JPS59220363A - Polyester laminated film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyester laminate film having excellent physical properties and adhesive properties as a film, and particularly to printing inks; vacuum-deposited films of aluminum, etc., or sputtering-deposited films;
Laminate material made of polyethylene, polypropylene, etc.: polyvinylidene chloride coated film to provide gas barrier properties, ethylene vinyl alcohol copolymer film, polyvinyl alcohol acid, etc.; adhesion or lamination properties, and photographic photosensitive properties. The present invention relates to a polyester laminate film that has excellent adhesion to a magnetic emulsion or a magnetic material for magnetic tape, as well as excellent adhesion or lamination with other materials such as aluminum foil or paper.

As is well known, polyester film (hereinafter referred to as PE5T film) exhibits stable properties over a wide temperature range of -60 to 150°C, and is strong, dimensionally stable, oil resistant, chemical resistant, moisture resistant, and transparent. It is a sanitary and safe material with excellent electrical insulation and electrical insulation properties. For this reason, it is used in a wide range of applications such as magnetic tape, gold and silver thread, labels, photographic films, adhesive tapes, packaging materials, various miscellaneous goods, and electrical insulation materials.

However, PE5T film generally has poor adhesion to other materials or coatings, so when laminating, coating, printing, etc., it is necessary to place an undercoat on the processed surface of PE5T film to improve adhesion to those materials. It was necessary to provide an anchor layer or physically or chemically modify the processed surface. Adhesives used as the undercoat layer include incyanate-based, polyethyleneimine-based, organic titanium-based, etc. Physical competitive modification methods include corona discharge treatment or combination with bonding strength monomers. Polymerization methods, polymer blend methods, and the like are known, but either method increases the number of processing steps, which inevitably increases costs. Moreover, the physical properties of polyester are better as it is pure, and when copolymerization, polymer blending, or addition of additives is performed, the physical properties of the film, particularly heat resistance, dimensional stability, mechanical properties, etc., deteriorate. Moreover, PE5T films are often recovered and reused, but depending on the type of coating film, the polymer often undergoes thermal deterioration or gels during the melting process.

-・According to the confirmation by the inventor of the box, PE5T
The physical and chemical properties mentioned above have a close correlation with the increase in density when heated to 150°Ci, as will be detailed later. The density increase is 35 x 10, which exhibits physical and chemical properties.
- ”g/cm or more. However, such a large increase in density means that it is highly crystalline, and as mentioned above, problems such as poor adhesion will clearly appear. Therefore, it is necessary to improve the adhesion in some way.

The present inventors have focused on these circumstances and have conducted various studies in an attempt to improve the adhesiveness without impairing the original properties of highly crystalline PE5T as described above. The present invention was completed as a result of such research, and consists of (A) a highly crystalline PE whose density increase is 35XIO-33/ca+8 or more when heat-treated at 150'O for 30 minutes;
On at least one side of the base layer (A) made of 5T, (B) the following low crystalline copolymerized PE5T (B-1): 5 to
60% by weight, copolymerized PE5T of the same (B-2): 30% by weight or less (excluding O), and highly crystalline PE5T of the same (B-3): 10% by weight or more. Surface layer (B) (B-1) Low crystalline copolymer PE5T whose density increase is 30X 10-3 g/cm8 or less when heat treated at 150°C for 30 minutes, (B-2) Block copolymer PE5T, (B -3) Highly crystalline PE5T having a density increase of 35X 10-33/cm3 or more when heat treated at 150°C for 30 minutes, the composition ratio of the surface layer (B) in the entire laminated film The gist is that the amount is 1 to 70% by weight.

In the present invention, the density increase during heat treatment is 35XlO-
The highly crystalline PE5T base layer (A) exhibiting 33/cm" or more guarantees the physical and chemical properties of the entire laminated film as well as the required properties such as heat resistance and dimensional stability.
Adhesion is ensured by the surface layer (B) consisting of a specific ratio blend of low crystalline copolymer PE5T (B-1), block copolymer PE5T (B-2), and high crystalline PE5T. The most important feature of the present invention lies in the structure of the surface layer (B).

That is, in the present invention, the material constituting the surface layer (B) is a low-crystalline copolymer P whose density increases little during heat treatment, as described above.
E S T (B-1), block copolymerized PE5T, and highly crystalline PE5T with a large increase in density during heat treatment are blended in specific amounts to form a film, and this surface layer (
B) has sufficient chemical resistance as a material constituting the surface layer of a laminated film and has excellent adhesive properties.

