JPS6015151A - Electricity suppressing 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 an antistatic polyester laminate film, and particularly to a polyester laminate film that has good adhesion to various materials and excellent antistatic properties.

Polyester (hereinafter referred to as PE5T) film exhibits stable properties over a wide temperature range, for example from -60 to 150°C, and is strong, dimensionally stable, oil resistant, chemical resistant, temperature resistant, transparent, etc. It is highly hygienic and safe, making it extremely suitable for packaging various materials. However, since PE5T film has extremely poor adhesion to other materials, there are problems in that adhesion during bag making, surface coating, printing, etc. are difficult.

In addition, the polymer itself of PE5T film has a high degree of electrical insulation.
1 because I'm watching 412 calls, when adding or IIv
1. Causes static disorder when handled. easy. Particularly in low humidity environments, static electricity is likely to be generated, which can cause problems when packaging powders and dry goods, as well as problems such as low acceleration speed and safety issues caused by spark emissions during printing. For drafting, examples include rubber powder build-up during erasing, automatic paper feeding failure in offset printing (2 to 3 sheets are misaligned), and dust build-up for projectors. The current situation is plagued by numerous problems.Furthermore, when powders or flakes are being packaged, especially when they are in a dry state, the packaged objects may stick to the bag due to frictional electrification inside the packaging bag. Not only does this damage the appearance, but some of the packaged items are also trapped in the heat seal during automatic bag making, making it impossible to adequately protect the contents. In the packaging of frozen foods, the packaging material is subject to a large local force due to the protrusions of the packaged object, which tends to cause pinholes and punctures 9 in the packaging material, resulting in damage to the packaging material. For such purposes, polyamide-based fills 1 are used, but they are not mechanically resistant to heat water after treatment due to their weak resistance to heat water due to the treatment of water boiling, high-temperature air, or pressurized hot water. In the case of packaging bags, for example, bags tend to break. This bag breakage is a serious problem because it is a problem in logistics after processing, packaging, transporting, handling, displaying, etc. ,Affl1/j+l properties, the method is to apply Aj type antistatic II- agent with known force V &(
However, this has not been achieved for polyester films.

This is because fibrous materials and planar materials such as films have different manufacturing methods, different shapes, and completely different usage surfaces, so even if they are said to have the same weight and weight, they have different characteristics. Required 11) One electric phenomenon is one! i＼〈It's different. In particular, the anti-static properties at low humidity are also not shown. Conventional films have been unsatisfactory to meet such demanding demands. Moreover, in the case of conventional PE5T films, the value of 1 tends to decrease in adhesion when trying to increase 11 to 1, and a PE5T film that has both antistatic +1 and adhesive properties has not been developed.

In addition, in the PE5T film of -Qp, other fisi (
/In contact with coatings, coatings, printing inks, etc.
In order to increase the
A method of sinking, 2. A method of corona discharge treatment on the surface,
3.Copolymerizability of other polar P1 monomers, polymer blending, etc. have been adopted, but both increase the processing time and therefore increase the manufacturing cost. Moreover, pure PE5T +1 is very good, so if you perform copolymerization or polymer blending, you can make it into a film, especially heat resistant M.
Stability and mechanical durability will be +1 or lower. Also PE5
Collect the T film (1 is often used, but 1-
In the contact r1+1 conversion treatment method as described above, the polymer often undergoes thermal deterioration or gelation during melting.

According to the present inventor's confirmation, the above-mentioned characteristics of PE5T have a negative correlation with the increase in livestock density when heated at 150°C, as will be explained in detail later. In particular, it was confirmed that the above-mentioned increase in stock density was 35XIO-3g/cm" or more for the excellent ones as mentioned above, especially those with 1 strand. However, such a large increase in gourd Taking into consideration the high crystallinity, the problem of 1) poor adhesion + I as mentioned in i) clearly appears.Furthermore, the high crystallinity of the cell P E S T fill 1, Since +1 is extremely large, it is necessary to take some measures to prevent static electricity damage as mentioned above.

The name of the present invention is based on these circumstances and improves adhesion to various materials (including coatings, printing inks, other laminating films, etc.) without impairing the original properties of IL and PE5T. At the same time, various studies have been conducted in an attempt to develop a PE5T film that does not cause electrostatic damage. The present invention was completed as a result of such research, and the structure of the antistatic P1 polyester laminated film is as follows: (A) 150'c! Increase in density when heat treated for 30 minutes at 35X10-3g/cm
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, and highly crystalline PE5T of the same (B-3): 10
Surface layer (B) consisting of a compound containing % by weight or more (B-1): Low crystalline copolymerized PE5T whose density increase when heat treated at 150°C for 30 minutes is 30X 10-3 g/am3 or less, ( B-2) Niblock copolymerized PE5T, (B-3):
The density increase when heat treated at 150°C for 30 minutes was 3.
Highly crystalline PE that is less than 5X l O-3g/cm"
5T, the half-life of the charging voltage measured with a static honest meter of the base layer is 60 seconds or less, and the composition ratio of the surface layer to the entire laminated film is 1 to 7.
The gist is that the content is 0% by weight.

