / mm ² , and the relationship between the two are within the range of the following equations (1) to (3). The heat-resistant multilayer adhesive wrap film according to claim 1, wherein the film is provided. (Equation 1) Y ≦ (1500-20X) / 3 (Equation 2) 0 ≦ X ≦ 50 (Equation 3) 0 ≦ Y ≦ 500 3. An aliphatic / aromatic copolymerized polyester resin (A) comprising oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 30-90 mol% of at least one monomer selected from 4-cyclohexanedicarboxylic acid,
10 to 70 mol% of at least one monomer selected from terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid as an aromatic acid component, and ethylene glycol and propylene glycol as alcohol components.
1,4-butanediol, 1,6-hexanediol,
1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, a copolymer comprising at least one monomer selected from polyethylene glycol,
The heat-resistant multilayer adhesive wrap film according to claim 1 or 2, wherein the heat-resistant multilayer wrap film is at least one selected from these polymers. 4. A resin mainly composed of an aliphatic / aromatic copolymerized polyester resin (A), comprising 50 to 99% by weight of the aliphatic / aromatic copolymerized polyester resin (A) and a resin other than the resin (A). The heat-resistant adhesive wrap film according to any one of claims 1 to 3, wherein the resin composition contains 1 to 50% by weight of the thermoplastic resin. 5. The aliphatic polyester resin (D) is an aliphatic polyester resin comprising an aliphatic dicarboxylic acid and an aliphatic dialcohol, or D-lactic acid, L as a monomer.
-Lactic acid, DL (racemic) form of the lactic acid, meso form of the lactic acid,
And glycolic acid, 3-hydroxyvaleric acid, ε-caprolactone, 2-hydroxy-2,2-dialkylacetic acid,
2-hydroxy-2,2-dialkylpropionic acid, 4
The heat-resistant multilayer adhesive according to any one of claims 1 to 4, wherein the adhesive is at least one selected from a resin consisting of at least one hydroxycarboxylic acid selected from -hydroxybutanoic acid and 3-hydroxyhexanoic acid. Wrap film. 6. The heat-resistant multilayer adhesive wrap according to claim 1, wherein the aliphatic / aromatic copolymerized polyester resin (A) has a crystallinity of 5 to 80%. the film. 7. The liquid additive (B) has a viscosity of at least 5 centipoise at 50 ° C.
The heat-resistant multilayer adhesive wrap film according to any one of claims 1 to 6, wherein the liquid is a liquid of 500 centipoise or less at ℃ and a boiling point of a main component thereof is 170 ° C or more. 8. The liquid additive (B) comprises at least one alcohol component selected from aliphatic alcohols, alicyclic alcohols, polyhydric alcohols, and polycondensates thereof, and aliphatic fatty acids and fatty acids. Free esters with at least one acid component selected from aromatic polycarboxylic acids and aromatic polycarboxylic acids, natural fatty acid esters, esters of aliphatic hydroxycarboxylic acids with alcohols and / or aliphatic fatty acids, and these alcohols , Modified esters, polyoxyethylene alkyl ethers, and their free esters, aliphatic polyester oligomers, cyclic dimers, mineral oils, liquid paraffins, and low-polymers composed of saturated hydrocarbon compounds. 8. A method according to claim 1, comprising at least one plasticizer selected. A heat-resistant multilayer adhesive wrap film as described in any of the above. 9. A film having a surface layer composed of a resin composition (E) containing a liquid additive (B) in a resin mainly composed of an aliphatic polyester resin (D), and an aliphatic / aromatic copolymer. It has an inner layer made of a resin mainly composed of a polyester resin (A) or a resin composition (C) containing a liquid additive (B) in the resin (A), and is composed of at least three layers. The heat-resistant multilayer adhesive wrap film according to any one of claims 1 to 8. 10. A film having a surface layer composed of a resin composition (E) composed of an aliphatic polyester-based resin (D), and a resin mainly composed of an aliphatic / aromatic copolymerized polyester resin (A), or It has an inner layer made of the resin composition (C) made of the resin (A), and the surface layer is made of the resin composition (E) having a lower crystal melting point than the inner layer and / or containing more liquid additive (B). Claim 1 characterized by the fact that
10. The heat-resistant multilayer adhesive wrap film according to any of 9. 11. A film comprising at least one layer containing a resin composition (C) comprising a resin mainly composed of an aliphatic / aromatic copolymerized polyester resin (A) and an aliphatic polyester-based resin (D). And at least one layer containing the resin composition (E) containing the liquid additive (B) in the resin to be used,
And at least one layer (R) containing a resin recovered from the layer according to any one of claims 1 to 10.
0. The heat-resistant multilayer adhesive wrap film according to any one of 0.