Therefore, by laminating this surface layer (B) on one or both sides of the base layer (A), which has excellent mechanical properties, it is possible to create an ideal film that has the original characteristics of PE5T film as described above and also has excellent adhesive properties. A typical laminated film can be obtained. Examples of dicarboxylic acids or condensation-polymerizable derivatives that can be used to produce the low-crystalline copolymerized PE5T include terephthalic acid, isophthalic acid, 1.5-(or 2,6- or 2-
゜7)-Naphthalene dicarboxylic acid, 4,4'-diphenylene dicarboxylic acid, bis(p-carboxyphenyl)
Methane, ethylene-bis-p-benzoic acid, 4,4'
-Diphenyloxycarbonate, ethylene bis(p-oxybenzoic acid), 1,3-trimethylene-bis(p-oxybenzoic acid), 1,4-7-tramethylene-bis(p-oxybenzoic acid)
-oxybenzoic acid) and 4,4'-sulfonyl dibenzoic acid, and the glycols include ethylene,
1.3-)rimethylene, 1.4-tetramethylene, 1.
6-hexamethylene, 1,8-octamethylene, l.

Glycols such as 10-decamethylene, cyclohexane-
1,4-diol, 1,4-cyclohexane dimetatool, 2,2,4-tetramethyl-1,3-cyclobutanediol and 2,2-dimethyl-1,3-propanediol, or p-sea Examples thereof include aralkylene glycols such as (hydroxymethyl)-benzene and p-di(β-hydroxyethoxy)-benzene. Also, the P
In addition to the above, typical alcohols used to modify E5T include adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, and 1,4-cyclohexanecarboxylic acid.
In addition to the above-mentioned typical glycols for modification, pentamethylene glycol, hepcumethylene glycol, eicosamethylene glycol, nonane methylene gelol, dodecane methylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1.3- Examples include propanediol, 1,3-butanediol, and 2,2,4-1-limethylpencunediol, but the acid component and glycol component constituting the low-crystalline copolymer PE5T are limited to these. It's not a translation. However, in order to achieve the purpose of the present invention, the most preferable PE5T contains terephthalic acid and ethylene glycol as main raw materials, and also contains isophthalic acid and ethylene glycol as acid components.
Amber, adipic acid, sebacic acid, azelaic acid, and glycol components such as tetramethylene glycol, polytetramethylene glycol, diethylene glycol,
Copolymerized PE containing 2,2-dimethyl=1,3-propanediol, propylene glycol, etc. as the third component
5T is an example. The copolymerization amount of the third component should be 5 mol % or more, and if it is less than 5 mol %, no further improvement in adhesive properties will be achieved. Regarding the surface layer (B), the adhesion improves as the proportion of the gametic crystalline copolymer PE5T increases.
Those containing more than % by weight will exhibit heat-sealing properties by themselves.

Next, what is block copolymerization P E S T (B-2)?
A block copolymer consisting of a highly crystalline segment I component and a low crystalline segment component, and the highly crystalline segment component has good affinity with the highly crystalline PEST (B-3) described below. In addition, since the low crystalline segment components have good affinity with the low crystalline copolymer P E S T (B-1), the block copolymer P
By coexisting EST (B-2), it becomes possible to obtain a surface layer CB) having both physical properties and adhesive properties. Typical t of such block copolymerized PE5T...
;B includes polyether red polyester elastomer, among which 7 to 95 of the total segment components
1r1. % is polyether glycol or copolyether glycol, and the alkylene moiety of these polyether glycol or copolyether glycol is an alkyl group having 2 to 12 carbon atoms.
Aryl of 0, 1. ((If you convert it to about 93-5% by weight)
is composed of polyester segments) is most suitable. This type of block copolymer, which belongs to the polymer class, usually has a melting point of 100°C or higher. Acid components used in the production of such polyether ester elastomers include terephthalic acid, isophthalic acid, phthalic acid, adipic acid, senohesic acid, succinic acid, azelaic acid, oxalic acid, dibenzoic acid, P, P. '-ethylene dibenzoic acid, 2,6-naphthalene dicarboxylic acid, etc., and glycol components include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, 1,6-hexamethylene glycol, and 1,4-cyclohexane. Examples include dimethatol, diethylene glycol, 2,2-dimethyl-1,3-propanediol, butylene glycol, pentamethylene glycol, and the like. Segment components constituting polyether ester include polyethers such as polyethylene oxide glycol, polypropylene oxide glycol, tetramethylene oxide glycol, copolymer glycol of ethylene oxide and propylene oxide, and copolymer glycol of ethylene oxide and tetrahydrofuran. , aliphatic polyesters such as polyneopentyl azelate, polyneopentyl adipate, and polyneopentyl sepacate, lactones such as poly-ε-caprolactone and polyvivalolactone, and polytetramethylene oxide glycol and polyethylene oxide glycol. Examples include reactants.