In the present invention, the increase in richness during heat treatment is 35X l
The base layer (A) made of highly crystalline PE5T exhibiting O-3g/cm"- or less ensures the physical and chemical properties of the entire film as well as the required properties such as heat resistance and dimensional stability. A) is subjected to an antistatic treatment as described below to make its own chargeability half-life 60 seconds or less, thereby imparting antistatic properties to the entire laminated film, while the low crystalline copolymer P E S T (B-1), block copolymerized P E S T (B-2) and highly crystalline P E S
Surface layer (B-3) consisting of a specific ratio blend with T (B-3)
), it is possible to provide a laminated film that has both antistatic properties and adhesive properties, which were impossible to obtain with conventional PE5T films.

As mentioned above, the material constituting the surface layer (B) is a low-crystalline copolymer PEST that exhibits little increase in density during heat treatment.
(B-1) and block copolymerization P E S T (B-2
) and highly crystalline PES with a large increase in electric potential during heat treatment.
The surface layer (B) has a strong affinity with the base layer (A) and adheres strongly to the base layer (A), and is suitable for printing. It has excellent adhesion with inks and coatings, and it also has hot water and heat resistance that can withstand boiling and retort processing, so the laminated film as a whole has good delamination resistance. In addition, printing processing, laminating, etc. can be easily performed.

-1- The dicarboxylic acids or derivatives capable of condensation polymerization used in the production of the low crystalline copolymer PEST (B-1) include terephthalic acid, isophthalic acid, 1.5-(or 2,6- or 2,7)-naphthalene dicarboxylic acid, 4.
4'-diphenylenedicarboxylic acid, bis(p-lupogysyphenyl)methane, ethylene-bis-p-amne, 9, folic acid, 4,4-diphenyloxycarboxylic acid, ethylenebis(p-oxybenzoic acid), l, 3-1-rimethylene-bis (p-oxybenzoic acid), 1,4-tetramethylene-bis (p-oxybenzoic acid), 4,4'-sulfonyl dibenzoic acid, etc., and as the glycol, Glycols such as ethylene, 1,3-trimethylene, 1,4-tramethylene, 1,6-hexamethylene, 1°8-octamethylene, 1,10-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-cy(hydroxymethyl)
Examples thereof include aralkylene glycols such as -benzene and P-di(β-hydroxyeth*cy)-benzene. In addition to the above, typical acids used for modifying PE5TI71 include adipic acid, pimelic acid, superric acid, azelaic acid, sepacic acid, and 1,4-cyclohexanecarboxylic acid, and typical glycols for modification include In addition to Haniki, hentamethylene glycol, heptamethylene glycol, eicosamethylene glycol, nonane methylene glycol, dodecane methylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,3
-butanediol and 2,2,4-1=limethyl pencune diol, etc., but the acid component and glycol component constituting the low-crystalline copolymerized PE5T are not limited to these. However, to achieve the purpose of the present invention, the most preferable PE5T is one whose main raw materials are terephthalic acid and ethylene glycol, with other acid components such as isophthalic acid, amber, adipic acid, sepacic acid, and azelaic acid. As glycol components, tetramethylene glycol, polytetramethylene glycol,
Examples include copolymerized PE5T containing diethylene glycol 12,2-dimethyl-1,3-propanediol and propyl non-glycol''9 as the third component.
The content of the ingredients should be 5 mol% or more, and if it is not 5 mol%, the adhesion +1 effect will not appear. Regarding the surface layer (B), -1-low crystal +1
In order to increase the blending ratio of copolymerized PE5T, Jpe3 is used;
A product containing 20 tons or more of the copolymerized PE5T exhibits heat-sealing properties by itself.

Next, block co-Φ polymer P E S T (B-2) refers to a block copolymer consisting of a highly crystalline segment component and a low crystalline segment component. Highly crystalline PEST (B-3)
It has good affinity with low crystallinity segment I.
The ingredients are the above-mentioned low crystal + 1 combination P E S T (B-1
) has a very good affinity with the block copolymerized P E S T (B-2), so that by coexisting the block copolymerized P E S T (B-2), low crystalline 1-N P E S T (B-3) and high crystal PE5T (B-1) can be uniformly kneaded into one piece, creating a surface layer with both physical properties and adhesive properties.
It becomes possible to Such block copolymerized PE5T
Typical examples include polyether/polyester elastomers, among which 7 to 95% of the total segment I components are polyether glycols or copolyether glycols, and η these polyether glycols or copolyether glycols. The alkylene <++ component of glycol is an alkyl group having 2 to 12 carbon atoms or an aryl group having 4 to 10 carbon atoms (in other words, about 93 to 5%
is made of polyester segments) is most suitable. This type of block copolymer, which is classified as a polymer, usually has a melting point of 100° C. or higher. Acid components used in the production of such polyether e-ester elas[・mer] include terephthalic acid, inphthalic acid, phthalic acid, adipic acid, sepacic acid, succinic acid, azelaic acid, oxalic acid, diamne, mortar, Fragrance%, 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,
Examples thereof include 1,4-cyclohexane dimetatool, diethylene glycol, 2,2-dimethyl-1,3-propanediol, butylene glycol, and pestamethylene glycol. Segment components constituting the polyether ester include polyethylene oxide glycol, polypropylene oxide glycol, tetramethylene oxide glycol, J (polymerized glycol of ethylene oxide and propylene oxide) S, copolymerization of ethylene oxide 2 and tetrahydrofuran Polyethers such as glycol, aliphatic polyesters such as polyneopentyl azeley-1, polyneopentyl adipe-1, polyneopentyl sepacket I, and lacquer such as poly-ε-caprolactone and polypiparolac l. Examples include reaction products of Ng 9 with polytetramethylene oxide glycol, polyethylene oxide glycol, and the like.

By the way, the adhesion +1 for various materials of item A material is -
It is said that silver is influenced by the type of functional groups on the surface of the polymer, surface irregularities, and even crystal +1. On the other hand, when the group of the present invention conducted intermittent analysis of the factors that affect the adhesion to various materials for various copolymerized PE5T, it was found that copolymerized PE5T with low crystallinity has excellent adhesion to various materials. , [1. There is a high correlation between the increase in density when heated at 150°C for 30 minutes and the adhesion to various materials, and furthermore, the increase in density is 3
0X 10-3g/Cm or less, more preferably 20
X I 0-3g/cm" or less) (Tunai PEST
It was confirmed that it has excellent adhesion to various materials. Moreover, when an appropriate amount of the above block copolymer PE5T is blended with this low crystalline copolymer PE5T, kneading with the other blended high crystalline PE5T can be performed more easily and uniformly, and the surface layer (B) It was found that the adhesion of the material was further improved.

Note that the increase in density of the low-crystalline copolymerized PE5T varies significantly depending on the type and mole number of the copolymerized components, so by selecting them appropriately, the copolymerized PE5T with a small increase in density can be obtained.
However, in the case of PET obtained from terephthalic acid and ethylene glycol, which is the most typical PE5T,
Among effective copolymerization components for reducing density increase (Δp), isophthalic acid is preferred as a resistant component, and as glycol components, 2,2-dimethyl-1°3-propanediol, diethylene glycol, 1.4% - Cyclohexane dimetatool, propylene glycol, etc. are preferred, and by copolymerizing 10 to 30 mol% of these, the Δp of copolymerized PE5T can be reliably increased to 30X 10-3 g/
cm" 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 copolymerization component, Δρ is 5× l0-3
g/Cl is 118 or less, and the adhesiveness of copolymerized 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 blocking resistance and surface smoothness, so it cannot be used as is. It is not appropriate to use it.

However, it has become clear that when an appropriate amount of highly crystalline PE5T, which will be described later, is added to these formulations, the adhesion can be improved without substantially impeding the chemical resistance or the like. That is, the surface layer (B), which is the most characteristic feature of the present invention, is the low crystalline copolymer P E S T (B-1): 5 to 6.
0% by weight, more preferably 10 to 50% by weight) and the Pronk Copolymer 5 (B-2): 30% by weight or less, more preferably 1 to 50% by weight.
10% by weight) and highly crystalline PE5T (described later): 10% by weight or more, more preferably 40% by weight or more. If the amount of the low-crystalline copolymer PEST (B-1) is less than 5% by weight, sufficient adhesion cannot be imparted to the surface layer (B). Moreover, the copolymerized P E S T (B-1) has good transparency due to its low crystallinity, and has the effect of increasing the transparency of the laminated film and increasing its suitability as a packaging film, etc. If the coverage is less than %, these effects will be insufficient and satisfactory transparency cannot be obtained. On the other hand 60
If it exceeds % by weight, the surface properties of the surface layer (B), ie, chemical resistance, solvent resistance, surface smoothness, blocking resistance, etc., will deteriorate and become unsuitable for practical use. In particular, copolymerization P E S T (
If the surface layer (B) contains too much B-1), the surface layer (B) will swell or dissolve when the product film is treated with a solvent such as methyl ethyl ketone, tetrahydrofuran, benzene, ethyl acetate, chloroform, or trichlene. This can cause problems such as 6. 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 copolymerized PE5T (B-1) in the surface layer (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) was significantly improved, and the surface layer (
B) The physical and chemical properties of itself are also improved. As mentioned earlier, this is block copolymerization P E S T (B-2
) due to the coexistence of low crystallinity copolymerization P E S T (B
This is considered to be because the affinity between -1) and highly crystalline PEST (B-3) increases, and the homogeneity of the surface layer (B) improves. However, when the blending amount of the block copolymerized PE5T (B-2) exceeds 30% by weight, the transparency of the surface layer (B) decreases, the chemical resistance and blocking resistance decrease, and furthermore, the surface hardness increases. When adhesive tape is applied and removed, the surface layer may stretch and cause ripple-like wrinkles. In addition, high crystal M: P E S T (B-3) is as described above.
It has the excellent properties inherent to PE5T, and the surface layer (B
) must be blended with a 10-fold star or more in order to provide appropriate physical and chemical properties and chemical and solvent resistance.

Next, (highly crystalline PE5T constituting layer (A) is PE5T obtained by condensation polymerization of dicarbonate and glycol.
The dicarboxylic acid or condensation-polymerizable derivative used in the production of 41 PEST is 1→, terephthalic acid, isophthalic acid, x, 5-(or 2,6- or 2
．． 7-) Naphthalene dicarboxylic acid, 4,4'-diphenylene dicarboxylic acid, bis(p-carboxyphenyl)methane, ethylene-bifu-p-benzoic acid, 1,4-tetramethylene-bis-p-amne, Oka W, 4, 4'-diphenyloxycarboxylic acid, ethylene-bis(p-oxyben, 0.0.M), 1.3 trimethylene-bis(p-oxyben W m ), 1,4-tetramethylene-bis(
p-Ogishi cheap 7! and 4,4'-sulfonylamine, and 4,4'-sulfonyl alcohol. Further, as the glycol component, glycols such as ethylene, 1,3-trimethylene, 1°4-tetramethylene, 1,6-hexamethylene, 1,8-octamethylene, 1,10-decamethylene, cyclohexane-134-diol, 1,4-cyclohequinanthimethanol, 2.2.4.4-tetramethyl-1,
3-cyclobutanediol, 2,2-dimethyl-1,3
-Propanediol etc. are exemplified, and p-di(H]-
(roxymethyl)henzen and p-di(β-hydroxye;
・Alkylene glycols of 9) can also be used. Among these, in the present invention, the most desirable PE5T constituting layer (A) are polyethylene terephthalate (PET) and polybutylene terephthalate (PET), but of course it is not limited to these, Base layer (A) detailed below
Request as! It is also possible to perform a lipolymer blend in which a third component is copolymerized within a range that does not harm l''+ +l.