Incidentally, the adhesive properties of polymeric materials are generally considered to be affected by the type of surface functional groups of the polymer, surface irregularities, and crystallinity. However, the present inventors have developed various copolymer PEs.
We conducted various tests on the factors that affect the adhesion of 5T to printing inks, photosensitive emulsions, magnetic tape binders, various laminating materials, etc., and found that copolymerized PE5T with low crystallinity has excellent adhesion. and 15
It was confirmed that there is a high correlation between the increase in density when heated at 0°C and the adhesiveness. In order to ensure adhesion that meets the lJ requirements of the present invention, copolymer P
As E5T, the density increase is 30X・IO-3g/c
+*8 or less, more preferably 20 x 10-3g/c++
It became clear that the following should be selected.The increase in density varies significantly depending on the type and number of moles of the copolymer components of copolymerized PE5T, so by adjusting these appropriately, the increase in density can be increased. However, in the case of PET (polyethylene terephthalate) obtained from terephthalic acid and ethylene glycol, which is the most typical PE5T, there is no effective copolymerized PE5T to reduce the density increase (Δρ). Among the polymerization components, the acid component is preferably isophthalic acid, and the glycol component is 2,
2-dimethyl-21°3-propanediol, diethylene glycol.

1.4-Cyclohexane dimetatool, propylene glycol, etc. are preferable, and by copolymerizing 10 to 30 mol% of these, the Δp of copolymerized PE5T can be reliably adjusted to 30
X10'-3g/cn+8 or less.

Among them, when 30 mol% of 2,2-dimethyl-1,3-propanediol, diethylene glycol, or 1,4-cyclohexane methanol is copolymerized as a copolymer component, Δρ becomes 5 X 10-33/cm8 or less, and the copolymerization The adhesiveness of polymerized PE5T is extremely excellent.

By the way, low crystallinity copolymer P with a small density increase
E5T mixed with a small amount of the block copolymerized PE5T exhibits extremely excellent adhesion, but on the other hand, it has poor chemical resistance and solvent resistance, as well as poor scratch resistance and surface strength. It is not appropriate to use it as a laminated material as it is.

However, these formulations contain an appropriate amount of the highly crystalline PE5T described below.
It has become clear that adhesion can be improved without substantially impairing chemical resistance etc. That is, the surface layer (B) for improving adhesion, which is the most characteristic feature of the present invention, is a low-crystalline copolymerized PE exhibiting the above-mentioned density increase.
5T(B-1): 5 to 60% by weight (more preferably lO
~5.0% by weight) and the block copolymer (B-2)
: 30% by weight or less (excluding O) (more preferably 1 to 10% by weight), and highly crystalline PE5T described below
: A mixture containing 10% by weight or more (more preferably 40% by weight or more) is formed into a film. If the amount of the low-crystalline copolymer p EST (B-1) is less than 5% by weight, sufficient adhesion cannot be imparted to the surface layer (B). Moreover, the copolymerization P E S T
(B-1) has good transparency due to its low crystallinity,
Although it has the effect of increasing the transparency of the laminated film and increasing its suitability as a packaging film, etc., if the amount is less than 5*% by weight, this effect becomes insufficient and it becomes impossible to obtain a satisfactory transparency. On the other hand, if it exceeds 60% by weight, the surface properties of the surface layer (B), ie, chemical resistance, solvent resistance, lubricity, scratch resistance, etc., deteriorate, making it unsuitable for practical use. Especially copolymerized PE
In surface layer CB) containing too much S T (B-1), copolymerization PF, S occurs when the product is immersed or coated in solvents such as methyl ethyl ketone, tetrahydro dirane, benzene, acid-resistant ethyl, chloroform, trichlene, etc. T
(B-1) causes problems such as swelling and dissolution. Moreover, if characters or designs are mistakenly written on such a film, there arises a problem that these inks or paints cannot be removed with an organic solvent. For this reason, in the present invention, the content of the low crystalline copolymer PEST (B-1) in the film (B) is set at 5 to 60% by weight.

Furthermore, even when the block copolymerized P E S T (B-2) is not blended, the surface layer (B) exhibits considerable adhesion; however, by blending an appropriate amount of the P E S T (B-2), the surface layer ( The adhesion of B) is greatly improved, and the physical and chemical properties of the surface layer (B) itself are also improved.

As mentioned earlier, this is block copolymerized PE5T (B-2
This is said to be because the coexistence of PE5T (B-1) with low crystallinity and PE5T (B-3) with high crystallinity increases the homogeneity of the surface layer (B). However, when the blend l11- of the block copolymer P E S T (B-2) exceeds 30% by weight, the transparency of the surface layer CB) decreases, and the chemical resistance and scratch resistance decrease,
Furthermore, the surface hardness may decrease and the surface layer may stretch when adhesive tape is applied and removed, resulting in ripple-like wrinkles.