9 The polymer JIT P E S T resin used for 41 is
The solid viscosity when measured at 25 to 30'C using a mixture of phenolute I and lachloroethane 1 with a volume ratio of 0-chlorophene / -, + 60 / 40 or a similar solvent system to these is 0.2 dl/g or better than 1-1 L
<if&'J0.4 dl/g or less, and particularly preferred PET has a hard J viscosity of about 0.5 to 1.3 dl/g.
However, as a result of various experiments, in order to achieve the object of the present invention, P constituting the base layer (A)
E5T is a highly crystalline P E S T whose density increase when heat treated at 150'C for 30 minutes is more than 35X 10-3 g/cm''-1, preferably more than 37X lO-3 g/cm''I-. It became clear that P with a viscosity of 0.1 lOdl/g
The density increase of ET homopolymer is 43X 10-3g
/cm", the density increase for a PET homopolymer with an intrinsic viscosity of 0.90 dl/g is 39X I O"'"g
/cm'', and all of them serve the purpose as materials for the base layer (A).

PE5T with such a large density increase has high crystallinity, and oriented crystallization is significantly promoted by V film, stretching, and heat setting. It is possible to obtain a packaging film with high strength, mechanical properties, dimensional stability, etc. of +4j, 1. However, the density increase is 35X 10”
If the bulk is less than 1 g/cm", the properties improvement effect mentioned above during film formation, stretching, and heat setting will be insufficient, and the mechanical properties such as strength, dimensional stability, etc. of the final packaging film will be deteriorated. becomes insufficient.

1-Although the highly crystalline PE5T film has such excellent physical and chemical properties, its antistatic properties remain unresolved. Therefore, in the present invention, the highly crystalline PE5T constituting the layer (A) is subjected to an antistatic treatment as described below to ensure the 11/1 electric property as a laminated film.

Next, as the treatment V for imparting antistatic properties to the base layer (A) film in item 1-, the following method is exemplified.

・↓・Kneading method: A method U1 in which 4 u of an antistatic agent is added at the final stage of polymerization of PE5T, or a method in which a group that cures the antistatic effect is grafted onto the molecular chain of PE5T or an antistatic monomer is copolymerized. is included in this, and with this method, antistatic properties can be added to the film material itself. Furthermore, when melt-extruding PE5T resin, there is a method in which the resin is sprinkled with an antistatic agent or a conductive substance, or the material for the base layer (A) is kneaded with antistatic polyester to form a film by extrusion. can also be adopted.

U-coat method A dispersion or solution of an organic solvent or water containing an antistatic agent is applied to the surface of the film using a coating machine, etc., and this treatment can be applied to a stretched film. It can also be carried out after forming an unstretched film or during the stretching process.

・3) Impregnation D: This is a method of impregnating the film in a dispersion or liquid of an organic solvent or water containing an antistatic agent.

・4. Thin film method: Gold, aluminum 11,
Conductive thin films made of metal thin films such as palladium, semiconductor thin films such as indium chloride or tin oxide, or multilayer films such as titanium oxide or SI4 can be formed by vapor deposition, sputtering, or CVD.
A method of forming by law etc.

Examples of antistatic agents used in the method described in 2.2 include the following.

First, antistatic agents that can be applied to the above-mentioned kneading method include surfactants, polymer electrolytes, conductive polymers, and conductive organic and inorganic substances, but the melt molding temperature of PE5T is The temperature is quite high at around 280 to 300°C, and the antistatic agent is required to be heat resistant to withstand the high temperatures.From this perspective, the most preferable materials are surfactants and conductive inorganic substances such as those listed below. be. That is, a surfactant is a compound having a lipophilic group and a wood-philic group in its molecule, and specific examples include those shown in 6.

Anionic surfactant: Sulfonic acid metal salt derivative; 3 carboxylic acid soaps represented by metal soaps such as magnesium stearate and calcium stearate; Higher alcohol sulfate esters such as sodium octyl sulfate and sodium stearate sulfate; Sodium dodecylbenzenesulfone sulfone Higher alkylaryl sulfonates such as.

Cationic surfactants such as aliphatic amines such as diaminoethylethanolamine.

Amphoteric surfactants: stearyl diglycine, etc.

Nonionic surfactants: glycerin 1,000 ether, polyoxyethylene sorbicun trioleate-1, etc.

Examples of the conductive inorganic substance include aluminum 11, fine powder of metals or metal oxides such as titanium, iron, copper, and zinc, carbon black, and soot.