In addition, highly crystalline PE5T (B-3) is
It has the excellent properties of wood, and in order to give the surface layer (B) appropriate physical and chemical properties and chemical and solvent resistance, it must be blended at □lO weight % or more. .

In this way, in the present invention, low crystalline copolymer PEST (B-1) and block copolymer P are used as materials for the surface layer (B).
EST (B-2) and highly crystalline PEST
By using a mixture of (B-3) in an appropriate ratio, a surface layer (B) having appropriate physical and chemical properties and excellent adhesiveness can be obtained.

Next, the highly crystalline PE5T constituting the base layer (A) is PE5T obtained by condensation polymerization of dicarboxylic acid and glycol, and the dicarboxylic acid or condensation polymerizable derivative used in the production of PE5T is: Terephthalic acid, isophthalic acid, 1.5-(or 2.6-or 2.7-) naphthalene dicarboxylic acid, 4,4'-diphenylene dicarboxylic acid, bis(p-carboxyphenyl)methane, ethylene-
Bis-p-benzoic acid, 1,4-tetramethylene-bis-
p-benzoic acid, 4,4'-diphenyloxycarboxylic acid, ethylene-bis(p-oxybenzoic acid), 1,3-trimethylene-bis(p-oxybenzoic acid), 1,4-tetramethylene-bis( P-oxybenzoic acid) and 4,4
'-Sulfonyl dibenzoic acid and the like. In addition, glycol components include ethylene, 1,3-trimethylene, l
I4-te]ramethylene, 1,6-hexamethylene, ■
, 8-octamethylene, 1,10-decamethylene and other glycols, cyclohexane-1,4-diol, 1.4
-Cyclohexane dimetatool, 2.2,4.4-teI
・Ramethyl-1,3-cyclobutanediol, 2.2-
Examples include dimethyl-1,3-propanediol,
Furthermore, p-di(hydroxymethyl)benzene and p-di(β
Aralkylene glycols such as -hydroxyethoxy)benzene can also be used. Among these, the most preferred PE5T constituting the base layer (A) in the present invention are polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), but they are of course not limited to these, and will be described in detail below. Base layer (
It is also possible to perform a repolymer blend in which a third component is copolymerized within a range that does not impede the required properties as A).

- Generally useful high molecular weight PE5T resins are prepared using 0-lylolophenol, a 60/40 volume Ji ratio phenol-tetrachloroethane mixture, or similar solvent systems.
Intrinsic viscosity is 0.2 dl/g when measured at ~30°C
More preferably, it is about 0.4 dl/g or more, and particularly preferable PET has an intrinsic viscosity of about 0.5 to 1.
However, as a result of various experiments, in order to achieve the purpose of the present invention, the PE constituting the base layer (A)
As 5T, highly crystalline P whose density increase when heat treated at 150°C for 30 minutes is 35 x 10-3 g/cI113 or more, more preferably 37XIO''g/cμ3 or more.
It became clear that E5T should be selected. Also, the intrinsic viscosity is 0. Said density increase of PET homopolymer of EiOdl/g is 43X 10-3 g/cm8. The density increase of the PET homopolymer with an intrinsic viscosity of 0.90 dl/g is 39X 10-3 g/cm3, both of which are
A) It serves the purpose as a material.

PE5T with such a large increase in density has high crystallinity, and oriented crystallization is significantly promoted by film formation, stretching, and heat setting. A laminated stretched film with excellent mechanical properties and dimensional stability can be obtained.

However, if the density increase is less than 35 x 10-''g/am8, the effect of improving the properties mentioned above during stretching and heat setting of the 119Q product will be insufficient, and the mechanical properties such as strength and dimensional stability of the final laminated film will be stabilized. Sexuality, etc. becomes insufficient.

The constituent materials of the base layer (A) and surface layer (B) used in the present invention are as described above, but these may include stabilizers, antioxidants, coloring inhibitors, lubricants, fillers, and plasticizers as necessary. , thickeners, thinners, antifoaming agents, antistatic agents, pigments, and other various additives can be added. In addition, the highly crystalline PE5T used in the surface layer (B) is the same as the highly crystalline PE5T used in the base layer (A).
It may be the same as 5T or different.

In the present invention, the surface layer (B) is formed on at least one side of the base layer (A) made of the highly crystalline PE5T by a method described later.
are laminated and stretched and heat-set to obtain a PE5T laminated film. During lamination, the proportion of the surface layer (B) in the entire laminated film is 1 to 70% by weight, more preferably 5 to 40% by weight. It is necessary to do so. However, if the proportion of the surface layer (B) is less than 1% by weight, sufficient adhesive strength cannot be obtained because the thickness of the surface layer (B) as an adhesion improving layer is insufficient. If this is exceeded, the base layer (A) as a reinforcing layer becomes too thin, resulting in poor heat resistance and mechanical properties of the laminated film, and the film deforms not only when external force is applied in a high-temperature atmosphere but also when external force is applied at room temperature. or break.

Next, a specific method for producing a PE5T laminated film will be described, but the present invention is not limited to the following method.

The most preferable molding method for PE5T laminated film is a coextrusion method, and in this method, the base layer (A) and surface layer (B) are extruded from two or three extruders, respectively, and laminated using a compiling adapter or the like. A PE5T laminated film can be easily obtained by this method. In this case, the materials constituting the surface layer (B) may be melted together in advance, or they may be extruded while being kneaded using a static mixer or the like. The shape of the die is Fran I and circular.
The two extrudates may be laminated either inside the die or outside the die. As other lamination formation methods, an extrusion lamination method or a dry or wet lamination method may be employed, and in these cases, it is preferable to interpose a suitable adhesive on the lamination surface. In this case, the base layer (A) and the surface layer (B) may be formed by, for example, the T-Guy method or the inflation method.

The most common form of laminated film is a two-layer film in which a base layer (A) and a surface layer (B) are laminated, or a three-layer film in which a surface layer (B) is laminated on both sides of a base layer (A). However, it is also possible to laminate a plurality of these other layers (A) and (B) to make a 10-layer film or a 20-layer film, and such multilayer films have excellent pinhole resistance and #i resistance. The impact performance etc. will be even better. An example of such a multilayer film is rSPE journal.

It can be produced according to the method described in June 1973, Vol. 294, etc.

The composition ratio of the base layer (A) and the surface layer (B) can be adjusted by adjusting the discharge amount from each extruder when using a coextrusion method, or by adjusting the amount of output from each extruder when using a lamination method.
) can be easily adjusted by changing the thickness.

The PE5T laminated film of the present invention may be in an unstretched state, but if it is stretched appropriately before and after lamination, the mechanical properties of the product film can be further improved. Can stretching be done according to a known method?
The most preferred stretching temperature is about 70-'100'0. In addition, the preferable stretching ratio is 1.
2 to 6 times, more preferably 1.5 to 6 times, and in the case of biaxial stretching, 1.2 to 6 times in the longitudinal direction and 1.2 to 6 times in the transverse direction. Furthermore, it is also possible to perform heat treatment, corona discharge treatment, etc. before and after lamination and stretching.

The laminated film of the present invention obtained in this way has excellent adhesiveness and transparency, and has dimensional stability of +flF! Due to its good thermal properties and surface properties, it is extremely useful for packaging various foods. In particular, this laminated film does not lose its bonding strength with laminate materials (paper, polyethylene, polypropylene, aluminum foil, etc.) even after boiling or retort processing, so it is suitable for packaging materials such as cooked food packaging and boil-in bags. It is also useful as a packaging material for water products because of its good water resistance. Furthermore, it has extremely good adhesion with vinylidene chloride film, which has excellent gas barrier properties, making it useful as a packaging material for processed meat and seafood products such as hams and sausages, as well as foods that are susceptible to deterioration such as bonito flakes and miso. It's also expensive. In addition to its use as a food packaging material, its excellent mechanical properties can be used for general packaging, adhesive tape, planar heating elements, plate making, photographic film, and tracing materials. It can be used as a material for applications, labels, various display boards, stamping foils, silver threads, etc., and its excellent electrical properties (insulating properties) can be used to cover electric wires, printed circuit boards, capacitors, etc. It has a wide range of suitability as a material for magnetic tapes, magnetic cards, floppy disks, etc. Moreover, the layers (A) and (B) constituting the laminated film of the present invention are both polyester structures, and will not cause thermal deterioration or gelation even when used recovered materials are turned into chips and remelted. Therefore, it has the advantage that it can be recovered and reused, and if these characteristics are considered together, it can be provided economically at a sufficiently low cost.

Next, the configuration and effects of the present invention will be explained in more detail with reference to Examples, but prior to that, the measurement methods and processing methods of various physical properties adopted in experiments will be clarified.

[Density increase: Δρ] Based on JIS K 7112, the density of the sample before and after heat treatment at 30'O is measured using a (water-calcium nitrate) liquid-based density gradient tube, and the difference is defined as Δρ. However, the heat treatment conditions are as follows.