Surfactants are also suitable as antistatic agents applied to the coating method described above, and specific examples include S quaternary ammonium salt type cationic surfactants, imidacillin type cationic surfactants, and betaine type amphoteric surfactants. agent, alkyl phosphorus ester-resistant anionic world 4 surfactant, polyoxyethylene alkyl ether Nt
M ester type anionic surfactant, polyoxyethylene alkylphenol ether sulfate ester 1 type 1 type anionic surfactant, polyoxyethylene aliphatic ester type nonionic surfactant, polyethylene alkyl ether type nonionic surfactant, polyoxyethylene alkyl ether type anionic surfactant Examples include ethylene alkylphenol ether type nonionic surfactants and polyoxyethylene alkylamine 42 nonionic surfactants. Also effective are water-soluble polymers and polymer compounds such as di-I-cellulose.

In addition to the antistatic agents shown in the kneading method and the coating method, the antistatic agents used in the impregnation method (white) above include high molecular weight polyglycol ether, polyalcohol, polyoxyethylene alkamino, and nrubitan conductor. Alternatively, other known antistatic agents can be used.

When impregnating with these antistatic agents, if you use a PEST Ill lubricant such as I-lichloroacetic acid, ethylene glycol, tricrene, or tetrachloroethane, you can firmly apply the antistatic agent to the film surface. be able to.

Finally, when applying the thin film method in 4), use aluminum, etc.! It is possible to provide high levels of Fljl conductivity with less kE 11 than conventional metallized polyester.

By antistatic treatment as described in -1-, the surface electrical resistance of the film is reduced from about 1017Ω/cm2 to 1017Ω/cm2 of the untreated film.
~10 Ω/cm, making it easier for electricity to leak or flow, making it difficult to charge. However, in order to put it into practical use as a packaging film, etc. The anti-static processing conditions must be adjusted so that the voltage M'i+& period (measured by a static Honesl meter as described later) is 60 seconds or less. This was determined experimentally as a requirement to virtually eliminate static electricity when packaging powdered materials and thin pieces that can be dried in 4 hours. 2 seconds or less), (if the layer (A) film is used, static electricity damage of the entire laminated film can be substantially eliminated.

In this way (= in the present invention, the surface layer (B) ensures interlayer adhesion and adhesion to other materials, and the base layer (A) ensures antistatic properties, and the PE5T frame layer film has both properties. The surface layer (B) can be further subjected to a corona discharge treatment to further improve its adhesion.The surface layer (B) can also be subjected to the same antistatic treatment as described in "-". In particular, if an antistatic treatment method using metallization processing is adopted, it is effective because the adhesion of the surface layer (B) itself is not inhibited.

The constituent materials of the base layer (A) and the surface layer (B) used in the present invention are as shown in [-], and these include stabilizers, antioxidants, color inhibitors, and erasers.・Agents, fillers,
Plasticizers, thickeners, thinners, antifoaming agents.

It is possible to blend various additives such as pigments. Further, the highly crystalline PE5T used in the surface layer (B) may be the same as or different from the highly crystalline PE5T constituting the base layer (A).

In the present invention, the surface layer (B) having excellent adhesive properties is laminated on at least one side of the base layer (A) having an excellent antistatic property of +1 and made of highly crystalline PE5T according to the method described in 7 below. and heat setting to obtain a laminated PE5T film. During lamination, the proportion of the surface layer (B) in the entire laminated film is 1 to 70% star-shaped, preferably 5 to 70%.
It is necessary to make the weighting ratio 40%. However, the surface layer (
If the ratio of B) is less than 1%, the thickness of the surface layer (B) as an adhesion improving layer will be insufficient, and sufficient adhesion force will not be obtained; on the other hand, if it exceeds 70%, If the base layer (A) as a reinforcing layer becomes too thin, the heat resistance and mechanical properties of the laminated film will be poor, and the film will deform or break not only when external force is applied in a high-temperature atmosphere but also when external force is applied at room temperature. There are things to do.

Next, I will explain the specific manufacturing method of the laminated film.
The present invention is not limited to the following method.

The most preferred molding method for laminated films is coextrusion,
With this method, one layer (A
) and surface layer (B) are extruded and laminated using a compa- ning adapter etc.
A laminated PE5T film can be obtained in '11. In this case, the material constituting the surface layer (B) may be melted in advance, or it may be extruded while being kneaded using a static mixer or the like. The shape of the die may be either flat or circular, and both extrudates may be laminated either within the die or outside the die. Other lamination methods include extrusion lamination, dry or wet lamination, and in these cases it is preferable to interpose a suitable adhesive on the laminated surface. In this case, the base layer (A) and the surface layer (B) may be formed by, for example, the T-die 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 multiple layers of these other layers (A) and (B) to make a 10-layer film or a 20-layer film, and such multilayer films have good pinhole resistance and impact resistance. etc. will be even better. Incidentally, such a multilayer film is described in, for example, rS PE Journal, 1
June 973, Vol.

It can be manufactured according to the method described in 29J 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 discharge amount from each extruder when using a lamination method.
) can be easily adjusted by changing the thickness.

Although the PE5T laminated film of the present invention may be in an unstretched state, the mechanical properties of the laminated film can be further improved by appropriately stretching the film before or after lamination. Can stretching be done according to a known method?
The most preferred stretching temperature is about 70 to 100°C.