[Heat treatment] A substantially amorphous and unoriented sample was sandwiched between aluminum foil (thickness 0.05 mm) manufactured by Nippon Seiho Co., Ltd., and subjected to hydraulic pressure using a hydraulic press (heat press) manufactured by Shindo Metal Industry Co., Ltd. Heat treated at 150°C for 30 minutes under pressure of 10 kg/cm2 gauge.

[Haze value] Measured according to JIS K 8714 using a new haze meter S type manufactured by Toyo Seiki.

[Strength and elongation] Based on JIS K 2318, it was measured in an atmosphere of 20°C, 165% R, H using a universal tensile testing machine "Tensilon UTM3" manufactured by Toyo Baldwin, and the average value in the longitudinal and transverse directions Find it as.

[Intrinsic viscosity and reduced specific viscosity of polymer] Mixed solvent of phenol/tetrachloroethane = 372 (
Polymer (80 mg) was dissolved in 20 cc) and heated to 30'C using an Uherode capillary viscometer. Measure the viscosity at The unit is dl/g.

[Thermal Shrinkage Rate] Based on JIS C2318, heat treatment was performed at a temperature of 150° C. for 1 hour, dimensional changes before and after the treatment were measured, and the average value in the vertical and horizontal directions was determined.

[Chemical resistance of film] Magic ink No. 500 on the surface of film (B)
Write B in black, approximately 2 cm square. Next, after the ink has sufficiently dried, the written characters on the film surface are wiped off with gauze soaked in chloroform, and the subsequent surface condition is observed. And if the surface is smooth and shiny, mark O.
If the surface is rough and has lost its luster, mark it with an X.

[Boiling Treatment] The film is placed in a bag made of 50 mesh stainless wire mesh, immersed in boiling water, and boiled for 30 minutes. For films with a sealant laminated on the surface, paper is inserted between the films to prevent them from fusing together.

[Retort processing] Dyeing processing machine rHUHT 212/350 manufactured by Nichiita Seisakusho
Using a small type Obermeyer, the film was placed in a wire mesh bag similar to that used in the second boiling treatment and placed in flowing hot water, and heat treated at 120°C for 30 minutes.

For films with a sealant laminated on the surface, paper is inserted between the films to prevent them from fusing together.

[Heat sealing] Heat sealing was performed at 170° C. at a speed of 1/min using a high-speed automatic bag making machine rHS 400 manufactured by Shibu Kikai Co., Ltd. The seal width was 1 cm.

[Heat-sealing strength] The heat-sealed film is cut into strips with a width of 15 mm, and the sealing strength is measured by T-peeling using the "Tensilon UTMa type" used for measuring strength and elongation. Peeling speed 20
0 mm/min, measurement atmosphere 20°C, 65% R, H.

[Lamination strength] Polyethylene or polypropylene is extrusion laminated or dry laminated on the surface of the pEsTgNt film,
This is cut into strips with a width of 15 mm and a length of 20 crrr. If you make a cut in a part of the tip of this strip and stretch it, the sealing material will stretch and the PE5T film and laminate layer will peel off, so apply this peeled end to the same "Tensilon" as above and peel it off with a T-shaped peeling mold. Measure the laminate strength. Peeling speed 200mm/min, atmosphere 20℃, 65%R
,H.

Examples Using terephthalic acid as the acid component and ethylene glycol as the glycol component, 2,2-dimethyl-1,3-tetrapane was added in an amount of 5 mol %, 10 mol %, 20 mol %, and 30 mol % based on the ethylene glycol. Diol (NPG
) were added to produce four types of low-crystalline copolymerized PE5T. The reduced specific viscosity of the obtained copolymerized PE5T is 0.82.
．． They were 0.83, 0.85 and 0.93.

On the other hand, terephthalic acid is used as the acid component, and butanediol (BD) and polytetramethylene glycol (PTMG: molecular weight too) (BD/PTM) are used as the glycol components.
G = 85.7/14.3 (mole ratio)] A polyether ester disstomer was produced using the following method. The reduced specific viscosity of this nidistomer was 1.85.

A predetermined amount of each pellet of the obtained low-crystalline copolymer PE5T, nidistomer, and high-crystalline PET with an intrinsic viscosity of 0.60 was placed in a bag and mixed to form a material for the surface layer (B). On the other hand, the above-mentioned highly crystalline PET having an intrinsic viscosity of 0.60 was used as the material for the base layer (4).

Two extruders were used for film formation, and the extrusion temperature was 280℃ for both.
~290°C, and high crystalline PET was placed in one extruder.
Further, the mixed pellets were supplied to the other extruder, and the pellets were coextruded into a film while being laminated in a T die, and then rapidly cooled to obtain a laminated film.