In addition, the preferred stretching ratio is 1.2 to 6 times in the case of single-car stretching, more preferably 1.5 to 6 times, and 1.2 to 6 times in the longitudinal direction and 1.2 times in the transverse direction in the case of biaxial stretching. ~6 times. Furthermore, the adhesion of the laminated film can be further improved by applying heat treatment or corona discharge treatment before and after lamination and stretching.

The PE5T laminated film of the present invention is constructed as described above, and has good antistatic properties and adhesive properties, as well as good transparency, and excellent dimensional stability, heat resistance, and surface properties. , its excellent properties can be effectively exhibited by using it in the following applications. In other words, this film has good adhesion to laminating agents such as paper, polyethylene, polypropylene, and aluminum foil, and is strong enough to withstand boiling and retort processing, so it is suitable for packaging forms such as cooked food packaging and boil-in fist bags. It can also be used effectively, and since the adhesive part has good water resistance, it can also be applied to water packaging. Furthermore, it has good adhesion with vinylidene chloride coated films to provide gas barrier properties, so it can be used for R+R meat such as ham and sausage, seafood products, bonito flakes, etc.
It is also ideal for packaging foods that are easily deteriorated, such as miso.

In addition, for general packaging other than those listed above, for adhesive tapes, for planar heating elements, for plate making, for gold and silver thread, for covering electric wires, for printed circuit boards, for capacitors, for magnetic tapes, for magnetic cards, and for floppy disks. Its excellent antistatic properties, adhesive properties, and physical and chemical properties can be effectively exhibited as a material such as.

Next, the configuration and effects of the present invention will be explained in more detail with reference to experimental examples, but prior to that, the methods for measuring various physical properties employed in the experiments will be clarified.

[Density increase: Δρ1 Based on JIS K 7+12, the density of the sample before and after heat treatment is measured at 30°C using a (water-calcium nitrate) liquid 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 0.05n+m) manufactured by Nippon Foil 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/cm” gauge.

[Antistatic Co2 Static Honest Meter RS410 manufactured by Rokunohe Shokai
4 type, 20°C, 165% R, H.

The half-life of the charging voltage was calculated. The voltage applied is 1 OKv.
After applying the voltage to the sample film No. 1-15CI11 for 1 minute, the attenuation of the charged voltage was observed using an oscilloscope, and the time (seconds) until the initial value of the charged voltage was halved was determined.

[Intrinsic viscosity and reduced specific viscosity of polymer] Mixed solvent of phenol/tetrachloroethane = 372 (
Polymer (80+ng) is dissolved in 20cc) and the viscosity at 30°C is measured using an Ubbelohde capillary viscometer. The unit is old/g.

[Heat shrinkage rate] In accordance with JIS C2318, heat treatment was performed at a temperature of 150°C for 1 hour, and the dimensional changes before and after the treatment were measured, and the average values in the vertical and horizontal directions were calculated.

[Chemical resistance] On the surface of the adhesive layer (B) of the laminated film, write B in a size of approximately 2 cm square with black marker ink No. 500, and after the ink was sufficiently dry, chloroform was soaked. Wipe off the writing on the surface of the film with a paper towel and observe the surface condition afterwards. If the surface is smooth and glossy, it is considered good (marked O), and if the surface is rough and has lost its luster, it is judged bad (marked x).

[Heat-Seal] Using a high-speed automatic bag-making machine rH3400 manufactured by Seibu Kikai Co., Ltd., heat-seal the bags at a rate of 30 bags per minute at a humidity of 200'O. The seal width is 1 cm.

[Heat I Seal Strength] 15mmlllf of the film that has been Hee I Sealed.
It was cut into a W book shape of m in length, and the sealing strength was determined to be S+++ in the form of a T-type f1124 using "Tensilon", which was used with a strength and elongation of 71111 constant. Peeling speed: 200 mm/min, measurement atmosphere: 20'0165%R,H.

[Lamination strength] Various types of filters were cut into 50 pieces with a width of 15 m + n x length of 20 cm.
T-film and sealing material in the form of T-type 711N 711~
to measure the laminate strength. Peeling speed is 200mm
/min, 7111 constant atmosphere is 20°C, 65% R, H.

[Boiling Treatment] The composite film was inserted into a 50-mesh stainless steel wire mesh bag, submerged in boiling water, and subjected to boiling water treatment for 30 minutes. In addition, for the composite filter laminated with a sealant, paper was inserted between the films to prevent the films from adhering to each other.

[Shi I/Ru I/Processing] “Dyeing processing machine rHU) IT 2+2/3 made by J-Saka Seisakusho
Using a 50-inch compact Obermeyer, the Sample 1 film was immersed in a wire mesh similar to the boiling treatment in flowing hot water and heat-treated at 120°C for 30 minutes. For films laminated with heat-sealing material, paper is inserted between the films to prevent fusion between the films.

[Total light transmission/V and haze value] In accordance with JIS K 8714, Oki 1 was determined using a new "Hazemeter S" manufactured by Toyo Seiki.

[Strength and elongation] JIS K 23+8 to No. 1 (according to Toyo Holdwin Co., Ltd.)
X1ll is determined in an atmosphere of 0°C, 165% R0H, and the average value in the vertical and horizontal directions is determined.

6 Experimental Example 1 Using terephthalic acid as the acid component and ethylene glycol as the glycol component, 10 mol%, 20 mol% or 3
0 mol% neopentyl f +) near −/l/(N
Three types of low-crystalline copolymerized PE5T were produced using PG) in combination. The reduced specific viscosity of the obtained copolymerized PE5T is 0.
, 83.0.85.0.93 di/g.