At this time, adjust the extrusion amount of the image material to make the base layer (4) and the surface layer (
Although the thickness ratio of B) was changed, the thickness of the laminated film in the unstretched state was about 250 μm in each case.

This laminated film was stretched 3.5 times in the longitudinal direction (at a temperature of 85°C) using four-wheels with different circumferential speeds, and then 3.7 times in the transverse direction (at a temperature of 105°C) using a tenter.
It was heat-set at 50° C. while being relaxed by 5% in the lateral direction, and the surface was further subjected to corona discharge treatment.

The thickness of the obtained laminated film was about 19 μm. On the surface layer (6) side of the obtained laminated film, polyol and isocyanate-based adhesives (Kuraide Yakuhin Co., Ltd. [Take2 Tsuku A-971J and Takenate A3J made by the company] were mixed in ethyl acetate at a ratio of 9/1). (dissolved to a concentration of 30%),
The surface was coated using a gravure roll with a depth of 80 μm and 100 meshes.

After preliminary drying, an unstretched polypropylene film (CP) having a thickness of 60 μm was laminated using a nipple roll at 50° C., and then aged at 40° C. for 2 days.

The CP surfaces of each of the obtained CP laminate films were overlapped and sealed with a heat sealer, and after subjecting this to boiling treatment and retort treatment, the glabellar 2-mineral strength between the laminated film and CP was measured. In addition, the strength of the heat-sealed portion of the untreated product was measured.

The results are summarized in Table 1.

In Table 1, in Comparative Example (1-1), the increase in density of the low-crystalline copolymer PE5T blended in the surface layer (B) is too large, and since no polyether ester elastomer is blended, the adhesion The sex is extremely bad. Also, comparative example (1
-2) has poor adhesive properties because it does not contain polyether ester elastomer. On the other hand, comparative example (1-
In case 3), the amount of low-crystalline copolymerized PE5T in the surface layer (B) is insufficient and the amount of polyether-ester elastomer is too large, and the adhesiveness is somewhat good, but the transparency is poor and the strength is weak. Comparative Examples (1-4) and (1-5) had poor adhesion because the amount of low-crystalline polymerized PE5T in the surface layer (B) was insufficient. Comparative Example (1-6) contains too much low-crystalline copolymerized PE5T in the surface layer CB>, and has very good adhesion but very poor chemical resistance, and when the film surface is rubbed with a chloroform-impregnated cloth, It got scratched easily. In Comparative Example (1-7), the composition ratio of the surface layer CB) in the entire laminated film was too small, resulting in poor adhesion. Comparative example (1-8
) is a film that is better than highly crystalline PE5T alone, and as a matter of course has extremely poor adhesion.

On the other hand, Examples (1-1) to (t-5) all satisfy the specified requirements of the present invention, and have extremely good adhesive properties and physical properties. Note that the laminated films of Examples had heat-sealing properties themselves, but Comparative Examples (1-1) and (
1-2), (1-3), (1-4), (1-5), (1
-7) and (1-8) had no heat sealability.

Examples Prephthalic acid was used as the acid component, ethylene glycol was used as the glycol component, and 1,4-cyclohexanedimethanol (CHDM
) was used to produce low-crystalline copolymerized PE S'r.

The reduced specific viscosity of each PE5T obtained was 0.83.0.
It was 85, ■, 05.

On the other hand, terephthalic acid was used as the acid component, and ethylene glycol (EG) and polytetoshimethylene glycol (PTMG) were used as the glycol components.

A polyether ester elastomer was produced. The molecular weight of PTMG used was 10001EG and PTMG.
The molar ratio was 87.7/12.3. The reduced specific viscosity of the obtained elastomer was 1.39.

The obtained low-crystalline copolymerized PE5T, elastomer, and high-crystalline PET with an intrinsic viscosity of 0.60 were weighed in predetermined amounts into a bag and mixed to form the material for the surface layer (B), and also as the material for the base layer (5). Using the same highly crystalline PET as above, coextrusion, stretching, heat setting, corona discharge treatment, CP lamination, and aging were sequentially performed in the same manner as in Experimental Example 1 to obtain a CP laminate film. Each of the obtained films was subjected to boiling treatment and retort treatment in the same manner as in Experimental Example 1, and the adhesive strength was measured, and the heat sealability was also examined.

The results are shown in Table 2.

326 In Table 2, Comparative Examples (2-1) and (2-2) both had poor adhesion because the density increase of the low-crystalline copolymer PE5T in the surface layer (B) was too large. In Comparative Example (2-3), the amount of low-crystalline copolymerized PE5T in the surface layer (■) was too large, so although the adhesion was extremely good, the chemical resistance of the film was poor. ζ with a chloroform-impregnated cloth
It was easily damaged. In Comparative Example (2-4'), the composition ratio of the surface layer (B) in the entire laminated film was too large, and although the adhesiveness was good, the physical properties of the film were poor. Similar to Comparative Example (2-3), Comparative Example (2-5) contained a large amount of low-crystalline copolymer PE5T, and had good adhesion but poor chemical resistance of the film. Comparative examples (i-6) to (2
-8) is an example in which the surface layer (B) does not contain low-crystalline copolymerized PE5T or polyether ester disstomer, and both have extremely poor adhesion. Comparative Example (2-8') is 1-9 example for ft#, which is a two-type blend of highly crystalline PE5T and polyether ester disstomer exceeding the specified amount as the surface layer (B), and has an extremely high haze value. It can be seen that the cost is high and lacks transparency.

Example Low crystalline polymerized PE5T was produced using terephthalic acid and isophthalic acid (IPA) together as acid components and ethylene glycol as the glycol component. The reduced specific viscosity of 5 mol % or 30 mol % of IPA was 0.82 or 0.85, respectively.

On the other hand, a polyether ester elastomer was produced using terephthalic acid as the acid component and ethylene glycol (EG) and polyethylene glycol (PEG) as the glycol components. The molecular weight of the PEG used was 8.
300, the molar ratio of EG and PEG is 99.7410
．． It was set at 26. The reduced specific viscosity of the obtained nidistomer is 0.
．． It was 74.

A blend of this elastomer, the low-crystalline copolymer PE5T, and high-crystalline PET with an intrinsic viscosity of 0.60 is applied to the surface layer (6).
The material for the base layer has an intrinsic viscosity of 0.6.
Coextrusion was carried out in the same manner as in Experimental Example 1 using highly crystalline PET having a thickness of about 250 μm to obtain an unstretched laminated film having a thickness of about 250 μm.

This laminated film was stretched at 90°C in the longitudinal and transverse directions using a film stretcher manufactured by T, M, and Long. O
After simultaneous biaxial stretching was performed at a stretching ratio of 4.0 times, the film was fixed in a metal frame and heat-set at 220° C. for 15 seconds, and the surface was further subjected to corona discharge treatment. Next, the same adhesive used in Experimental Example 1 was applied uniformly to the treated surface with a wire bar, and after pre-drying, unstretched PC with a thickness of 60 μm was layered and passed through a rubber press roll heated to 50 ° C. After laminating, 40℃
It was aged for 2 days. Thereafter, the CP surfaces of each film were stacked and sealed with Heat Seat 2-, and the physical properties and adhesive properties of the films were measured in the same manner as in Experimental Example 1.

The results are shown in Table 3.

Example: Terephthalic acid was used as the acid component, and EG and propylene glycol (PG) or EG and 1 were used as the glycol components.
．． Experimental Example 3 was used as a polyether ester elastomer and high crystalline PE5T using low crystalline copolymerized PE5T obtained using 4-butanediol (1,4-BD).
A CP laminate film was produced in the same manner as in Experimental Example 3 using the same material. The adhesive properties and physical properties of each film obtained are summarized in Table 3.

As is clear from Table 3, Comparative Example (3-t).

Both (4-1) and (4-2) have poor adhesion because the density increase of the low-crystalline copolymerized PE5T in the surface layer (8) is too large. In Comparative Example (3-2), the amount of low-crystalline copolymerized PE5T in the surface layer (B) was too large, so although the adhesiveness was good, the physical properties of the film, especially the chemical resistance, were extremely poor. Examples (3-1) and (a) that meet the requirements of the present invention
-2) and (4-1) both have extremely good adhesive properties and film properties.

329-

Claims (1)

[Scope of Claims] (A) On at least one side of a base layer made of highly crystalline polyester having a density increase of 35XIO-3g/cm8 or more when heat-treated at 150°C for 30 minutes, (B) The following (B-1) ) low crystallinity copolymerized polyester =
5 to 60% by weight and copolymerized polyester of (B-2) =
30% by weight or less (excluding O), and (B-3)
Surface layer (B-1) consisting of a blend containing 10% by weight or more of highly crystalline polyester l A low-crystalline copolymer with a density increase of 30XlO-3g/c- or less when heat-treated at 50°C for 30 minutes Polyester, (B-2) Block copolymer polyester, (B-3)
Density increase is 35X when heat treated at 150℃ for 30 minutes
1. A polyester laminate film, characterized in that the surface layer (B) accounts for 1 to 70% by weight of the entire laminate film, comprising a highly crystalline polyester having a crystallinity of 10 −3 g/cm 8 or more.