On the other hand, terephthalic acid is used as the acid component, butanediol (BD) and polytetramethylene glycol (PTMCI molecular weight took) (BD/PTM) are used as the glycol components.
G=85.7/14.3 (molar ratio)] to produce a polyether ester elastomer. The reduced specific viscosity of this elastomer was 1.85 dl/g.

The resulting low-crystalline copolymerized PE5T, elastomer, and pellets of high-crystalline PET with an intrinsic viscosity of 0.60 dl/g were put into a bag and mixed in predetermined amounts to form a material for the surface layer (B). On the other hand, the material for the base layer has an intrinsic viscosity of 0.60.
The above-mentioned highly crystalline PE5T of d+/g was used.

Two extruders were used for film formation, and the extrusion temperature was 28.
0 to 290°C, one extruder was filled with highly crystalline PET.
and feeding the mixed pellets to the other extruder, respectively,
The materials were coextruded into a film while being laminated in a T die, and then rapidly cooled to obtain a laminated film. At this time, the thickness ratio of the base layer and surface layer was changed by adjusting the extrusion amount of the image material, but the thickness of the laminated film in the unstretched state was approximately 250 μm in each case.
Met. This film was stretched 3.5 times (85° C.) in the longitudinal direction using rolls having different circumferential speeds. Next, an antistatic agent (a cationic surfactant manufactured by Miyoshi Oil Co., Ltd. [Myuron AS102J] and an anionic surfactant [Myuron ACJ and water/methyl alcohol = 10/
A solution prepared by diluting the mixed solvent of 1 with 0.5% of the former and 2 of the latter with a very diluted solution] was applied with a fountain coater to a total area of about 31 m2, and after drying, it was coated with a tenter in the horizontal direction by 3.7 times (
After stretching (105°C), the film was heat-set at 220°C while being relaxed by 5 inches in the transverse direction. After that, the surface layer of this laminated film (B
) side surface was subjected to corona discharge treatment. The thickness of the obtained film was 19 μm. A polyol and isocyanate-based adhesive [manufactured by Orbable Yakuhin Co., Ltd.] Takelac A-971J and Takenate A3J (weight ratio of 1) was diluted with ethyl acetate to give a concentration of 30q6 on the surface layer (B) side of this PE5T laminated film. 100 meshes were coated using a gravure roll with a depth of 80 μm, pre-dried iL, and laminated with an unstretched polypropylene film (CP) with a thickness of 60 μm and a nipple roll (temperature 5
0℃). After aging at 40°C for 2 days, 62 sides were overlapped and sealed with a heat sealer, and the CP laminate film was boiled or retorted, then PE5T
The interlayer lamination strength between the laminated film and CP, the strength of the heat-sealed portion, antistatic properties, etc. were measured. For comparison, a performance test was conducted in exactly the same manner except that the antistatic treatment of the base layer (3) was omitted.

The results are summarized in Table 1.

As is clear from Table 1, Comparative Example (1-1) has a surface layer (
Since BJ does not contain polyether ester elastomer, the lamination strength and sealing strength of the CP laminate film are poor, and the antistatic properties are extremely poor because the base layer (5) is not subjected to antistatic treatment. . Comparative example (1-'2) is a surface layer (low crystalline copolymerized PE5T in BJ).
Since neither polyether nor ester elastomer is blended, and the base layer has not been subjected to antistatic treatment, both the lamination strength and antistatic properties of the CP laminate film are extremely poor. In contrast, Example (1-1)
Samples (1-4) to (1-4) satisfy the specified requirements of the present invention, have good lamination strength and seal strength, and exhibit excellent antistatic properties.

Experimental Example 2 Using terephthalic acid as the acid component and ethylene glycol as the glycol component, 3 molti, 10 molti or 3 molti
0 molar 1,4-cyclohexane dimetatool (CH
DM) to produce low crystalline copolymerized PE5T. The reduced specific viscosity of the obtained copolymerized PE5T is 0.83.0.
．． It was 85.i.05 dl/g.

On the other hand, terephthalic acid is used as the acid component, and ethylene glycol (EG) and polytetramethylene glycol (PTMG: molecular weight 1000) CE are used as the glycol components.
G/PTMG=87.7/12.3 (molar ratio)] to produce a polyether ester elastomer.

The reduced specific viscosity of this elastomer was 1.39.

In addition, as an antistatic agent, bishydroxyethylene terephthalate and 1 polyethylene glycol # manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
'4000J (the latter copolymerization amount is 57% by weight),
A polyester-polyether block copolymer (WEL) obtained by polymerizing at 275° C. under reduced pressure in the presence of a catalyst (40 mmol % each of zinc acetate and antimony trioxide) was used.

Copolymerized with the above elastomer PE5T and intrinsic viscosity 0.6
Experimental Example 1 After obtaining a two-layer PE5T laminated film (5) and (B) in the same manner as above, it was stretched in the same manner to form the surface layer (B) of the laminated film.
The side surfaces were subjected to corona discharge treatment and CP was laminated thereon, followed by aging in the same manner. This CP laminate film and CP
The laminate strength, sealing strength, and antistatic property after boiling treatment or retort treatment were examined for the CP laminate film that was heat-sealed on the surface.

The results are shown in Table 2.

As is clear from Table 2, Comparative Example (2-1) and Comparative Example (2-1)
2-2) has poor antistatic properties because the base layer (4) is not subjected to antistatic treatment. Moreover, these are superficial)
Since the density of the low-crystalline copolymer PE5T (B-1) blended in is too large, the lamination strength and sealing strength of the CP laminate film are also low.

On the other hand, Examples (2-1) to (2-4) satisfy all the specified requirements, and have obtained good results in all aspects such as antistatic properties, lamination strength, and seal strength.

Experimental Example 3 Terephthalic acid and 5 or 10 molar isophthalic acid (IPA) were used together as the acid component, and ethylene glycol was used as the glycol component to produce low-crystalline copolymerized PE5.
T was manufactured. The reduced specific viscosities of this copolymerized PE5T were 0.82 and 0.85 dl/g, respectively.

On the other hand, the acid component is terephthalic acid, and the glycol components are ethylene glycol (EG) and polyethylene glycol (PEG3 molecular weight 8300) [EG / P E
c, = 99.7410.26 (molar ratio) was used to prepare a polyether 9 ester elastomer. The reduced specific viscosity of this nidistomer was 0.74 dL/g.

As the antistatic agent, alkylphosphonate (AS) or sodium dodecylbenzenesulfonate (DBS) was used either alone or in combination with WEL used in Experimental Example 2.

The above copolymer PE5T and elastomer and intrinsic viscosity 0.6
0 di/g high crystalline PET was used as the material for the surface layer (B), and the same high crystalline PE as above was used as the material for the base layer (3).
T and the above antistatic agent were used in combination and coextruded in the same manner as in Experimental Example 1 to form a base layer (5) and a surface layer (B) of PE5T.
A laminated film was produced. The thickness of this film is approximately 25
It was 077 m.

Using a film stretcher manufactured by T, M, Long, the film was stretched at 90° C. in the longitudinal and transverse directions for 4.
0x simultaneous biaxial stretching, fixed in a metal frame at 220℃
After heat setting for 15 seconds, the surface of the surface layer (B) was subjected to corona discharge treatment. The thickness of the obtained film was approximately 16 μm. On the surface layer (Bl side surface) of this PE5T laminated film, the polyol-isocyanate adhesive (30% solution) used in Experimental Example 1 was applied uniformly with a wire bar, and after pre-drying, an unstretched polygon with a thickness of 60 μm was applied. Pyrene films (CP) were layered and laminated by passing through a rubber press roll heated to 50°C, and then aging at 40°C for 2 days.Then, the CP sides were brought together and sealed with a heat sealer.The obtained CP laminate film After boiling or retort processing, the glabella lamination strength and heat seal strength of the PE5T laminated film and CP were measured, and the performance such as antistatic property was also examined.The results are shown in Table 3.

In Table 3, Comparative Examples (3-1) and (3-2) do not contain any antistatic agent in the base layer (5), so the antistatic properties are not improved at all. Furthermore, since Comparative Example (3-2) does not contain highly crystalline PET as the material for the surface layer (B), although the adhesiveness is good, the physical properties of the laminated film are poor overall and the chemical resistance is also poor. be.

Comparative example (3-3) is a low-crystalline copolymer P in the surface layer (B).
Since the amount of E5T is insufficient and the amount of nidistomer is too large, the heat sealing strength is low, the haze value of the laminated film is high, and the transparency is poor. In contrast to these examples (,3
-1) to (3-a) satisfy all of the requirements stipulated by the present invention, and therefore good results are obtained in all performances.

Experimental Example 4 Terephthalic acid was used as the acid component, and ethylene glycol (EG) and propylene glycol (PG) or 1,4-butanediol (1,4-BD) were used as the glycol component.
) was used in combination to produce low-crystalline copolymer PE5T. and polyether ester elastomer and highly crystalline P
As E5T, the same one used in Experimental Example 3 was used (however, no electrostimulating agent was used), and the same procedure as in Experimental Example 3 was followed by lamination, coextrusion, stretching, corona discharge treatment of the surface layer (B), and CP. The film was laminated. The surface of the base layer side of the obtained laminated film was coated with 2X using a vacuum evaporation device 1-EBV-6DA model manufactured by Japan Vacuum Technology Co., Ltd.
Depositing aluminum under a vacuum of 10' Torr,
A performance test was conducted in the same manner as above.

The results are shown in Table 4, and the antistatic properties can be significantly improved by performing the aluminum vapor deposition treatment.

Claims (1)

[Scope of Claims] (A) On one or both sides of a base layer made of highly crystalline boester having a density increase of 35X l O-3 g/cm" or more when heat-treated at 150°C for 30 minutes, (B) the following ( B-
1) low crystalline copolymerized polyester 5 to 60% by weight, (B-2) copolymerized polyester: 30% by weight or less,
and (B-3) Highly crystalline polyester: Surface layer CB-1) consisting of a compound containing 10% by weight or more: Density increase when heat treated at 150'C for 30 minutes is 30 x 10-3 g/Cm3 The following low crystalline copolymerized polyesters, (B-2) Niblock copolymerized polyesters, (B-3)
: l Highly crystalline polyester having a redundancy increase of 35X IO-33/cm8 or more when heat treated at 50°C for 30 minutes, the electrostatic charge measured with a static honest meter of the base layer has a half-life of 60 seconds or less, and the composition ratio of the surface layer to the entire laminated film is 1 to 7.
An antistatic polyester laminated film characterized in that the content is 0% by weight.